TW201642367A - 焊料電極的製造方法、焊料電極、積層體的製造方法、積層體、電子零件及射出成形焊料用感光性樹脂組成物 - Google Patents

焊料電極的製造方法、焊料電極、積層體的製造方法、積層體、電子零件及射出成形焊料用感光性樹脂組成物 Download PDF

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TW201642367A
TW201642367A TW105112583A TW105112583A TW201642367A TW 201642367 A TW201642367 A TW 201642367A TW 105112583 A TW105112583 A TW 105112583A TW 105112583 A TW105112583 A TW 105112583A TW 201642367 A TW201642367 A TW 201642367A
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Taiwan
Prior art keywords
solder
electrode
substrate
producing
resist
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TW105112583A
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English (en)
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TWI681474B (zh
Inventor
Jun Mukawa
Seiichirou Takahashi
Kouichi Hasegawa
Shirou Kusumoto
Yoshikazu Yamaguchi
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Jsr Corp
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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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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • 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
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3468—Applying molten solder
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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Abstract

本發明是一種焊料電極的製造方法，其包括：步驟（1），在具有電極墊的基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），在所述開口部填充熔融焊料；且所述感光性樹脂組成物至少含有苯并噁唑前驅物。本發明的焊料電極的製造方法如IMS法等般，即便在焊料填充時抗蝕劑受到高熱的情況下，亦可防止抗蝕劑表面的龜裂產生，並可提高焊料填充能力，因此可恰當地製造適合於目的的焊料電極。

Description

焊料電極的製造方法及其用途
本發明是有關於一種焊料電極的製造方法、焊料電極、積層體的製造方法、積層體、電子零件、及感光性樹脂組成物。
射出成形焊料（Injection Molded Solder，IMS）法是用以形成焊料圖案（焊料凸塊）的方法之一。至今為止，作為在晶圓等基板上形成焊料圖案的方法，使用焊膏法、鍍敷法等。然而，在該等方法中，存在不但焊料凸塊的高度控制困難，而且無法自由選擇焊料組成等的制約。相對於此，在IMS法中，已知並無該等制約的優點。
IMS法如專利文獻1～專利文獻4所示般，是特徵在於一邊使可將熔融的焊料射出成形的噴嘴與抗蝕劑密接，一邊在抗蝕劑圖案間流入焊料的方法。 [現有技術文獻] [專利文獻]
[專利文獻1]日本專利特開平06-055260號公報 [專利文獻2]日本專利特開2007-294954號公報 [專利文獻3]日本專利特開2007-294959號公報 [專利文獻4]日本專利特表2013-520011號公報
