TW201446827A - 電子零件用硬化性組合物、連接構造體及連接構造體之製造方法 - Google Patents

電子零件用硬化性組合物、連接構造體及連接構造體之製造方法 Download PDF

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TW201446827A
TW201446827A TW103101876A TW103101876A TW201446827A TW 201446827 A TW201446827 A TW 201446827A TW 103101876 A TW103101876 A TW 103101876A TW 103101876 A TW103101876 A TW 103101876A TW 201446827 A TW201446827 A TW 201446827A
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Taiwan
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electrode
curable composition
connection
conductive particles
conductive
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TW103101876A
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English (en)
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TWI582125B (zh
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Hideaki Ishizawa
Takashi Kubota
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Sekisui Chemical Co Ltd
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    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
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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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    • 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

本發明提供一種可快速地硬化、進而即便於將銅電極連接之情形時亦可提高導通性之電子零件用硬化性組合物。本發明之電子零件用硬化性組合物係用於銅電極之連接。本發明之電子零件用硬化性組合物包含：熱硬化性化合物、潛伏性硬化劑、及具有芳香族骨架之咪唑化合物。

Description

電子零件用硬化性組合物、連接構造體及連接構造體之製造方法
本發明係關於一種用於銅電極之連接之電子零件用硬化性組合物。又，本發明係關於一種使用上述電子零件用硬化性組合物之連接構造體及連接構造體之製造方法。
熱硬化性樹脂組合物可廣泛用於電子、建築及車輛等各種用途。又，有時為了將各種連接對象構件之電極間電性連接，而將導電性粒子調配於上述熱硬化性樹脂組合物。包含導電性粒子之熱硬化性樹脂組合物被稱為各向異性導電材料。
上述各向異性導電材料係用於IC晶片與軟性印刷電路基板之連接、及IC晶片與具有ITO電極之電路基板之連接等。例如，於IC晶片之電極與電路基板之電極之間配置各向異性導電材料後進行加熱及加壓，藉此可利用導電性粒子將該等電極電性連接。
作為上述熱硬化性樹脂組合物之一例，於下述專利文獻1中揭示有包含(a)環氧樹脂與(b)硬化促進劑之組合物。於專利文獻1之實施例中，使用有咪唑類作為上述(b)硬化促進劑。於專利文獻1中提出使用上述組合物作為半導體密封用膜狀接著劑。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2009-256588號公報
近年來，為了將電子零件之電極間等有效率地進行連接，而要求縮短組合物之硬化所需要之加熱時間。藉由縮短加熱時間，可抑制獲得之電子零件之熱劣化。
專利文獻1中記載有可製造如下半導體裝置，即於半導體裝置中將組合物用於密封之情形時作業性優異，即便於加熱至300℃以上之情形時亦可充分抑制空隙之產生，並且連接可靠性與絕緣可靠性足夠優異。然而，如專利文獻1所記載之先前之硬化性組合物，其存在並不充分地快速熱硬化之情況。又，銅電極之表面通常經耐熱預助焊劑處理。於為了將此種銅電極電性連接而使用先前之硬化性組合物之情形時，有導通性變低之情況。
本發明之目的在於提供一種可快速地硬化、進而即便於將銅電極連接之情形時亦可提高導通性之電子零件用硬化性組合物，以及使用該電子零件用硬化性組合物之連接構造體及連接構造體之製造方法。
根據本發明之較廣態樣，提供一種電子零件用硬化性組合物，其係用於銅電極之連接者，且包含：熱硬化性化合物、潛伏性硬化劑、及具有芳香族骨架之咪唑化合物。
於本發明之電子零件用硬化性組合物之一特定態樣中，上述潛伏性硬化劑為微膠囊型咪唑硬化劑。
於本發明之電子零件用硬化性組合物之一特定態樣中，該電子零件用硬化性組合物包含導電性粒子。
