TWI445792B - 黏著劑組成物、連接結構體、連接結構體的製造方法以及黏著劑組成物的應用 - Google Patents

黏著劑組成物、連接結構體、連接結構體的製造方法以及黏著劑組成物的應用 Download PDF

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Publication number
TWI445792B
TWI445792B TW100119007A TW100119007A TWI445792B TW I445792 B TWI445792 B TW I445792B TW 100119007 A TW100119007 A TW 100119007A TW 100119007 A TW100119007 A TW 100119007A TW I445792 B TWI445792 B TW I445792B
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Taiwan
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circuit member
group
adhesive composition
connection terminal
connection
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TW100119007A
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English (en)
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TW201204798A (en
Inventor
Hiroyuki Izawa
Shigeki Katogi
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Hitachi Chemical Co Ltd
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    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
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    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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Description

黏著劑組成物、連接結構體、連接結構體的製造方法以及黏著劑組成物的應用
本實施形態是有關於一種黏著劑組成物、連接結構體、連接結構體的製造方法以及黏著劑組成物的應用。
於半導體元件及液晶顯示元件中，為了使元件中的各種構件結合的目的，自先前以來使用各種黏著劑。對黏著劑的要求是以黏著性為代表，涉及耐熱性、高溫高濕狀態下的可靠性等。另外，用於黏著的被黏附體是印刷配線板或以聚醯亞胺(polyimide)、聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)、聚碳酸酯(polycarbonate，PC)、聚萘二甲酸乙二酯(polyethylene naphthalate，PEN)等有機基材為代表，使用銅、鋁等金屬或ITO(indium tin oxide，銦與錫的複合氧化物)、SiN、SiO2 等具有多種多樣的表面狀態的基材，必需根據各被黏附體來進行分子設計。
自先前以來，上述半導體元件或液晶顯示元件用的黏著劑是使用利用高黏著性且表現出高可靠性的環氧樹脂的熱硬化性樹脂(例如參照專利文獻1)。樹脂的構成成分通常使用環氧樹脂、與環氧樹脂具有反應性的酚樹脂等硬化劑、促進環氧樹脂與硬化劑的反應的熱潛在性觸媒。熱潛在性觸媒是在室溫等儲存溫度下不反應而在加熱時表現出高反應性的物質，成為決定硬化溫度及硬化速度的重要因素，就黏著劑的於室溫下的儲存穩定性及加熱時的硬化速 度的觀點而言，使用各種化合物。實際步驟中的硬化條件是藉由在170℃~250℃的溫度下硬化1小時~3小時，而獲得所需的黏著。
然而，最近，有在PET、PC、PEN等耐熱性低的有機基材上形成半導體元件或液晶顯示元件及配線的情況，但存在藉由硬化時的加熱而對有機基材及周邊構件造成不良影響的顧慮，因此要求更低溫硬化下的黏著。為了利用上述環氧樹脂等來達成低溫下快速硬化，必需使用活化能低的熱潛在性觸媒，但難以兼具室溫附近的儲存穩定性。