[發明所欲解決之課題]關於IMS法，為了填充熔融焊料，而將加熱至高溫、通常為250℃以上的IMS頭推抵至抗蝕劑表面而進行。因此，存在因高熱引起的負載作用於抗蝕劑表面，在抗蝕劑表面產生龜裂、或產生抗蝕劑的潰爛，而焊料嵌入性降低的問題。
本發明的目的是提供一種如IMS法等般，在焊料填充時抗蝕劑受到高熱的情況下，亦可防止抗蝕劑表面的龜裂產生，並謀求焊料填充能力的提高的技術。 [解決課題之手段]
本發明的焊料電極的製造方法包括：步驟（1），在具有電極墊的基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），在所述開口部填充熔融焊料；且所述焊料電極的製造方法的特徵在於： 所述感光性樹脂組成物至少含有苯并噁唑前驅物。
在所述焊料電極的製造方法中，所述感光性樹脂組成物可進一步含有感光劑。 所述焊料電極的製造方法可進一步包括：步驟（4），將所述抗蝕劑剝離。 本發明的焊料電極是藉由所述焊料電極的製造方法而製造的焊料電極。
本發明的第1積層體的製造方法包括：步驟（1），在具有電極墊的第1基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），一邊加熱一邊將熔融焊料填充至所述開口部，而形成焊料電極；步驟（5），經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構；且所述積層體的製造方法的特徵在於： 所述感光性樹脂組成物至少含有苯并噁唑前驅物。
本發明的第2積層體的製造方法包括：步驟（1），在具有電極墊的第1基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），一邊加熱一邊將熔融焊料填充至所述開口部，而形成焊料電極；步驟（4），在步驟（3）之後，將所述抗蝕劑剝離；步驟（5），在步驟（4）之後，經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構；且所述積層體的製造方法的特徵在於： 所述感光性樹脂組成物至少含有苯并噁唑前驅物。
本發明的積層體是藉由所述第1積層體的製造方法或第2積層體的製造方法而製造的積層體。 本發明的電子零件是具有所述積層體的電子零件。 本發明的射出成形焊料用感光性樹脂組成物至少含有苯并噁唑前驅物。 [發明的效果]
本發明的焊料電極的製造方法如IMS法等般，在焊料填充時抗蝕劑受到高熱的情況下，亦可防止抗蝕劑表面的龜裂產生，並可提高焊料填充能力，因此可恰當地製造適合於目的的焊料電極。
本發明的積層體的製造方法藉由IMS法可恰當地製造適合於目的的焊料電極，因此可恰當地製造具有電性連接結構的積層體。
＜焊料電極的製造方法＞ 本發明的焊料電極的製造方法包括：步驟（1），在具有電極墊的基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），在所述開口部填充熔融焊料；且所述焊料電極的製造方法的特徵在於：所述感光性樹脂組成物至少含有苯并噁唑(benzoxazole)前驅物。
本發明的焊料電極的製造方法中，所述步驟（1）中所用的感光性樹脂組成物含有苯并噁唑前驅物的方面與先前法不同。所述步驟（1）～步驟（3）中的操作可與先前法同樣地進行。 以下，一邊參照圖1（1）～圖1（4），一邊對本發明的焊料電極的製造方法進行說明。
（步驟（1）） 步驟（1）中，如圖1（1）所示般，在具有電極墊2的基板1上形成感光性樹脂組成物的塗膜3。 基板1例如為半導體基板、玻璃基板、矽基板、以及在半導體板、玻璃板及矽板的表面設置各種金屬膜等而形成的基板等。基板1具有大量的電極墊2。
塗膜3是藉由在基板1上將感光性樹脂組成物進行塗佈等而形成。作為感光性樹脂組成物的塗佈方法，並無特別限定，例如可列舉：噴霧法、輥塗法、旋塗法、狹縫模塗法、棒塗法、噴墨法。塗膜3的膜厚通常為1 μm～500 μm，較佳為5 μm～200 μm，更佳為10 μm～100 μm。
所述感光性樹脂組成物至少含有苯并噁唑前驅物。苯并噁唑前驅物受熱後在分子內反應，急速地變為具有耐熱性的結構。因此，由所述感光性樹脂組成物形成的抗蝕劑當在IMS法等的焊料填充時加熱至高溫時，抗蝕劑所含的苯并噁唑前驅物急速地變為具有耐熱性的結構，因此耐熱性提高，其結果認為可防止抗蝕劑表面的龜裂產生，焊料嵌入性提高。