於本發明之電子零件用硬化性組合物之一特定態樣中，上述導電性粒子係導電性之外側之表面為焊料之導電性粒子。
於本發明之電子零件用硬化性組合物之一特定態樣中，上述硬 化性組合物為膏。
根據本發明之較廣態樣，提供一種連接構造體，其具備：表面具有第1電極之第1連接對象構件、表面具有第2電極之第2連接對象構件、及將上述第1連接對象構件與上述第2連接對象構件連接之連接部，且上述連接部係藉由使上述之電子零件用硬化性組合物硬化而形成，上述第1電極及上述第2電極中之至少一者為銅電極，且上述第1電極與上述第2電極被電性連接。
於本發明之連接構造體之一特定態樣中，上述電子零件用硬化性組合物包含導電性粒子，且上述第1電極與上述第2電極由上述導電性粒子電性連接。
根據本發明之較廣態樣，提供一種連接構造體之製造方法，其具備：於表面具有第1電極之第1連接對象構件、與表面具有第2電極之第2連接對象構件之間配置上述之電子零件用硬化性組合物之步驟；及藉由使上述電子零件用硬化性組合物硬化而形成將上述第1連接對象構件與上述第2連接對象構件連接之連接部，從而獲得將上述第1電極與上述第2電極電性連接之連接構造體的步驟，且上述第1電極及上述第2電極中之至少一者為銅電極。
於本發明之連接構造體之製造方法之一特定態樣中，上述電子零件用硬化性組合物包含導電性粒子，且獲得上述第1電極與上述第2電極由上述導電性粒子電性連接而成的連接構造體。
本發明之電子零件用硬化性組合物包含熱硬化性化合物、潛伏性硬化劑、及具有芳香族骨架之咪唑化合物，因此可快速地硬化。進而，使用本發明之電子零件用硬化性組合物將銅電極連接之情形時，可提高導通性。
1、11‧‧‧連接構造體
2、12‧‧‧第1連接對象構件
2a、12a‧‧‧第1電極
3、13‧‧‧連接部
4、14‧‧‧第2連接對象構件
4a、14a‧‧‧第2電極
5‧‧‧導電性粒子
21‧‧‧導電性粒子
21a‧‧‧表面
22‧‧‧樹脂粒子
22a‧‧‧表面
23‧‧‧導電層
24‧‧‧第1導電層
24a‧‧‧表面
25‧‧‧焊料層
25a‧‧‧熔融之焊料層部分
31‧‧‧導電性粒子
32‧‧‧焊料層
41‧‧‧焊料粒子
圖1係模式性地表示使用本發明之一實施形態之電子零件用硬化性組合物之連接構造體的剖面圖。
圖2係模式性地表示圖1所示之連接構造體之變化例之剖面圖。
圖3係模式性地表示可用於本發明之一實施形態之電子零件用硬化性組合物之導電性粒子的剖面圖。
圖4係表示導電性粒子之變化例之剖面圖。
圖5係表示導電性粒子之另一變化例之剖面圖。
以下，對本發明之詳細內容進行說明。
(電子零件用硬化性組合物)
本發明之電子零件用硬化性組合物(以下，有時簡稱為硬化性組合物)包含：熱硬化性化合物、潛伏性硬化劑、及具有芳香族骨架之咪唑化合物。上述硬化性組合物可用於銅電極之連接。上述硬化性組合物可用於電子零件。上述硬化性組合物可較佳地用於電子零件之連接。上述硬化性組合物較佳為電子零件用連接材料。上述硬化性組合物較佳為電子零件用電路連接材料。
本發明之電子零件用硬化性組合物具有上述之組成，因此可快速地硬化。進而，本發明之電子零件用硬化性組合物具有上述之組成，因此於將銅電極連接之情形時，可提高導通性。
又，銅電極之表面通常經耐熱預助焊劑處理。於本發明中，即便將此種經耐熱預助焊劑處理之銅電極進行連接，亦可提高導通性。上述具有芳香族骨架之咪唑化合物大大有助於提高銅電極之導通性。另一方面，於僅使用具有芳香族骨架之咪唑化合物且未使用潛伏性硬化劑之情形時，無法使上述熱硬化性化合物充分硬化，或組合物之保存穩定性變低，或組合物之硬化速度變慢。於本發明中，主要藉由上述潛伏性硬化劑而使上述熱硬化性化合物快速硬化，且主要藉由上述 具有芳香族骨架之咪唑化合物而提高銅電極之導通性。因此，於本發明中，就銅電極之連接而言，組合潛伏性硬化劑與具有芳香族骨架之咪唑化合物具有較大意義。
進而，於本發明中，可提高硬化物之耐濕熱性。又，亦可提高硬化物之耐熱衝擊性。
以下，對本發明之電子零件用硬化性組合物所含有之各成分之詳細內容進行說明。
[熱硬化性化合物]
作為上述熱硬化性化合物，可列舉：氧雜環丁烷化合物、環氧化合物、環硫化合物、(甲基)丙烯酸系化合物、酚化合物、胺基化合物、不飽和聚酯化合物、聚胺基甲酸酯化合物、聚矽氧化合物及聚醯亞胺化合物等。上述熱硬化性化合物可僅使用1種，亦可併用2種以上。
環氧化合物具有硬化物之接著力較高、且硬化物之耐水性及耐熱性亦優異之性質。因此，上述熱硬化性化合物較佳為環氧化合物。
作為上述環氧化合物，可列舉：雙酚型環氧化合物、酚系酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、聯苯酚型環氧化合物、間苯二酚型環氧化合物、萘型環氧化合物、茀型環氧化合物、苯酚芳烷基型環氧化合物、萘酚芳烷基型環氧化合物、二環戊二烯型環氧化合物、蒽型環氧化合物、具有金剛烷骨架之環氧化合物、具有三環癸烷骨架之環氧化合物、及於骨架具有三核之環氧化合物等。作為上述雙酚型環氧化合物，可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物及雙酚S型環氧化合物等。
上述環氧化合物亦可具有環氧基及自由基聚合性基。上述自由基聚合性基意指可藉由自由基進行加成聚合之基。作為上述自由基聚合性基，可列舉包含不飽和雙鍵之基等。作為上述自由基聚合性基之 具體例，可列舉：烯丙基、異丙烯基、順丁烯二醯基、苯乙烯基、乙烯基苄基、(甲基)丙烯醯基及乙烯基等。再者，所謂(甲基)丙烯醯基意指丙烯醯基與甲基丙烯醯基。
就進一步提高組合物之快速硬化性及硬化物之耐濕熱性之觀點而言，上述自由基聚合性基較佳為具有乙烯基，更佳為(甲基)丙烯醯基。於上述自由基聚合性基為(甲基)丙烯醯基之情形時，上述自由基聚合性基具有乙烯基。