如上所述中，將丙烯酸酯衍生物或甲基丙烯酸酯衍生物等自由基聚合性化合物與作為自由基聚合起始劑的過氧化物併用的自由基硬化型黏著劑受到關注。由於作為反應活性種的自由基富有反應性，故而自由基硬化可短時間硬化(例如參照專利文獻2)。然而，自由基硬化系的黏著劑由於加熱時的硬化收縮大，故而與使用環氧樹脂的情況相比較，黏著強度差。關於如上所述的黏著強度的下降，提出有藉由應用胺基甲酸酯丙烯酸酯(urethane acrylate)而賦予可撓性，改善黏著強度的方法(例如參照專利文獻3)。另外，提出有藉由對被黏附體為ITO、SiN、SiO2 等的無機基材添加矽烷偶合劑等黏著助劑，而改善黏著強度的方法(例如參照專利文獻4)。
先前技術文獻
專利文獻
專利文獻1：日本專利特開平1-113480號公報
專利文獻2：國際公開第98/44067號小冊子
專利文獻3：日本專利第3503740號公報
專利文獻4：日本專利特開昭62-62874號公報
然而，作為熱塑性樹脂的PET、PC、PEN等有機基材為直鏈狀，另外，利用由苯環引起的分子間的相互作用而容易形成結晶部分，因此極其難以形成與黏著劑組成物或矽烷偶合劑的共價鍵。因此，上述專利文獻4中記載的方法中，未獲得充分的黏著強度。另外，由於PET、PC、PEN等的表面平滑，故而由物理性錨固效果(增黏效果)引起的黏著效果小。因此，必需應用獲得對被黏附體的潤濕性或充分可撓性的黏著劑組成物，但上述專利文獻3所記載的方法中，未獲得對被黏附體的充分潤濕性或可撓性。
因此，本發明的目的在於提供一種對於聚對苯二甲酸乙二酯、聚碳酸酯、聚萘二甲酸乙二酯等有機基材，即便於低溫的硬化條件下亦可獲得優異的黏著強度且於長時間的可靠性試驗(高溫高濕試驗)後亦可維持穩定的性能(黏著強度或連接電阻)的黏著劑組成物，使用該黏著劑組成物的電路構件的連接結構體、連接結構體的製造方法以及黏著劑組成物的應用。
為了達成上述目的，本發明提供一種黏著劑組成物，用於將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件連接，上述第一電路構件及/或上述第二電路構件是由包含玻璃轉移溫度為 200℃以下的熱塑性樹脂的基材所構成，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且上述(b)自由基聚合性化合物包含具有25mN/m~40mN/m的臨界表面張力的胺基甲酸酯(甲基)丙烯酸酯(urethane(meth)acrylate)。
上述黏著劑組成物藉由含有包含具有25mN/m~40mN/m的臨界表面張力的胺基甲酸酯(甲基)丙烯酸酯的(b)自由基聚合性化合物，與包含Tg為200℃以下的熱塑性樹脂的基材(例如PET、PC、PEN等)的潤濕性提高，可進行低溫硬化下的黏著，可提高電路構件間的黏著強度。另外，即便於長時間的可靠性試驗後亦可維持穩定的性能。
另外，本發明的黏著劑組成物中，(b)自由基聚合性化合物中所含的胺基甲酸酯(甲基)丙烯酸酯較佳為下述通式(A)所表示的化合物。
[式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯(ε-caprolactone)的開環化合物所衍生的基團、或者下述通式(B)所表示的基團，R4 表示下述通式(B)所表示的基團，R5 表示飽和脂肪族基或者飽和脂環基，a表示1~40的整數。]
[化2]
[式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同。]
臨界表面張力與凝集能量密度之間存在比例關係，因此考慮藉由導入凝集能量密度高的官能基而提高臨界表面張力。因此，藉由(b)自由基聚合性化合物中所含的胺基甲酸酯(甲基)丙烯酸酯為上述通式(A)所表示的結構，凝集能量密度提高，與包含黏著劑組成物及Tg為200℃以下的熱塑性樹脂的基材(例如PET、PC、PEN等)的潤濕性提高，由包含PET或PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著強度提高，可獲得優異的連接可靠性。另外，藉由(b)自由基聚合性化合物中所含的胺基甲酸酯(甲基)丙烯酸酯為上述通式(A)所表示的結構，而對黏著劑組成物賦予適度的可撓性，由包含PET或PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著強度提高，可獲得優異的連接可靠性。