由感光性樹脂組成物形成的塗膜在後述的步驟（2）中藉由曝光而交聯。但是，通常僅藉由曝光，感光性樹脂組成物中所含的交聯劑不會完全消耗，未消耗的交聯劑殘存於抗蝕劑中。因此，僅藉由進行曝光，抗蝕劑的交聯不完全，抗蝕劑的強度不會充分提高。如先前法般認為，在所述狀態下藉由IMS法而將高溫的頭推抵至抗蝕劑的表面來填充熔融焊料時，抗蝕劑不耐受自IMS頭受到的熱，而產生龜裂或潰爛。相對於此，在本發明的焊料電極的製造方法中，如所述般，抗蝕劑藉由加熱而耐熱性急速地提高，因此不會產生龜裂或潰爛。
另外，在使用不含苯并噁唑前驅物的感光性樹脂組成物的先前的IMS法中，認為在正填充熔融焊料的過程中藉由熱而會進行由殘存在抗蝕劑內的交聯劑引起的交聯反應，而強化抗蝕劑，但感光性樹脂組成物所使用的多官能丙烯酸酯等交聯劑由於交聯反應速度慢，因此認為在交聯反應充分進行之前，因自IMS頭受到的熱而產生龜裂或潰爛。
作為苯并噁唑前驅物，例如可列舉：將二羧酸及二羥基二胺作為原料而得的聚苯并噁唑前驅物。作為所述二羧酸，可列舉：間苯二甲酸、對苯二甲酸、2,2-雙(4-羧基苯基)六氟丙烷、4,4'-聯苯二甲酸、4,4'-二羧基二苯醚、4,4'-二羧基四苯基矽烷、雙(4-羧基苯基)碸、2,2-雙(對羧基苯基)丙烷、5-第三丁基間苯二甲酸、5-溴間苯二甲酸、5-氟間苯二甲酸、5-氯間苯二甲酸、2,6-萘二甲酸等芳香族系二羧酸，1,2-環丁二羧酸、1,4-環己二羧酸、1,3-環戊二羧酸、草酸、丙二酸、丁二酸等脂肪族系二羧酸等。該等可單獨使用或組合兩種以上而使用。該等中，就耐熱性的方面而言，較佳為芳香族系二羧酸。
作為所述二羥基二胺，可列舉：3,3'-二胺基-4,4'-二羥基聯苯、4,4'-二胺基-3,3'-二羥基聯苯、雙(3-胺基-4-羥基苯基)丙烷、雙(4-胺基-3-羥基苯基)丙烷、雙(3-胺基-4-羥基苯基)碸、雙(4-胺基-3-羥基苯基)碸、雙(3-胺基-4-羥基苯基)六氟丙烷、雙(4-胺基-3-羥基苯基)六氟丙烷、雙(3-胺基-4-羥基苯基)丙烷、雙(4-胺基-3-羥基苯基)丙烷、4,6-二胺基間苯二酚、4,5-二胺基間苯二酚、雙(4-胺基-3-羧基苯基)甲烷等芳香族系二胺。藉由使用芳香族系二胺，而可獲得耐熱性良好的聚苯并噁唑前驅物。
苯并噁唑前驅物的藉由凝膠滲透層析（Gel Permeation Chromatography，GPC）法測定的聚苯乙烯換算的重量平均分子量（Mw），較佳為3,000～200,000，更佳為5,000～100,000。
關於所述感光性樹脂組成物中的苯并噁唑前驅物的含量，若將所述組成物中所含的全部固體成分設為100質量%，則通常為50質量%以上，較佳為60質量%～95質量%，更佳為70質量%～90質量%。
所述感光性樹脂組成物除了苯并噁唑前驅物以外，還可含有在先前法中所用的感光性樹脂組成物中通常含有的成分。 所述感光性樹脂組成物可為正型亦可為負型。所述感光性樹脂組成物是正型還是負型，由感光性樹脂組成物中所含的感光劑的種類決定。在所述感光性樹脂組成物為正型時，包含萘醌二疊氮(naphthoquinone diazide)作為必須成分，在為負型時，包含光酸產生劑及陽離子系交聯劑作為必須成分。
含有所述萘醌二疊氮化合物的塗膜對鹼性顯影液為難溶，但萘醌二疊氮化合物藉由光照射，醌二疊氮基分解產生羧基，而變為鹼易溶。因此，含有萘醌二疊氮化合物的塗膜藉由光照射而自鹼難溶性變為鹼易溶性。
所述萘醌二疊氮化合物是具有1個以上酚性羥基的化合物與1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸的酯化合物。
作為萘醌二疊氮化合物，例如可列舉：4,4'-二羥基二苯基甲烷、4,4'-二羥基二苯醚、2,3,4-三羥基二苯甲酮、2,3,4,4'-四羥基二苯甲酮、2,3,4,2',4'-五羥基二苯甲酮、三(4-羥基苯基)甲烷、三(4-羥基苯基)乙烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、1,3-雙[1-(4-羥基苯基)-1-甲基乙基]苯、1,4-雙[1-(4-羥基苯基)-1-甲基乙基]苯、4,6-雙[1-(4-羥基苯基)-1-甲基乙基]-1,3-二羥基苯、1,1-雙(4-羥基苯基)-1-[4-[1-(4-羥基苯基)-1-甲基乙基]苯基]乙烷等與1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸的酯化合物。 萘醌二疊氮化合物可單獨使用一種，亦可併用兩種以上。
所述光酸產生劑是藉由光照射而形成酸的化合物。藉由所述酸作用於陽離子系交聯劑的陽離子反應性基而形成交聯結構，因此包含光酸產生劑及陽離子系交聯劑的塗膜藉由光照射而對鹼性顯影液變為難溶。 作為光酸產生劑，例如可列舉：鎓鹽化合物、含有鹵素的化合物、碸化合物、磺酸化合物、磺醯亞胺化合物、重氮甲烷化合物。該等中，就可形成伸長物性優異的硬化膜而言，較佳為鎓鹽化合物、含有鹵素的化合物。