就進一步提高組合物之快速硬化性之觀點而言，上述環氧化合物較佳為於兩末端具有環氧基。就進一步提高硬化物之耐濕熱性之觀點而言，上述環氧化合物較佳為於支鏈具有乙烯基，較佳為具有(甲基)丙烯醯基，較佳為於支鏈具有(甲基)丙烯醯基。
就進一步提高組合物之快速硬化性及硬化物之耐濕熱性之觀點而言，上述環氧化合物之重量平均分子量較佳為500以上，更佳為1000以上，且較佳為150000以下，更佳為50000以下，進而較佳為15000以下。
上述環氧化合物之重量平均分子量係表示藉由凝膠滲透層析法(GPC)而測定之以聚苯乙烯換算計之重量平均分子量。
上述環氧化合物更佳為使用二醇化合物與具有2個環氧基之化合物的反應物。上述環氧化合物較佳為藉由使具有乙烯基之化合物或具有環氧基之化合物與二醇化合物和具有2個環氧基之化合物的反應物進行反應而獲得。
上述環氧化合物較佳為於支鏈具有1個以上乙烯基，更佳為於支鏈具有合計2個以上之乙烯基。乙烯基之數量越多，越可進一步縮短加熱時間，進而可進一步提高硬化物之接著性及耐濕熱性。
上述環氧化合物較佳為具有2個以上酚性羥基之化合物、與具有2個以上環氧基之化合物的反應物。
作為上述具有2個以上酚性羥基之化合物，可列舉：雙酚化合物、間苯二酚及萘酚等。作為上述雙酚化合物，可列舉：雙酚F、雙酚A、雙酚S、雙酚SA及雙酚E等。
作為上述具有2個以上環氧基之環氧化合物，可列舉脂肪族環氧化合物及芳香族環氧化合物等。作為上述脂肪族環氧化合物，可列舉：於碳數3~12之烷基鏈之兩末端具有縮水甘油醚基之化合物、以及具有下述結構單元之聚醚型環氧化合物，該結構單元係具有碳數2~4之聚醚骨架，且2~10個該聚醚骨架連續鍵結。
上述環氧化合物較佳為藉由使具有自由基聚合性基之化合物與雙酚F或間苯二酚與1,6-己二醇二縮水甘油醚或間苯二酚二縮水甘油醚之反應物(以下，有時記載為反應物X)進行反應而獲得。於該反應中，以自由基聚合性基殘留之方式進行反應。使用此種化合物而合成之環氧化合物可進一步快速地硬化，進而可使硬化物之接著性及耐濕熱性進一步提高。上述具有自由基聚合性基之化合物較佳為(甲基)丙烯酸或異氰酸(甲基)丙烯醯氧基乙酯。
作為上述反應物X，可列舉：雙酚F與1,6-己二醇二縮水甘油醚之第1反應物、間苯二酚與1,6-己二醇二縮水甘油醚之第2反應物、間苯二酚與間苯二酚二縮水甘油醚之第3反應物、及雙酚F與間苯二酚二縮水甘油醚之第4反應物。
上述第1反應物係於主鏈具有源自雙酚F之骨架與源自1,6-己二醇二縮水甘油醚之骨架所鍵結而成之結構單元，且於兩末端具有源自1,6-己二醇二縮水甘油醚之環氧基。上述第2反應物係於主鏈具有源自間苯二酚之結構單元與源自1,6-己二醇二縮水甘油醚之結構單元，且於兩末端具有源自1,6-己二醇二縮水甘油醚之環氧基。上述第3反應物係於主鏈具有源自間苯二酚之骨架與源自間苯二酚二縮水甘油醚之骨架，且於兩末端具有源自間苯二酚二縮水甘油醚之環氧基。上述 第4反應物係於主鏈具有源自雙酚F之骨架與源自間苯二酚二縮水甘油醚之骨架，且於兩末端具有源自間苯二酚二縮水甘油醚之環氧基。
就容易合成、可使環氧化合物進一步快速地硬化、進而使硬化物之接著性及耐濕性進一步提高之觀點而言，上述第1、第2、第3、第4反應物中，較佳為上述第1反應物、上述第2反應物或上述第3反應物。上述反應物X較佳為上述第1反應物，亦較佳為上述第2反應物，進而亦較佳為上述第3反應物。
[潛伏性硬化劑]
作為上述潛伏性硬化劑，可列舉：潛伏性咪唑硬化劑、潛伏性胺硬化劑、潛伏性酚硬化劑、三氟化硼-胺錯合物及有機酸醯肼等。上述潛伏性硬化劑可具有芳香族骨架，亦可不具有芳香族骨架。上述潛伏性硬化劑可僅使用1種，亦可併用2種以上。
作為上述潛伏性咪唑硬化劑之市售品，可列舉：日本曹達公司製造之包藏咪唑化合物「TEP-2MZ」、「TEP-2E4MZ」及「TEP-1B2MZ」、以及四國化成工業公司製造之「CUREDUCT P-0505」等。
作為上述潛伏性胺硬化劑，可列舉：雙氰胺、改性胺化合物及胺加成物化合物等。
作為上述改性胺化合物之市售品，可列舉：T & K TOKA公司製造之「Fujicure FXR-1020」、「Fujicure FXR-1030」及「Fujicure FXR-1081」等。作為上述胺加成物化合物，可列舉：Ajinomoto Fine-Tech公司製造之「Amicure PN-23」、「Amicure PN-H」、「Amicure PN-31」、「Amicure PN-40」、「Amicure PN-50」、「Amicure PN-F」、「Amicure PN-23J」、「Amicure PN-31J」、「Amicure PN-40J」、「Amicure PN-40」、「Amicure MY-24」、「Amicure MY-H」及「Amicure 25」等。
作為上述有機酸醯肼之市售品，可列舉：Ajinomoto Fine-Tech公 司製造之「Amicure VDH」、「Amicure VDH-J」、「Amicure UDH」及「Amicure UDH-J」等。
就進一步提高組合物之快速硬化性之觀點而言，上述潛伏性硬化劑較佳為潛伏性咪唑硬化劑，更佳為微膠囊型咪唑硬化劑。就進一步提高組合物之保存穩定性之觀點而言，上述潛伏性硬化劑更佳為微膠囊型潛伏性硬化劑，更佳為微膠囊型咪唑硬化劑。
作為上述微膠囊型咪唑硬化劑之市售品，可列舉：旭化成E-MATERIALS公司製造之「Novacure HX3941HP」、「Novacure HX3921HP」、「Novacure HX3721」、「Novacure HX3722」、「Novacure HX3748」、「Novacure HX3088」、「Novacure HX3741」、「Novacure HX3742」及「Novacure HX3613」等。