另外，本發明提供一種黏著劑組成物，用於將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件連接，上述第一電路構件及/或上述第二電路構件是由包含玻璃轉移溫度為200℃以下的熱塑 性樹脂的基材所構成，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且上述(b)自由基聚合性化合物包含下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯。
[式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯的開環化合物所衍生的基團、或者下述通式(B)所表示的基團，R4 表示下述通式(B)所表示的基團，R5 表示飽和脂肪族基或者飽和脂環基，a表示1~40的整數。]
[式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同。]
藉由(b)自由基聚合性化合物中所含的胺基甲酸酯(甲 基)丙烯酸酯為上述通式(A)所表示的結構，本黏著劑組成物的凝集能量密度提高，與包含黏著劑組成物及Tg為200℃以下的熱塑性樹脂的基材(例如PET、PC、PEN等)的潤濕性提高，由包含PET或PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著強度提高，可獲得優異的連接可靠性。另外，藉由(b)自由基聚合性化合物中所含的胺基甲酸酯(甲基)丙烯酸酯為上述通式(A)所表示的結構，而對黏著劑組成物賦予適度的可撓性，由包含PET或PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著強度提高，可獲得優異的連接可靠性。進而，即便於長時間的可靠性試驗後亦可維持穩定的性能。
本發明的黏著劑組成物中較佳為，胺基甲酸酯(甲基)丙烯酸酯為使用脂肪族聚酯二醇而獲得的化合物。藉由胺基甲酸酯(甲基)丙烯酸酯為使用脂肪族聚酯二醇而獲得的化合物，黏著劑組成物的可撓性提高，由包含PET或PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著強度提高，可獲得優異的連接可靠性。
另外，本發明的黏著劑組成物中較佳為，胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量為8000以上且小於25000。藉由胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量在上述範圍內，與PET、PC、PEN等有機基材的黏著強度進一步提高，可獲得優異的連接可靠性。
另外，本發明的黏著劑組成物中較佳為，(b)自由基聚合性化合物含有1種以上的具有磷酸基的乙烯基化合 物、及1種以上的具有磷酸基的乙烯基化合物以外的自由基聚合性化合物。藉由(b)自由基聚合性化合物具備如上所述的構成，尤其與包含金屬的基材的黏著強度進一步提高。
另外，本發明的黏著劑組成物中較佳為，(a)熱塑性樹脂含有選自由苯氧基(phenoxy)樹脂、聚胺基甲酸酯(polyurethane)樹脂、聚酯胺基甲酸酯(polyester urethane)樹脂、丁醛(butyral)樹脂、丙烯酸樹脂及聚醯亞胺樹脂所組成組群中的至少1種。藉由含有如上所述的樹脂作為(a)熱塑性樹脂，黏著劑組成物的耐熱性、黏著性進一步提高。
另外，本發明的黏著劑組成物中亦較佳為更含有(d)導電性粒子。藉由含有(d)導電性粒子，可對黏著劑組成物賦予良好的導電性或者異向導電性，因此可更適合用於具有連接端子的電路構件彼此的黏著用途等。另外，可更充分降低經由上述黏著劑組成物而電性連接的電路構件的連接電阻。
另外，本發明提供一種電路構件的連接結構體，包括主面上具有第一連接端子的第一電路構件、主面上具有第二連接端子的第二電路構件、及連接構件，並且以使第一連接端子及第二連接端子對向的方式配置上述第一電路構件及上述第二電路構件，其中包含上述黏著劑組成物的連接構件介於上述第一電路構件與上述第二電路構件之間，而且第一連接端子及第二連接端子為電性連接，上述第一 電路構件及/或上述第二電路構件是由含有玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成。
藉由第一電路構件及/或第二電路構件為由含有玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成的電路構件，與黏著劑組成物的潤濕性提高，黏著強度進一步提高，可獲得優異的連接可靠性。
上述玻璃轉移溫度為200℃以下的熱塑性樹脂較佳為選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種。藉由上述電路構件為由含有聚對苯二甲酸乙二酯等的基材所構成的電路構件，與黏著劑組成物的潤濕性提高，黏著強度進一步提高，可獲得優異的連接可靠性。