作為鎓鹽化合物，例如可列舉：錪鹽、鋶鹽、鏻鹽、重氮鎓鹽、吡啶鎓鹽。作為較佳的鎓鹽的具體例，可列舉：二苯基錪三氟甲磺酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽、二苯基錪六氟磷酸鹽、二苯基錪四氟硼酸鹽、三苯基鋶三氟甲磺酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、4-第三丁基苯基-二苯基鋶三氟甲磺酸鹽、4-第三丁基苯基-二苯基鋶對甲苯磺酸鹽、4,7-二-正丁氧基萘基四氫噻吩嗡三氟甲磺酸鹽、4-(苯硫基)苯基二苯基鋶三(五氟乙基)三氟磷酸鹽。
作為含有鹵素的化合物，例如可列舉：含有鹵化烷基的烴化合物、含有鹵化烷基的雜環式化合物。作為較佳的含有鹵素的化合物的具體例，可列舉：1,10-二溴-正癸烷、1,1-雙(4-氯苯基)-2,2,2-三氯乙烷、苯基-雙(三氯甲基)-均三嗪、4-甲氧基苯基-雙(三氯甲基)-均三嗪、苯乙烯基-雙(三氯甲基)-均三嗪、萘基-雙(三氯甲基)-均三嗪等均三嗪衍生物。
作為碸化合物，例如可列舉：β-酮碸化合物、β-磺醯基碸化合物及該等化合物的α-重氮化合物。作為較佳的碸化合物的具體例，可列舉：4-三苯甲醯甲基碸、均三甲苯基苯甲醯甲基碸、雙(苯甲醯甲磺醯基)甲烷。
作為磺酸化合物，例如可列舉：烷基磺酸酯類、鹵化烷基磺酸酯類、芳基磺酸酯類、亞胺基磺酸酯類。作為較佳的磺酸化合物的具體例，可列舉：安息香甲苯磺酸酯、鄰苯三酚三-三氟甲磺酸酯、鄰硝基苄基三氟甲磺酸酯、鄰硝基苄基對甲苯磺酸酯。
作為磺醯亞胺化合物，例如可列舉：N-(三氟甲基磺醯氧基)丁二醯亞胺、N-(三氟甲基磺醯氧基)鄰苯二甲醯亞胺、N-(三氟甲基磺醯氧基)二苯基順丁烯二醯亞胺、N-(三氟甲基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺、N-(三氟甲基磺醯氧基)萘基醯亞胺。
作為重氮甲烷化合物，例如可列舉：雙(三氟甲基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷、雙(苯基磺醯基)重氮甲烷。
光酸產生劑可單獨使用一種，亦可併用兩種以上。 所述陽離子系交聯劑發揮出作為交聯成分（硬化成分）的作用。作為陽離子系交聯劑，例如可列舉：具有2個以上經烷基醚化的胺基的化合物（以下亦稱為「含有胺基的化合物」）、含有氧雜環丙烷環的化合物、含有氧雜環丁烷環的化合物、含有異氰酸酯基的化合物（包括經嵌段化者）、含有醛基的酚化合物、含有羥甲基的酚化合物。但是具有環氧基的矽烷偶合劑自含有氧雜環丙烷環的化合物除外，具有異氰酸酯基的矽烷偶合劑自含有異氰酸酯基的化合物除外。作為經烷基醚化的胺基，例如可列舉：下述式所示的基團。
[化1]（式中，R11 表示亞甲基或伸烷基，R12 表示烷基。）
作為含有胺基的化合物，例如可列舉：(聚)羥甲基化三聚氰胺、(聚)羥甲基化甘脲、(聚)羥甲基化苯代三聚氰胺、(聚)羥甲基化脲等氮化合物中的活性羥甲基（CH2 OH基）的一部分或全部（至少2個）經烷基醚化的化合物。此處，作為構成烷基醚的烷基，例如可列舉：甲基、乙基、丁基，該等可彼此相同，亦可不同。此外，未經烷基醚化的羥甲基可在一分子內自縮合，亦可在二分子間縮合，其結果可形成寡聚物成分。具體可使用：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。
作為含有氧雜環丙烷環的化合物，只要在分子內含有氧雜環丙烷環即可，並無特別限定，例如可列舉：苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚型環氧樹脂、三酚型環氧樹脂、四酚型環氧樹脂、苯酚-伸二甲苯基型環氧樹脂、萘酚-伸二甲苯基型環氧樹脂、苯酚-萘酚型環氧樹脂、苯酚-二環戊二烯型環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂。
作為含有氧雜環丙烷環的化合物的具體例，例如可列舉：間苯二酚二縮水甘油醚、季戊四醇縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、甘油聚縮水甘油醚、苯基縮水甘油醚、新戊二醇二縮水甘油醚、乙二醇/聚乙二醇二縮水甘油醚、丙二醇/聚丙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、山梨糖醇聚縮水甘油醚、丙二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚。