相對於上述熱硬化性化合物100重量份，上述潛伏性硬化劑之含量較佳為1重量份以上，更佳為5重量份以上，且較佳為65重量份以下，更佳為55重量份以下。若上述潛伏性硬化劑之含量為上述下限以上及上述上限以下，則組合物之快速硬化性及銅電極間之導通性平衡良好地變高。
[具有芳香族骨架之咪唑化合物]
上述具有芳香族骨架之咪唑化合物並非潛伏性硬化劑。關於上述具有芳香族骨架之咪唑化合物，係將潛伏性硬化劑除外。上述硬化性組合物所含有之潛伏性硬化劑、與上述硬化性組合物所含有之具有芳香族骨架之咪唑化合物不同。上述具有芳香族骨架之咪唑化合物可僅使用1種，亦可併用2種以上。
作為上述芳香族骨架，可列舉：芳基骨架、萘骨架及蒽骨架等。就有效提高銅電極間之導通性之觀點而言，上述芳香族骨架較佳為芳基骨架，更佳為苯基骨架。
作為上述具有芳香族骨架之咪唑化合物，可列舉：2-苯咪唑、2- 苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯咪唑、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽、2-苯基-4-甲基-5-二羥基甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、及2-苯基-4-甲基-5-羥基甲基咪唑等。
相對於上述熱硬化性化合物100重量份，上述具有芳香族骨架之咪唑化合物之含量較佳為0.1重量份以上，更佳為0.5重量份以上，且較佳為10重量份以下，更佳為5重量份以下。若上述具有芳香族骨架之咪唑化合物之含量為上述下限以上及上述上限以下，則組合物之快速硬化性及銅電極間之導通性平衡良好地變高。
[其他成分]
上述硬化性組合物亦可視需要進而含有助焊劑、接著力調整劑、無機填充劑、溶劑、儲存穩定劑、離子捕捉劑或矽烷偶合劑等。
上述硬化性化合物較佳為含有助焊劑。藉由使用助焊劑，從而銅電極之導通性進一步變高。可使用公知之助焊劑作為上述助焊劑。上述助焊劑可僅使用1種，亦可併用2種以上。
上述助焊劑並無特別限定。可使用通常用於焊料接合等之助焊劑作為該助焊劑。作為上述助焊劑，例如可列舉：氯化鋅、氯化鋅與無機鹵化物之混合物、氯化鋅與無機酸之混合物、熔鹽、磷酸、磷酸之衍生物、有機鹵化物、肼、有機酸及松脂等。
作為上述熔鹽，可列舉氯化銨等。作為上述有機酸，可列舉乳酸、檸檬酸、硬脂酸及麩胺酸等。作為上述松脂，可列舉活化松脂及非活化松脂等。上述助焊劑較佳為松脂。藉由使用松脂，從而電極間之連接電阻進一步變低。
上述松脂係以松香酸為主成分之松香類。上述助焊劑較佳為松香類，更佳為松香酸。藉由使用該較佳之助焊劑，從而電極間之連接電阻進一步變低。又，上述助焊劑較佳為具有羧基之有機酸。作為具 有羧基之化合物，可列舉：於烷基鏈鍵結有羧基之化合物、於芳香環鍵結有羧基之化合物等。於該等具有羧基之化合物中，亦可於烷基鏈或芳香環進而鍵結有羥基。鍵結於烷基鏈或芳香環之羧基之數量較佳為1~3個，更佳為1或2個。於烷基鏈鍵結有羧基之化合物中之烷基鏈之碳數較佳為3以上，且較佳為8以下，更佳為6以下。作為於烷基鏈鍵結有羧基之化合物之具體例，可列舉己酸(碳數5、羧基1個)及戊二酸(碳數4、羧基2個)等。作為具有羧基與羥基之化合物之具體例，可列舉蘋果酸及檸檬酸等。作為於芳香環鍵結有羧基之化合物之具體例，可列舉：苯甲酸、鄰苯二甲酸、苯甲酸酐及鄰苯二甲酸酐等。
相對於上述熱硬化性化合物100重量份，上述助焊劑之含量較佳為0.5重量份以上，更佳為1重量份以上，且較佳為10重量份以下，更佳為5重量份以下。若上述助焊劑之含量為上述下限以上及上限以下，則助焊劑之添加效果進一步有效地顯現。因此，組合物中之助焊劑效果變高，例如銅電極之導通性進一步變高。
(包含導電性粒子之電子零件用硬化性組合物)
於上述硬化性組合物包含導電性粒子之情形時，可使用上述硬化性組合物作為導電材料。上述導電材料較佳為各向異性導電材料。
上述導電性粒子係將連接對象構件之電極間電性連接。具體而言，上述導電性粒子例如將電路基板與半導體晶片之電極間電性連接。上述導電性粒子只要為具有導電性之粒子，則無特別限定。上述導電性粒子只要於導電性之表面具有導電部即可。
作為上述導電性粒子，例如可列舉：有機粒子、除金屬粒子外之無機粒子、有機無機混合粒子或金屬粒子等之表面由導電層(金屬層)被覆而成之導電性粒子、或實際上僅由金屬構成之金屬粒子等。
於圖3中以剖面圖表示可用於本發明之一實施形態之電子零件用硬化性組合物之導電性粒子。
圖3所示之導電性粒子21具有樹脂粒子22(基材粒子)、與配置於樹脂粒子22之表面22a上之導電層23。導電層23被覆樹脂粒子22之表面22a。導電性粒子21係樹脂粒子22之表面22a由導電層23被覆之被覆粒子。因此，導電性粒子21於表面21a具有導電層23。除樹脂粒子22外，亦可使用金屬粒子等。
導電層23具有配置於樹脂粒子22之表面22a上之第1導電層24、與配置於該第1導電層24之表面24a上之焊料層25(焊料、第2導電層)。導電層23之外側之表面層為焊料層25。因此，導電性粒子21具有作為導電層23之一部分之焊料層25，進而於樹脂粒子22與焊料層25之間具有作為導電層23之一部分之與焊料層25不同之第1導電層24。如上所述，導電層23可具有多層構造，可具有2層以上之積層構造。