另外，本發明的電路構件的連接結構體中較佳為，第一電路構件或者第二電路構件中的一方的電路構件是由含有選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種的基材所構成，且第一電路構件或者第二電路構件中的另一方的電路構件是由含有選自由聚醯亞胺樹脂及聚對苯二甲酸乙二酯所組成組群中的至少1種的基材所構成。藉由第一電路構件與第二電路構件由如上所述的基材所構成，本連接結構體的與黏著劑組成物的潤濕性及黏著強度進一步提高，可獲得優異的連接可靠性。
本發明提供一種電路構件的連接結構體的製造方法，包括以下步驟：將主面上具有第一連接端子的第一電路構 件、與主面上具有第二連接端子的第二電路構件，以使第一連接端子及第二連接端子對向的方式配置，其中介於上述第一電路構件與上述第二電路構件之間上述黏著劑組成物；以及將黏著劑組成物加熱，使其硬化而將第一電路構件與第二電路構件連接。依據本製造方法，藉由將第一電路構件與第二電路構件以上述黏著劑組成物來連接，可獲得具有優異的連接可靠性的電路構件的連接結構體。
另外，本發明提供一種作為黏著劑組成物的應用，用於將第一電路構件與第二電路構件連接，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且上述(b)自由基聚合性化合物包含具有25mN/m~40mN/m的臨界表面張力的胺基甲酸酯(甲基)丙烯酸酯，上述第一電路構件於主面上具有第一連接端子，上述第二電路構件於主面上具有第二連接端子，且至少一方的電路構件是由包含玻璃轉移溫度200℃以下的熱塑性樹脂的基材所構成。含有包含具有25mN/m~40mN/m的臨界表面張力的胺基甲酸酯(甲基)丙烯酸酯的(b)自由基聚合性化合物的本黏著劑組成物由於與包含Tg為200℃以下的熱塑性樹脂的基材(例如PET、PC、PEN等)的潤濕性提高，可進行於低溫硬化下的黏著，故而適宜作為用於連接電路構件的黏著劑組成物來應用。
上述應用中較佳為，胺基甲酸酯(甲基)丙烯酸酯為下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯。藉由胺基甲酸酯(甲基)丙烯酸酯為下述通式(A)所表示的結構， 電路構件間的黏著強度提高，可獲得優異的連接可靠性。
[式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯的開環化合物所衍生的基團、或者下述通式(B)所表示的基團，R4 表示下述通式(B)所表示的基團，R5 表示飽和脂肪族基或者飽和脂環基，a表示1~40的整數。]
[式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同。]
另外，本發明提供一種作為黏著劑組成物的應用，用於將第一電路構件與第二電路構件連接，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且上述(b)自由基聚合性化合物包含 下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯，上述第一電路構件於主面上具有第一連接端子，上述第二電路構件於主面上具有第二連接端子，且至少一方的電路構件是由包含玻璃轉移溫度200℃以下的熱塑性樹脂的基材所構成。藉由胺基甲酸酯(甲基)丙烯酸酯為下述通式(A)所表示的結構，電路構件間的黏著強度提高，可獲得優異的連接可靠性。
[式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯的開環化合物所衍生的基團、或者下述通式(B)所表示的基團，R4 表示下述通式(B)所表示的基團，R5 表示飽和脂肪族基或者飽和脂環基，a表示1~40的整數。]
[式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1 ~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同。]
上述應用中較佳為，胺基甲酸酯(甲基)丙烯酸酯為使用脂肪族聚酯二醇而獲得的化合物。藉由胺基甲酸酯(甲基)丙烯酸酯為使用脂肪族聚酯二醇而獲得的化合物，黏著劑組成物的可撓性提高，由包含PET或PC、PEN等熱塑性樹脂的基材所構成的電路構件間的黏著強度提高，可獲得優異的連接可靠性。
上述應用中較佳為，胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量為8000以上且小於25000。藉由胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量在上述範圍內，與PET、PC、PEN等有機基材的黏著強度進一步提高，可獲得優異的連接可靠性。