作為含有氧雜環丁烷環的化合物，只要在分子內含有氧雜環丁烷環即可，並無特別限定，例如可列舉：式（d-1）～式（d-3）所示的化合物。
[化2]式（d-1）～式（d-3）中，A表示直接鍵、或亞甲基、伸乙基、伸丙基等伸烷基；R表示甲基、乙基、丙基等烷基；R1 表示亞甲基、伸乙基、伸丙基等伸烷基；R2 表示甲基、乙基、丙基、己基等烷基，苯基、伸二甲苯基等芳基，下述式所示的基團（式中，R及R1 分別與式（d-1）～式（d-3）中的R及R1 同義），
[化3]下述式（i）所示的二甲基矽氧烷殘基，亞甲基、伸乙基、伸丙基等伸烷基，伸苯基，下述式（ii）～式（vi）所示的基團；i與R2 的價數相等，為1～4的整數。另外，下述式（i）～式（vi）中的「*」表示鍵結部位。
[化4]式（i）及式（ii）中，x及y分別獨立地為0～50的整數。式（iii）中，Z為直接鍵、或以-O-、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-CO-或-SO2 -表示的2價基。
作為式（d-1）～式（d-3）所示的化合物的具體例，例如可列舉：1,4-雙{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}苯（商品名「OXT-121」、東亞合成公司製造）、3-乙基-3-{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷（商品名「OXT-221」、東亞合成公司製造）、4,4'-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]聯苯（宇部興產製造、商品名「艾塔納科（ETERNACOLL）OXBP」）、雙[(3-乙基-3-氧雜環丁基甲氧基)甲基-苯基]醚、雙[(3-乙基-3-氧雜環丁基甲氧基)甲基-苯基]丙烷、雙[(3-乙基-3-氧雜環丁基甲氧基)甲基-苯基]碸、雙[(3-乙基-3-氧雜環丁基甲氧基)甲基-苯基]酮、雙[(3-乙基-3-氧雜環丁基甲氧基)甲基-苯基]六氟丙烷、三[(3-乙基-3-氧雜環丁基甲氧基)甲基]苯、四[(3-乙基-3-氧雜環丁基甲氧基)甲基]苯、下述式（d-a）～式（d-d）所示的化合物。
[化5]此外，除了該等化合物以外，亦可使用高分子量的具有多價氧雜環丁烷環的化合物。例如可列舉：氧雜環丁烷寡聚物（商品名「歐力多（Oligo）-OXT」、東亞合成公司製造）、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分別獨立地為0～10000的整數，較佳為1～10的整數。式（d-f）中，Y為伸乙基、伸丙基等伸烷基、或以-CH2 -Ph-CH2 -表示的基團（式中，Ph表示伸苯基）。 陽離子系交聯劑可單獨使用一種，亦可併用兩種以上。
（步驟（2）） 在步驟（2）中，如圖1（2）所示般，藉由將塗膜3選擇性曝光，進而進行顯影，而在與各電極墊2對應的區域形成具有開口部4的抗蝕劑5。即，以形成容納各電極墊2的開口部4的方式，對塗膜3進行部分曝光，然後進行顯影，而形成容納各電極墊2的開口部4。其結果在與各電極墊2對應的區域獲得具有開口部4的抗蝕劑5。開口部4是貫通抗蝕劑5的孔。關於曝光及顯影，可根據先前法進行。開口部4的最大寬度通常為塗膜3的膜厚的0.1倍～10倍、較佳為0.5倍～2倍。
（步驟（3）） 在步驟（3）中，一邊加熱一邊將熔融焊料填充至開口部4。冷卻後，如圖1（3）所示般，在各開口部4形成焊料電極6。 一邊加熱一邊將熔融焊料填充至開口部4的方法並無特別限制，可採用IMS法的通常的填充方法。在IMS法中，通常一邊將熔融焊料加熱至250℃以上一邊進行填充。
如所述般，在本發明的焊料電極的製造方法中，由於所述感光性樹脂組成物含有藉由熱而變為耐熱性高的結構的苯并噁唑前驅物，因此如IMS法般在將高溫的頭推抵至抗蝕劑5的表面而填充熔融焊料時，亦可抑制抗蝕劑5表面的龜裂的產生及潰爛的產生。
藉由本發明的焊料電極的製造方法以所述的方式製造的焊料電極，於不會在抗蝕劑產生龜裂或潰爛的狀態下形成，因此無形狀等的混亂，而成為適合於目的的電極。
所述焊料電極的製造方法在步驟（3）之後可進一步具有步驟（4）：將抗蝕劑5自基板1剝離。圖1（4）表示在步驟（3）之後將抗蝕劑5自基板1剝離的狀態。
藉由本發明的焊料電極的製造方法而製造的焊料電極，既可如圖1（3）所示般與抗蝕劑5一起利用，亦可如圖1（4）所示般在無抗蝕劑5的狀態下利用。