如上述般，導電層23具有2層構造。如圖4所示之變化例般，導電性粒子31亦可具有焊料層32作為單層之導電層。只要導電性粒子中之導電層之至少外側之表面層(表面)為焊料層(焊料)即可。其中，導電性粒子21與導電性粒子31中，導電性粒子21由於導電性粒子之製作容易故而較佳。又，亦可使用如圖5所示之變化例般於核心不具有基材粒子而並非核殼粒子之焊料粒子，即導電性粒子41。導電性粒子41之中心部亦由焊料形成。
導電性粒子21、31、41可用於上述導電材料。
上述導電部並無特別限定。作為構成上述導電部之金屬，可列舉：金、銀、銅、鎳、鈀及錫等。作為上述導電層，可列舉：金層、銀層、銅層、鎳層、鈀層或含有錫之導電層等。
就使電極與導電性粒子之接觸面積變大而進一步提高電極間之導通可靠性的觀點而言，上述導電性粒子較佳為具有樹脂粒子、與配置於該樹脂粒子之表面上之導電層(第1導電層)。就進一步提高電極間之導通可靠性之觀點而言，上述導電性粒子較佳為至少導電性之外 側之表面為低熔點金屬層之導電性粒子。就進一步提高耐濕熱性及導通性之觀點而言，上述導電性粒子更佳為具有基材粒子、與配置於該基材粒子之表面上之導電層，且該導電層之至少外側之表面為低熔點金屬層。上述導電性粒子更佳為具有樹脂粒子、與配置於該樹脂粒子之表面上之導電層，且該導電層之至少外側之表面為低熔點金屬層。
上述低熔點金屬層係含有低熔點金屬之層。該所謂低熔點金屬，係指熔點為450℃以下之金屬。低熔點金屬之熔點較佳為300℃以下，更佳為160℃以下。又，上述低熔點金屬較佳為含有錫。低熔點金屬所含有之金屬100重量%中，錫之含量較佳為30重量%以上，更佳為40重量%以上，進而較佳為70重量%以上，尤佳為90重量%以上。若上述低熔點金屬中之錫之含量為上述下限以上，則低熔點金屬與電極之連接可靠性進一步變高。再者，上述錫之含量可使用高頻電感耦合電漿發光分光分析裝置(堀場製作所公司製造之「ICP-AES」)、或螢光X射線分析裝置(島津製作所公司製造之「EDX-800HS」)等進行測定。就進一步提高耐濕熱性及導通性之觀點而言，上述導電性粒子較佳為導電性之外側之表面為焊料之導電性粒子。
於導電部之外側之表面為低熔點金屬層之情形時，低熔點金屬層熔融而接合於電極，從而低熔點金屬層使電極間導通。例如，低熔點金屬層與電極容易面接觸而並非點接觸，因此連接電阻變低。又，藉由使用至少導電性之外側之表面為低熔點金屬層之導電性粒子，從而低熔點金屬層與電極之接合強度變高，結果，低熔點金屬層與電極之剝離變得進一步難以產生，而導通可靠性有效地變高。
構成上述低熔點金屬層之低熔點金屬並無特別限定。上述低熔點金屬較佳為錫、或含有錫之合金。該合金可列舉：錫-銀合金、錫-銅合金、錫-銀-銅合金、錫-鉍合金、錫-鋅合金、錫-銦合金等。其中，就對電極之潤濕性優異方面而言，上述低熔點金屬較佳為錫、 錫-銀合金、錫-銀-銅合金、錫-鉍合金、錫-銦合金。更佳為錫-鉍合金、錫-銦合金。
又，上述低熔點金屬較佳為焊料。構成上述焊料之材料並無特別限定，但較佳為基於JIS Z3001：焊接用語而液相線為450℃以下之填充金屬材。作為上述焊料之組成，例如可列舉包含鋅、金、鉛、銅、錫、鉍、銦等之金屬組成。其中，較佳為低熔點且無鉛之錫-銦系(117℃共晶)、或錫-鉍系(139℃共晶)。即，上述焊料較佳為不含鉛，且較佳為含有錫與銦之焊料、或含有錫與鉍之焊料。
為了進一步提高上述低熔點金屬與電極之接合強度，上述低熔點金屬亦可含有鎳、銅、銻、鋁、鋅、鐵、金、鈦、磷、鍺、碲、鈷、鉍、錳、鉻、鉬、鈀等金屬。就更進一步提高低熔點金屬與電極之接合強度之觀點而言，上述低熔點金屬較佳為含有鎳、銅、銻、鋁或鋅。就進一步提高低熔點金屬與電極之接合強度之觀點而言，用以提高接合強度之該等金屬之含量於低熔點金屬100重量%中，較佳為0.0001重量%以上且較佳為1重量%以下。
上述導電性粒子較佳為具有樹脂粒子、與配置於該樹脂粒子之表面上之導電層，且該導電層之外側之表面為低熔點金屬層，於上述樹脂粒子與上述低熔點金屬層(焊料層等)之間具有與上述低熔點金屬層不同之第2導電層。於該情形時，上述低熔點金屬層為上述導電層整體之一部分，且上述第2導電層為上述導電層整體之一部分。
上述與低熔點金屬層不同之上述第2導電層較佳為含有金屬。構成該第2導電層之金屬並無特別限定。作為該金屬，例如可列舉：金、銀、銅、鉑、鈀、鋅、鉛、鋁、鈷、銦、鎳、鉻、鈦、銻、鉍、鍺及鎘、以及該等之合金等。又，亦可使用摻錫氧化銦(ITO)作為上述金屬。上述金屬可僅使用1種，亦可併用2種以上。
上述第2導電層較佳為鎳層、鈀層、銅層或金層，更佳為鎳層或 金層，進而較佳為銅層。導電性粒子較佳為具有鎳層、鈀層、銅層或金層，更佳為具有鎳層或金層，進而較佳為具有銅層。將具有該等較佳導電層之導電性粒子用於電極間之連接，藉此電極間之連接電阻進一步變低。又，於該等較佳之導電層之表面更容易形成低熔點金屬層。再者，上述第2導電層亦可為焊料層等低熔點金屬層。導電性粒子亦可具有複數層之低熔點金屬層。
上述低熔點金屬層之厚度較佳為0.1μm以上，更佳為0.5μm以上，進而較佳為1μm以上，且較佳為50μm以下，更佳為10μm以下，進而較佳為5μm以下，尤佳為3μm以下。若上述低熔點金屬層之厚度為上述下限以上，則導電性充分變高。若上述低熔點金屬層之厚度為上述上限以下，則樹脂粒子與低熔點金屬層之熱膨脹率之差變小，而低熔點金屬層變得難以剝離。
於導電層為低熔點金屬層以外之導電層之情形時，或導電層具有多層構造之情形時，導電層之整體厚度較佳為0.1μm以上，更佳為0.5μm以上，進而較佳為1μm以上，且較佳為50μm以下，更佳為10μm以下，進而較佳為5μm以下，尤佳為3μm以下。