上述應用中較佳為，(b)自由基聚合性化合物含有1種以上的具有磷酸基的乙烯基化合物、及1種以上的具有磷酸基的乙烯基化合物以外的自由基聚合性化合物。藉由(b)自由基聚合性化合物具備如上所述的構成，尤其與包含金屬的基材的黏著強度進一步提高。
上述應用中較佳為，(a)熱塑性樹脂含有選自由苯氧基樹脂、聚胺基甲酸酯樹脂、聚酯胺基甲酸酯樹脂、丁醛樹脂、丙烯酸樹脂及聚醯亞胺樹脂所組成組群中的至少1種。藉由含有如上所述的樹脂作為(a)熱塑性樹脂，耐熱性、黏著性進一步提高。
上述應用中較佳為，黏著劑組成物更含有(d)導電性 粒子。藉由含有(d)導電性粒子，可對黏著劑組成物賦予良好的導電性或者異向導電性，另外，可更充分地降低電性連接的電路構件的連接電阻。
依據本發明，可提供一種對於聚對苯二甲酸乙二酯、聚碳酸酯、聚萘二甲酸乙二酯等有機基材，即便於低溫的硬化條件下亦可獲得優異的黏著強度，且即便於長時間的可靠性試驗(高溫高濕試驗)後亦可維持穩定的性能(黏著強度或連接電阻)的黏著劑組成物，使用該黏著劑組成物的電路構件的連接結構體，電路構件的連接結構體的製造方法以及黏著劑組成物的應用。
以下，根據情況，一邊參照圖式一邊對本發明的較佳實施形態進行詳細說明。此外，圖式中，對同一或者相當部分標註同一符號，省略重複的說明。另外，本實施形態中，所謂(甲基)丙烯酸是表示丙烯酸或者與其對應的甲基丙烯酸，所謂(甲基)丙烯酸酯是表示丙烯酸酯或者與其對應的甲基丙烯酸酯，所謂(甲基)丙烯醯基是表示丙烯醯基或者甲基丙烯醯基。
本實施形態中的所謂「玻璃轉移溫度(Tg)」，是指使用TA Instruments公司製造的黏彈性分析儀「RSA-3」(商品名)，於升溫速度5℃/min、頻率10Hz、測定溫度-150℃~300℃的條件下，對膜狀的有機基材測定而得的Tg附近的tanδ峰值溫度的值。
另外，本實施形態中的所謂「臨界表面張力(γc )」，是指實際測量剛對製成膜狀的胺基甲酸酯(甲基)丙烯酸酯分別在23℃下滴加1μl的純水、潤濕張力試驗用混合溶液No.50、60(和光純藥工業(股)製造)之後的與胺基甲酸酯(甲基)丙烯酸酯表面所形成的角(接觸角θ)，以各液體的表面張力為x軸且以COSθ為y軸而製圖時，通過3點的直線成為Y=1時的表面張力。此外，關於當通過上述純水、No.50、60的測定所得的3點的直線為Y=1時X成為負值的情況，亦可使用純水、潤濕張力試驗用混合溶液No.60、1-溴萘(和光純藥工業(股)製造)來進行與上述相同的測定，使用通過所得的3點的直線成為Y=1時的表面張力的值。
另外，本實施形態中，所謂「重量平均分子量」及「數量平均分子量」，是指依據表1所示的條件，藉由凝膠滲透層析法(gel permeation chromatograph，GPC)，使用標準聚苯乙烯的校正曲線進行測定而得的值。
本實施形態的黏著劑組成物是用於將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件連接的黏著劑組成物，第一電路構件及/或第二電路構件是由包含玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且(b)自由基聚合性化合物包含具有25mN/m~40mN/m的臨界表面張力的胺基甲酸酯(甲基)丙烯酸酯。
本實施形態的黏著劑組成物中所含有的(a)熱塑性樹脂是指具有如下性質的樹脂(高分子)：藉由加熱而成為黏度高的液狀狀態，利用外力而自由變形，若加以冷卻並去除外力，則於保持其形狀的狀態下變硬，將該過程重複進行。另外，亦包括包含具有上述性質的反應性官能基的樹脂(高分子)。(a)熱塑性樹脂的Tg較佳為0℃~190℃，更佳為20℃~170℃。
如上所述的熱塑性樹脂可使用：聚醯亞胺樹脂、聚醯胺(polyamide)樹脂、苯氧基樹脂、(甲基)丙烯酸樹脂、胺基甲酸酯樹脂、聚酯胺基甲酸酯樹脂、聚乙烯基丁醛(polyvinylbutyral)樹脂等。該些樹脂可單獨使用或者將2種以上混合使用。進而，該些熱塑性樹脂中亦可包含矽氧烷(siloxane)鍵或氟取代基。該些樹脂若為所混合的樹脂彼此完全相溶，或者產生微相分離而白濁的狀態，則可適宜使用。
於將黏著劑組成物製成膜狀而利用的情況，上述熱塑 性樹脂的分子量越大，越容易獲得良好的膜形成性，另外可將對作為膜狀黏著劑組成物的流動性產生影響的熔融黏度設定於較廣範圍。(a)熱塑性樹脂的重量平均分子量較佳為5000~150000，更佳為10000~80000。若該值小於5000，則存在難以獲得良好的膜形成性的傾向，若超過150000，則存在難以獲得與其他成分的良好相溶性的傾向。