＜積層體的製造方法＞ 本發明的第1積層體的製造方法包括：步驟（1），在具有電極墊的第1基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），一邊加熱一邊將熔融焊料填充至所述開口部，而形成焊料電極；步驟（5），經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構；且所述感光性樹脂組成物至少含有苯并噁唑前驅物。
本發明的第2積層體的製造方法包括：步驟（1），在具有電極墊的第1基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），一邊加熱一邊將熔融焊料填充至所述開口部，而形成焊料電極；步驟（4），在步驟（3）之後，將所述抗蝕劑剝離；步驟（5），在步驟（4）之後，經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構；且所述感光性樹脂組成物至少含有苯并噁唑前驅物。
第1積層體的製造方法及第2積層體的製造方法中的步驟（1）～步驟（3）、及第2積層體的製造方法中的步驟（4），與所述焊料電極的製造方法中的步驟（1）～步驟（5）分別實質相同。即，第1積層體的製造方法是在所述焊料電極的製造方法中的步驟（1）～步驟（3）之後進行步驟（5）的方法，第2積層體的製造方法是在所述焊料電極的製造方法中的步驟（1）～步驟（4）之後進行步驟（5）的方法。
在第1積層體的製造方法及第2積層體的製造方法中，所述焊料電極的製造方法中的基板相當於第1基板。 第1積層體的製造方法是在所述步驟（1）～步驟（3）之後進行步驟（5）：經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構。
圖2（5-1）表示藉由第1積層體的製造方法而製造的積層體10。積層體10具有以如下方式形成的電性連接結構：經由藉由所述步驟（1）～步驟（3）而製造的圖1（3）所示的狀態的焊料電極6，將所述第1基板1的電極墊2、與具有電極墊12的第2基板11的電極墊12連接。
在將第1基板1與第2基板11以形成有電極墊的面相對的方式相對放置時，第2基板11所具有的電極墊12設置於與第1基板1的電極墊2對向的位置。使第2基板11的電極墊12與圖1（3）所示的狀態的焊料電極6接觸，進行加熱及/或壓接，藉此經由焊料電極6使第1基板1的電極墊2與第2基板11的電極墊12電性連接，而形成電性連接結構，獲得積層體10。所述加熱溫度通常為100℃～300℃，所述壓接時的力通常為0.1 MPa～10 MPa。
在圖1（3）所示的狀態下，在第1基板1上載置抗蝕劑5，因此積層體10具有：第1基板1、焊料電極6、第2基板11、被第1基板1及第2基板11夾持的抗蝕劑5。
第2積層體的製造方法是在所述步驟（1）～步驟（4）之後進行步驟（5）：經由所述焊料電極，形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構。
圖2（5-2）表示藉由第2積層體的製造方法而製造的積層體20。積層體20具有以如下方式形成的電性連接結構：經由藉由所述步驟（1）～步驟（4）而製造的圖1（4）所示的狀態的焊料電極6，將所述第1基板1的電極墊2、與具有電極墊12的第2基板11的電極墊12連接。
使第2基板11的電極墊12與圖1（4）所示的狀態的焊料電極6接觸，進行加熱及/或壓接，藉此經由焊料電極6使第1基板1的電極墊2與第2基板11的電極墊12電性連接，而形成電性連接結構，獲得積層體20。
在圖1（4）所示的狀態下，由於在第1基板1上未載置抗蝕劑5，因此積層體20由第1基板1、焊料電極6、及第2基板11形成。 如所述般，藉由本發明的積層體的製造方法而製造的積層體，可在第1基板與第2基板之間具備抗蝕劑，亦可不具備抗蝕劑。在如積層體10般具備抗蝕劑時，所述抗蝕劑用作底層填料。
藉由本發明的積層體的製造方法而製造的積層體，藉由IMS法而具有適合於目的的電性連接結構，因此由於焊料組成的選擇性擴大，而可應用於半導體元件、顯示元件、及功率器件等各種電子零件。 藉由本發明的積層體的製造方法而製造的積層體，可應用於半導體元件、顯示元件、及功率器件等電子零件。 [實施例]
以下，根據實施例對本發明進行更具體地說明，但本發明並不限定於該等實施例。在以下的實施例等的記載中，「份」以「質量份」的含義而使用。 1.物性的測定方法 （聚苯并噁唑前驅物及鹼可溶性樹脂的重量平均分子量（Mw）的測定方法） 在下述條件下藉由凝膠滲透層析法測定聚苯并噁唑前驅物及鹼可溶性樹脂的重量平均分子量（Mw）。 ·管柱：將東曹（Tosoh）公司製造的管柱TSK-M及TSK2500串列連接 ·溶劑：四氫呋喃 ·溫度：40℃ ·檢測方法：折射率法 ·標準物質：聚苯乙烯 ·GPC裝置：東曹製造、裝置名「HLC-8220-GPC」