上述導電性粒子之平均粒徑較佳為100μm以下，更佳為20μm以下，進而較佳為未達20μm，進而更佳為15μm以下，尤佳為10μm以下。導電性粒子之平均粒徑較佳為0.5μm以上，更佳為1μm以上。就進一步提高經受熱歷程之情形之連接構造體之連接可靠性的觀點而言，導電性粒子之平均粒徑尤佳為1μm以上且10μm以下，最佳為1μm以上且4μm以下。導電性粒子之平均粒徑亦較佳為3μm以下。
因係適合上述導電材料中之導電性粒子之尺寸，且可使電極間之間隔進一步變小，故導電性粒子之平均粒徑尤佳為1μm以上且100μm以下。
上述導電性粒子之「平均粒徑」係表示數量平均粒徑。導電性 粒子之平均粒徑係藉由利用電子顯微鏡或光學顯微鏡對任意50個導電性粒子進行觀察並算出平均值而求出。
上述導電性粒子之表面亦可經絕緣性粒子等絕緣性材料、助焊劑等進行絕緣處理。絕緣性材料、助焊劑等較佳為藉由利用連接時之熱進行軟化、流動而自連接部被去除。藉此，可抑制電極間之短路。
上述導電性粒子之含量並無特別限定。上述硬化性組合物100重量%中，上述導電性粒子之含量較佳為0.1重量%以上，更佳為0.5重量%以上，且較佳為40重量%以下，更佳為20重量%以下，進而較佳為15重量%以下。若上述導電性粒子之含量為上述下限以上及上述上限以下，則可容易地將導電性粒子配置於應連接之上下之電極間。進而，不可連接之鄰接之電極間變得難以經由複數個導電性粒子而電性連接。即，可防止相鄰之電極間之短路。
(電子零件用硬化性組合物之用途)
上述硬化性組合物可用以將各種連接對象構件進行接著。其中，上述硬化性組合物可用於銅電極之連接。上述硬化性組合物可為膜，亦可為膏。上述硬化性組合物較佳為膏。若上述硬化性組合物為膏，則初期之連接電阻進一步變低。進而，亦可有效地維持被暴露於衝擊或高溫高濕後之連接電阻較低。
於上述硬化性組合物為包含導電性粒子之導電材料之情形時，該導電材料可用作導電膏、或導電膜等。於上述導電材料被用作導電膜之情形時，亦可使不含有導電性粒子之膜積層於含有導電性粒子之該導電膜。再者，膜包括片。上述硬化性組合物較佳為膏狀之導電膏。上述導電膏較佳為各向異性導電膏。上述導電膜較佳為各向異性導電膜。
上述硬化性組合物可較佳地用以獲得如下連接構造體，該連接構造體具備表面具有第1電極之電極第1連接對象構件、表面具有第2 電極之第2連接對象構件、及將上述第1連接對象構件與上述第2連接對象構件連接之連接部。上述連接部係藉由使上述硬化性組合物硬化而形成。上述連接構造體中，上述第1電極及上述第2電極中之至少一者為銅電極。將上述第1電極與上述第2電極電性連接。更佳為上述第1電極及上述第2電極兩者為銅電極。
較佳為上述電子零件用硬化性組合物包含導電性粒子，且獲得上述第1電極與上述第2電極由上述導電性粒子電性連接之連接構造體。
本發明之連接構造體之製造方法具備：於表面具有第1電極之第1連接對象構件與表面具有第2電極之第2連接對象構件之間配置上述電子零件用硬化性組合物的步驟；及藉由使上述電子零件用硬化性組合物硬化而形成將上述第1連接對象構件與上述第2連接對象構件連接之連接部，從而獲得將上述第1電極與上述第2電極電性連接之連接構造體的步驟。上述第1電極及上述第2電極中之至少一者為銅電極。
於本發明之連接構造體之製造方法中，較佳為上述電子零件用硬化性組合物包含導電性粒子，且獲得上述第1電極與上述第2電極由上述導電性粒子電性連接之連接構造體。
於圖1中以剖面圖模式性地表示使用本發明之一實施形態之硬化性組合物的連接構造體之一例。
圖1所示之連接構造體1具備：第1連接對象構件2、第2連接對象構件4、及將第1連接對象構件2與第2連接對象構件4連接之連接部3。連接部3為硬化物層，且係藉由使包含導電性粒子5之電子零件用硬化性組合物(導電材料)硬化而形成。
第1連接對象構件2於表面(上表面)具有複數個第1電極2a。第2連接對象構件4於表面(下表面)具有複數個第2電極4a。第1電極2a與第2電極4a中之至少一者為銅電極。第1電極2a與第2電極4a由1個或複數 個導電性粒子5電性連接。因此，第1、第2連接對象構件2、4由導電性粒子5電性連接。
第1、第2電極2a、4a間之連接係通常藉由如下方式進行：將第1連接對象構件2與第2連接對象構件4以介隔上述硬化性組合物且第1、第2電極2a、4a彼此相對向之方式進行重合後，於使上述硬化性組合物硬化時進行加壓。通常導電性粒子5由於加壓而被壓縮。
上述第1、第2連接對象構件並無特別限定。作為上述第1、第2連接對象構件，具體而言，可列舉：半導體晶片、電容器及二極體等電子零件以及印刷基板、軟性印刷基板、玻璃環氧基板及玻璃基板等電路基板等電子零件等。
再者，上述硬化性組合物亦可不含導電性粒子。於該情形時，不藉由導電性粒子將第1、第2連接對象構件之電極間電性連接，例如使電極彼此接觸而可將電極間電性連接。
於圖2中以剖面圖模式性地表示圖1所示之連接構造體之變化例。
圖2所示之連接構造體11具備：第1連接對象構件12、第2連接對象構件14、及將第1連接對象構件12與第2連接對象構件14連接之連接部13。連接部13為硬化物層，且係藉由使不含導電性粒子之電子零件用硬化性組合物(導電材料)硬化而形成。
第1連接對象構件12於表面(上表面)具有複數個第1電極12a。第2連接對象構件14於表面(下表面)具有複數個第2電極14a。第1電極12a與第2電極14a中之至少一者為銅電極。第1電極12a與第2電極14a例如為凸塊電極。第1電極12a與第2電極14a不經由導電性粒子而相互接觸，藉此被電性連接。因此，第1、第2連接對象構件12、14被電性連接。
於上述硬化性組合物為導電材料之情形時，該導電材料例如可 用於軟性印刷基板與玻璃基板之連接(FOG(Film on Glass，鍍膜玻璃))、半導體晶片與軟性印刷基板之連接(COF(Chip on Film，薄膜覆晶))、半導體晶片與玻璃基板之連接(COG(Chip on Glass，玻璃覆晶))、或軟性印刷基板與玻璃環氧基板之連接(FOB(Film on Board，鍍膜板))等。其中，上述導電材料較佳用於FOG用途或COG用途，更佳用於COG用途。上述硬化性組合物較佳為用於軟性印刷基板與玻璃基板之連接、或半導體晶片與軟性印刷基板之連接的導電材料，更佳為用於半導體晶片與軟性印刷基板之連接之導電材料。
以下，列舉實施例及比較例而對本發明具體地進行說明。本發明並不僅限於以下之實施例。
準備以下之調配成分。
(熱硬化性化合物)
熱硬化性化合物1(含有環氧基之聚合物，日油公司製造之「MARPROOF G-01100」，重量平均分子量：12000，Tg：47℃，環氧當量：170g/eq)
熱硬化性化合物2(間苯二酚型環氧化合物，Nagase chemteX公司製造之「EX-201」)
熱硬化性化合物3(三三縮水甘油醚，日產化學公司製造之「TEPIC-SS」)
(潛伏性硬化劑)
潛伏性硬化劑1(包藏咪唑化合物，日本曹達公司製造之「TEP-2MZ」)
潛伏性硬化劑2(環氧基-咪唑加成物，四國化成工業公司製造之「CUREDUCT P-0505」)
潛伏性硬化劑3((微膠囊型潛伏性硬化劑)，旭化成E-MATERIALS公司製造之「Novacure HX3921HP」)
潛伏性硬化劑4((微膠囊型潛伏性硬化劑)，旭化成E-MATERIALS公司製造之「Novacure HX3941HP」)
(具有芳香族骨架之咪唑化合物)
含有芳香族骨架之咪唑化合物1(四國化成工業公司製造之「2-苯咪唑」)
含有芳香族骨架之咪唑化合物2(四國化成工業公司製造之「2-苯基-4-甲基咪唑」)
含有芳香族骨架之咪唑化合物3(和光純藥工業公司製造之「苯并咪唑」)
含有芳香族骨架之咪唑化合物4(和光純藥工業公司製造之「2-甲基苯并咪唑」)
(其他咪唑化合物)
其他咪唑化合物(並非潛伏性硬化劑，不具有芳香族骨架，四國化成工業公司製造之「2-甲基咪唑」)
(導電性粒子)
導電性粒子1：SnBi焊料粒子(福田金屬公司製造之「Sn58Bi-20」，平均粒徑4.5μm)
導電性粒子2：(樹脂核心焊料被覆粒子，以下述步驟進行製作)
將二乙烯苯樹脂粒子(積水化學工業公司製造之「Micropearl SP-207」，平均粒徑7μm，軟化點330℃，10%K值(23℃)4GPa)進行無電鍍鎳，而於樹脂粒子之表面上形成厚度0.1μm之底層鍍鎳層。繼而，將形成有底層鍍鎳層之樹脂粒子進行電鍍銅，而形成厚度1μm之銅層。進而，使用含有錫及鉍之電鍍液進行電鍍，而形成厚度1μm之焊料層。以上述方式製作於樹脂粒子之表面上形成有厚度1μm之銅層、且於該銅層之表面形成有厚度1μm之焊料層(錫：鉍=43重量%：57重量%)的導電性粒子(平均粒徑14μm，CV值22%，樹脂核心焊料被 覆粒子)。
導電性粒子3：二乙烯苯樹脂粒子之鍍Au粒子(積水化學工業公司製造之「Au-210」，平均粒徑10μm)
(其他成分)
填料(奈米二氧化矽、Tokuyama公司製造之「MT-10」)
接著賦予劑(信越化學工業公司製造之「KBE-403」)
助焊劑(和光純藥工業公司製造之「戊二酸」)
苯氧基樹脂(新日鐵住金化學公司製造之「YP-50S」)
(實施例1~21及比較例1~3)
將下述表1~3所示之成分以下述表1~3所示之調配量進行調配，並使用行星式攪拌機以2000rpm進行5分鐘攪拌，藉此獲得各向異性導電膏。
(實施例22)
使苯氧基樹脂(新日鐵住金化學公司製造之「YP-50S」)10重量份以固形物成分成為50重量%之方式溶解於甲基乙基酮(MEK)中，而獲得溶解液。將下述表3所示之除苯氧基樹脂外之成分以下述表3所示之調配量與上述溶解液之總量進行調配，使用行星式攪拌機以2000rpm進行5分鐘攪拌後，使用棒式塗佈機以乾燥後之厚度成為30μm之方式塗佈於脫模PET(聚對苯二甲酸乙二酯)膜上。藉由在室溫下進行真空乾燥而去除MEK，藉此獲得各向異性導電膜。
(評價)
(1)~(3)之評價項目所使用之連接構造體(FOB)之製作：準備於L/S為100μm/100μm之電極圖案中於上表面具有70根銅電極之玻璃環氧基板(FR-4基板)。又，準備於L/S為100μm/100μm之電極圖案中於下表面具有70根銅電極之軟性印刷基板。FR-4基板與軟性印刷基板之圖案係以藉由重疊而可形成菊鏈之方式進行設計。
將獲得之各向異性導電膏以厚度成為200μm之方式塗佈於上述玻璃環氧基板之上表面，而形成各向異性導電膏層。繼而，於各向異性導電膏層上以電極彼此相對向之方式積層上述軟性印刷基板。其後，以各向異性導電膏層之溫度成為170℃(實際壓接溫度)之方式調整加熱壓接頭之溫度，並且將加壓壓接頭置於軟性印刷基板之上表面，施加1MPa之壓力，於170℃下使各向異性導電膏層硬化直至硬化結束，而獲得連接構造體(FOB)。
(1)硬化速度
對獲得上述連接構造體時藉由加熱而各向異性導電膏層硬化為止之時間進行測定。具體而言，於獲得上述連接構造體之步驟中，於將各向異性導電膏塗佈於上述玻璃環氧基板後，於170℃加熱板上對各向異性導電膏層之表面之黏性(利用安田精機製作所製造之滾球黏性試驗器，啟動路程：100mm，測定部：100mm，傾斜角度30°，滾球 1/16於測定部未停止程度之黏著性)消失為止的凝膠化時間進行評價。利用下述基準判定硬化速度。
[硬化速度之判定基準]
○：表面之黏性消失為止之凝膠化時間未達3秒鐘
×：表面之黏性消失為止之凝膠化時間為3秒鐘以上
(2)導通性
使用獲得之連接構造體，利用4端子法對20處之連接電阻進行評價。利用下述之基準判定導通性。
[導通性之判定基準]
○○：連接電阻之平均值為8.0Ω以下
○：連接電阻之平均值超過8.0Ω且為10.0Ω以下