2.抗蝕劑形成用組成物的準備 [合成例1]聚苯并噁唑前驅物的合成 在燒瓶中加入間苯二甲酸20 g及N-甲基吡咯啶酮100 g，將燒瓶內容物冷卻至5℃後，滴加亞硫醯氯29 g，反應30分鐘，而獲得間苯二甲醯氯的溶液。
繼而，在燒瓶中加入N-甲基吡咯啶酮100 g，添加雙(3-胺基-4-羥基苯基)六氟丙烷26 g及1,3-雙(4-胺基苯氧基)苯9 g，攪拌溶解後，添加吡啶20 g。將溶液的溫度保持為5℃，在所述溶液中歷時30分鐘滴加所述間苯二甲醯氯的溶液後，繼續攪拌60分鐘進行反應。將反應液投入至3升水中，將所產生的析出物過濾分離後，藉由純水清洗所述析出物，而獲得聚苯并噁唑前驅物。聚苯并噁唑前驅物的重量平均分子量為20,000。
[合成例2]鹼可溶性樹脂的合成 在經氮氣置換的帶有乾冰/甲醇回流器的燒瓶中，加入作為聚合起始劑的2,2'-偶氮雙異丁腈5.0 g、及作為聚合溶劑的二乙二醇乙基甲醚90 g，進行攪拌。在所得的溶液中，添加甲基丙烯酸10 g、對異丙烯基苯酚15 g、甲基丙烯酸三環[5.2.1.02,6 ]癸酯25 g、丙烯酸異冰片酯20 g、及丙烯酸正丁酯30 g，開始攪拌，升溫至80℃為止。然後，在80℃下加熱6小時進行反應。
在加熱結束後，將反應液滴加至大量的環己烷中，使反應產物凝固。將所述凝固物水洗，將所述凝固物再溶解於與凝固物相同質量的四氫呋喃中後，將所得的溶液滴加至大量的環己烷中再次進行凝固。進行合計3次所述再溶解及凝固作業後，將所得的凝固物在40℃下真空乾燥48小時，而獲得鹼可溶性樹脂。鹼可溶性樹脂的重量平均分子量為10,000。
[實施例1]感光性樹脂組成物1的製備 使用所述合成例1中合成的聚苯并噁唑前驅物100份、1,1-雙(4-羥基苯基)-1-[4-[1-(4-羥基苯基)-1-甲基乙基]苯基]乙烷與1,2-萘醌二疊氮-5-磺酸的縮合物（後者相對於前者的莫耳比：2.0）10份、N-甲基-2-吡咯啶酮100份，將該等混合、攪拌，而獲得均勻的溶液。藉由孔徑為10 μm的膠囊過濾器對所述溶液進行過濾，而製備感光性樹脂組成物1。
[製備例1]感光性樹脂組成物2的製備 使用所述合成例2中合成的鹼可溶性樹脂100份、聚酯丙烯酸酯（商品名「亞羅尼斯（Aronix）M-8060」、東亞合成（股）製造）50份、二苯基(2,4,6-三甲基苯甲醯基)氧化膦（商品名「路西林（LUCIRIN）TPO」、巴斯夫（BASF）（股）製造）4份、2,2-二甲氧基-1,2-二苯基乙烷-1-酮（商品名「豔佳固（IRGACURE）651」、巴斯夫（股）製造）19份、丙二醇單甲醚乙酸酯80份，將該等混合、攪拌，而獲得均勻的溶液。藉由孔徑為10 μm的膠囊過濾器對所述溶液進行過濾，而製備感光性樹脂組成物2。
[實施例2] 於在矽板上具有大量銅電極墊的基板上，使用旋塗機塗佈實施例1中所製備的感光性樹脂組成物1，藉由加熱板以120℃加熱5分鐘，而形成厚度為20 μm的塗膜。繼而，使用對準器（蘇斯（Suss）公司製造、型號「MA-200」），經由圖案遮罩以照射強度300 mJ/cm2 對所述塗膜進行波長為420 nm的光的曝光。曝光後，使塗膜與2.38質量%氫氧化四甲基銨水溶液接觸240秒，藉由流水清洗塗膜並顯影，而在與電極墊對應的部分形成具有開口部的抗蝕劑保持基板。藉由電子顯微鏡進行觀察，結果各開口部的開口是直徑為30 μm的圓形，各開口部的深度為20 μm。此外，開口部的最大寬度為30 μm。
將具有所述開口部的抗蝕劑保持基板在1質量%硫酸水溶液中在23℃下浸漬1分鐘後，進行水洗、乾燥。在乾燥後的基板的開口部，一邊將在250℃下使SAC305（製品名、無鉛焊料、千住金屬工業（股））熔融而得的熔融焊料加熱至250℃，一邊歷時10分鐘進行填充。藉由電子顯微鏡觀察熔融焊料填充後的抗蝕劑保持基板，結果確認到抗蝕劑無龜裂，並且熔融焊料良好地填充，焊料電極良好地形成。
然後，在混合二甲基亞碸90份、氫氧化四甲基銨3份及水7份而得的溶液中，在50℃下將形成有焊料電極的抗蝕劑保持基板浸漬20分鐘，而自基板剝離抗蝕劑。將所得的具備焊料電極的基板進行水洗並乾燥。
對於另外的具有銅電極墊的基板，在所述具有銅電極墊的基板上，經由所述焊料電極，以兩者取得電性連接結構的方式，載置另外的具有銅電極墊的基板。在所述具有2片銅電極墊的基板上，使用黏晶機裝置，以兩者壓接的方式，在250℃下施加30秒的0.3 MPa的壓力，而製造依序包含具有銅電極墊的基板、焊料電極、具有銅電極墊的基板的積層體。
[比較例1] 於在矽板上具有大量銅電極墊的基板上，使用旋塗機塗佈製備例1中所製備的感光性樹脂組成物2，藉由加熱板以120℃加熱5分鐘，而形成厚度為20 μm的塗膜。繼而使用對準器（蘇斯公司製造、型號「MA-200」），經由圖案遮罩以照射強度300 mJ/cm2 對所述塗膜進行波長為420 nm的光的曝光。曝光後，使塗膜與2.38質量%氫氧化四甲基銨水溶液接觸240秒，藉由流水清洗塗膜並顯影，而在與電極墊對應的部分形成具有開口部的抗蝕劑保持基板。藉由電子顯微鏡進行觀察，結果各開口部的開口是直徑為30 μm的圓形，各開口部的深度為20 μm。此外，開口部的最大寬度為30 μm。
將具有所述開口部的抗蝕劑保持基板在1質量%硫酸水溶液中在23℃下浸漬1分鐘後，進行水洗、乾燥。在乾燥後的基板的開口部，一邊將在250℃下使SAC305（製品名、無鉛焊料、千住金屬工業（股））熔融而得的熔融焊料加熱至250℃，一邊歷時10分鐘進行填充。藉由電子顯微鏡觀察熔融焊料填充後的抗蝕劑保持基板，結果確認到抗蝕劑產生龜裂。此外，熔融焊料無法良好地填充。
1、11‧‧‧基板
2、12‧‧‧電極墊
3‧‧‧塗膜
4‧‧‧開口部
5‧‧‧抗蝕劑
6‧‧‧焊料電極
10、20‧‧‧積層體
圖1（1）～圖1（4）是本發明的焊料電極的製造方法的各步驟中的包含基板的結構體的示意剖面圖。 圖2（5-1）及圖2（5-2）是本發明的積層體的示意剖面圖。
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Claims (13)

  1. 一種焊料電極的製造方法，其包括：步驟（1），在具有電極墊的基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），在所述開口部填充熔融焊料；且所述焊料電極的製造方法的特徵在於： 所述感光性樹脂組成物至少含有苯并噁唑前驅物。
  2. 如申請專利範圍第1項所述的焊料電極的製造方法，其中所述苯并噁唑前驅物具有以二羧酸及二羥基二胺為來源的結構。
  3. 如申請專利範圍第2項所述的焊料電極的製造方法，其中所述二羧酸為芳香族系二羧酸。
  4. 如申請專利範圍第2項或第3項中任一項所述的焊料電極的製造方法，其中所述二羥基二胺為芳香族系二胺。
  5. 如申請專利範圍第1項至第4項中任一項所述的焊料電極的製造方法，其中所述感光性樹脂組成物進一步含有感光劑。
  6. 如申請專利範圍第5項所述的焊料電極的製造方法，其中所述感光劑為萘醌二疊氮化合物。
  7. 如申請專利範圍第1項至第6項中任一項所述的焊料電極的製造方法，其進一步包括：步驟（4），將所述抗蝕劑剝離。
  8. 一種焊料電極，其是藉由如申請專利範圍第17項中任一項所述的焊料電極的製造方法而製造。
  9. 一種積層體的製造方法，其包括：步驟（1），在具有電極墊的第1基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），一邊加熱一邊將熔融焊料填充至所述開口部，而形成焊料電極；步驟（5），經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構，且所述積層體的製造方法的特徵在於： 所述感光性樹脂組成物至少含有苯并噁唑前驅物。
  10. 一種積層體的製造方法，其包括：步驟（1），在具有電極墊的第1基板上形成感光性樹脂組成物的塗膜；步驟（2），藉由將所述塗膜選擇性曝光，進而進行顯影，而在與電極墊對應的區域形成具有開口部的抗蝕劑；步驟（3），一邊加熱一邊將熔融焊料填充至所述開口部，而形成焊料電極；步驟（4），在步驟（3）之後，將所述抗蝕劑剝離；步驟（5），在步驟（4）之後，經由所述焊料電極，而形成所述第1基板的電極墊與具有電極墊的第2基板的電極墊的電性連接結構，且所述積層體的製造方法的特徵在於： 所述感光性樹脂組成物至少含有苯并噁唑前驅物。
  11. 一種積層體，其是藉由如申請專利範圍第9項或第10項中任一項所述的積層體的製造方法而製造。
  12. 一種電子零件，其具有如申請專利範圍第11項所述的積層體。
  13. 一種射出成形焊料用感光性樹脂組成物，其至少含有苯并噁唑前驅物。
TW105112583A 2015-05-08 2016-04-22 焊料電極的製造方法、焊料電極、積層體的製造方法、積層體、電子零件及射出成形焊料用感光性樹脂組成物 TWI681474B (zh)

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