△：連接電阻之平均值超過10.0Ω且為15.0Ω以下
×：連接電阻之平均值超過15.0Ω
(3)耐熱衝擊性
分別準備10個所獲得之連接構造體，將於-30℃下保持5分鐘、繼而升溫至80℃並保持5分鐘後、降溫至-30℃的過程設為1循環，每1循環設為1小時而進行冷熱循環試驗。500循環後，分別取出10個連接構造體。
針對500循環之冷熱循環試驗後之10個連接構造體，計算上下電極間發生導通不良之個數。利用下述之基準判定耐熱衝擊性。
[耐熱衝擊性之判定基準]
○○：於全部10個連接構造體中，自冷熱循環試驗前之連接電阻起之連接電阻上升率為5%以下
○：於全部10個連接構造體中，自冷熱循環試驗前之連接電阻起之連接電阻上升率超過5%且為10%以下
×：於10個連接構造體中，自冷熱循環試驗前之連接電阻起之連接電阻上升率超過10%的連接構造體為1個以上
(4)耐濕熱性
藉由偏壓試驗而對耐濕熱性進行評價。具體而言，準備於上表面具有L/S為100μm/100μm之70根梳形銅電極圖案之玻璃環氧基板(FR-4基板)。又，準備於下表面具有L/S為100μm/100μm之70根梳形銅電極圖案之軟性印刷基板。利用與(1)~(3)之評價項目所使用之連接構造體之製作方法相同的方法，獲得連接構造體。FR-4基板與軟性印刷基板之圖案係以藉由重疊而可形成梳形圖案之方式進行設計。利用下述之基準判定耐濕熱性。
[耐濕熱性之判定基準]
○○：電阻值為108Ω以上
○：電阻值為5×107Ω以上且未達108Ω
△：電阻值為107Ω以上且未達5×107Ω
×：電阻值未達107Ω
(5)保存穩定性
將各向異性導電膏於23℃下靜置48小時，使用E型黏度計TV-33(東機產業公司製造)對靜置前後之黏度變化進行測定。根據靜置前後之黏度變化，利用下述之基準判定保存穩定性。
[保存穩定性之判定基準]
○○：靜置48小時後之黏度/初期黏度未達1.2
○：靜置48小時後之黏度/初期黏度為1.2以上且未達1.5
×：靜置48小時後之黏度/初期黏度為1.5以上
(6)保存穩定性
將各向異性導電膏於40℃下靜置48小時，使用E型黏度計TV-33(東機產業公司製造)對靜置前後之黏度變化進行測定。根據靜置前後之黏度變化，利用下述之基準判定保存穩定性。
[保存穩定性之判定基準]
○○：靜置48小時後之黏度/初期黏度未達1.2
○：靜置48小時後之黏度/初期黏度為1.2以上且未達1.35
△：靜置48小時後之黏度/初期黏度為1.35以上且未達1.5
×：靜置48小時後之黏度/初期黏度為1.5以上
將結果示於下述之表1~3。
表示使用上表面具有銅電極之玻璃環氧基板(連接對象構件)與下表面具有銅電極之軟性印刷基板(連接對象構件)的連接構造體之評價結果。確認，於該等2個連接對象構件中僅一電極為銅電極而另一個為鋁電極之情形時，亦可獲得與表1~3所示之評價結果相同傾向之評價結果。再者，於該等2個連接對象構件之電極雙方為鋁電極之情形時，實施例與比較例之評價結果差異較小。即，於2個連接對象構件之電極中之至少一者為銅電極之情形時，與2個連接對象構件之電極雙方為鋁電極之情形相比，實施例與比較例之評價結果差異較大。根據上述情況，確認藉由將本發明之電子零件用硬化性組合物用於銅電極之連接，而有效發揮本發明之效果。
又，於實施例16~21中，潛伏性硬化劑為微膠囊型咪唑硬化劑，因此於相對高溫(40℃)下之保存穩定性相當優異。
1‧‧‧連接構造體
2‧‧‧第1連接對象構件
2a‧‧‧第1電極
3‧‧‧連接部
4‧‧‧第2連接對象構件
4a‧‧‧第2電極
5‧‧‧導電性粒子

Claims (11)

  1. 一種電子零件用硬化性組合物，其係用於銅電極之連接者，且包含：熱硬化性化合物、潛伏性硬化劑、及具有芳香族骨架之咪唑化合物。
  2. 如請求項1之電子零件用硬化性組合物，其中上述潛伏性硬化劑為微膠囊型咪唑硬化劑。
  3. 如請求項1之電子零件用硬化性組合物，其包含導電性粒子。
  4. 如請求項2之電子零件用硬化性組合物，其包含導電性粒子。
  5. 如請求項3之電子零件用硬化性組合物，其中上述導電性粒子係導電性之外側之表面為焊料之導電性粒子。
  6. 如請求項4之電子零件用硬化性組合物，其中上述導電性粒子係導電性之外側之表面為焊料之導電性粒子。
  7. 如請求項1至6中任一項之電子零件用硬化性組合物，其為膏。
  8. 一種連接構造體，其具備：表面具有第1電極之第1連接對象構件、表面具有第2電極之第2連接對象構件、及將上述第1連接對象構件與上述第2連接對象構件連接之連接部，且上述連接部係藉由使如請求項1至7中任一項之電子零件用硬化性組合物硬化而形成，上述第1電極及上述第2電極中之至少一者為銅電極，且上述第1電極與上述第2電極被電性連接。
  9. 如請求項8之連接構造體，其中上述電子零件用硬化性組合物包含導電性粒子，且 上述第1電極與上述第2電極由上述導電性粒子電性連接。
  10. 一種連接構造體之製造方法，其具備：於表面具有第1電極之第1連接對象構件與表面具有第2電極之第2連接對象構件之間配置如請求項1至7中任一項之電子零件用硬化性組合物的步驟，及藉由使上述電子零件用硬化性組合物硬化而形成將上述第1連接對象構件與上述第2連接對象構件連接之連接部，從而獲得將上述第1電極與上述第2電極電性連接之連接構造體的步驟，且上述第1電極及上述第2電極中之至少一者為銅電極。
  11. 如請求項10之連接構造體之製造方法，其中上述電子零件用硬化性組合物包含導電性粒子，且獲得上述第1電極與上述第2電極由上述導電性粒子電性連接之連接構造體。
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