本實施形態的黏著劑組成物中，以黏著劑組成物總量為基準，(a)熱塑性樹脂的含量較佳為5質量%~80質量%，更佳為15質量%~70質量%。若該含量小於5質量%，則於將黏著劑組成物製成膜狀而利用的情況，尤其存在難以獲得良好的膜形成性的傾向，若超過80質量%，則存在難以獲得良好的黏著劑組成物的流動性的傾向。
本實施形態的黏著劑組成物中所含有的(b)自由基聚合性化合物是指藉由自由基聚合起始劑的作用而產生自由基聚合的化合物，亦可為藉由賦予光或熱等活化能而使其自身產生自由基的化合物。(b)自由基聚合性化合物例如可適宜使用具有藉由乙烯基、(甲基)丙烯醯基、烯丙基、順丁烯二醯亞胺基等活性自由基而聚合的官能基的化合物。
(b)自由基聚合性化合物具體而言可列舉：環氧(甲基)丙烯酸酯(epoxy(meth)acrylate)寡聚物、胺基甲酸酯(甲基)丙烯酸酯寡聚物、聚醚(甲基)丙烯酸酯(polyether(meth)acrylate)寡聚物、聚酯(甲基)丙烯酸酯(polyester(meth)acrylate)寡聚物等寡聚物；三羥甲基丙烷三(甲基) 丙烯酸酯(trimethylolpropane tri(meth)acrylate)、聚乙二醇二(甲基)丙烯酸酯(polyethylene glycol di(meth)acrylate)、聚伸烷基二醇二(甲基)丙烯酸酯(polyalkylene glycol di(meth)acrylate)、(甲基)丙烯酸二環戊烯酯(dicyclopentenyl(meth)acrylate)、(甲基)丙烯酸二環戊烯氧基乙酯(dicyclopentenyloxy ethyl(meth)acrylate)、新戊二醇二(甲基)丙烯酸酯(neopentyl glycol di(meth)acrylate)、二季戊四醇六(甲基)丙烯酸酯(dipentaerythritol hexa(meth)acrylate)、異三聚氰酸(isocyanuric acid)改質2官能(甲基)丙烯酸酯、異三聚氰酸改質3官能(甲基)丙烯酸酯、雙苯氧基乙醇茀丙烯酸酯(bisphenoxyethanol fluorene acrylate)、使(甲基)丙烯酸加成於雙酚茀二縮水甘油醚(bisphenol fluorene diglycidyl ether)的縮水甘油基上而成的環氧(甲基)丙烯酸酯、雙苯氧基乙醇茀丙烯酸酯、使(甲基)丙烯酸加成於雙酚茀二縮水甘油醚的縮水甘油基上而成的環氧(甲基)丙烯酸酯、於使乙二醇或丙二醇加成於雙酚茀二縮水甘油醚的縮水甘油基上而成的化合物中導入有(甲基)丙烯醯基氧基的化合物、下述通式(C)及通式(D)所表示的化合物等。
[式(C)中，R8 及R9 分別獨立地表示氫原子或者甲基，d及e分別獨立地表示1~8的整數。]
[式(D)中，R10 及R11 分別獨立地表示氫原子或者甲基，f及g分別獨立地表示0~8的整數。]
另外，(b)自由基聚合性化合物即便是於單獨在30℃下靜置的情況為蠟(wax)狀、蠟狀、結晶狀、玻璃狀、粉狀等的無流動性且表現出固體狀態的化合物，亦可無特別限制地使用。如上所述的(b)自由基聚合性化合物具體而言可列舉：N,N'-亞甲基雙丙烯醯胺(N,N'-methylene bisacrylamide)、二丙酮丙烯醯胺(diacetone acrylamide)、N-羥甲基丙烯醯胺、N-苯基甲基丙烯醯胺、2-丙烯醯胺-2-甲基丙磺酸、異三聚氰酸三(2-丙烯醯基氧基乙基)酯、N-苯基順丁烯二醯亞胺(N-phenyl maleimide)、N-(鄰甲基苯基)順丁烯二醯亞胺、N-(間甲基苯基)順丁烯二醯亞胺、N-(對甲基苯基)-順丁烯二醯亞胺、N-(鄰甲氧基苯基)順丁烯二醯亞胺、N-(間甲氧基苯基)順丁烯二醯亞胺、N-(對甲氧基苯基)-順丁烯二醯亞胺、N-甲基順丁烯二醯亞胺、N- 乙基順丁烯二醯亞胺、N-辛基順丁烯二醯亞胺、4,4'-二苯基甲烷雙順丁烯二醯亞胺、間伸苯基雙順丁烯二醯亞胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷雙順丁烯二醯亞胺、4-甲基-1,3-伸苯基雙順丁烯二醯亞胺、N-甲基丙烯醯氧基順丁烯二醯亞胺、N-丙烯醯氧基順丁烯二醯亞胺、1,6-雙順丁烯二醯亞胺-(2,2,4-三甲基)己烷、N-甲基丙烯醯基氧基丁二酸醯亞胺、N-丙烯醯基氧基丁二酸醯亞胺、甲基丙烯酸2-萘基酯、丙烯酸2-萘基酯、季戊四醇四丙烯酸酯、二乙烯基伸乙基尿素、二乙烯基伸丙基尿素、甲基丙烯酸2-聚苯乙烯基乙酯、N-苯基-N'-(3-甲基丙烯醯基氧基-2-羥基丙基)-對苯二胺、N-苯基-N'-(3-丙烯醯基氧基-2-羥基丙基)-對苯二胺、甲基丙烯酸四甲基哌啶基酯、丙烯酸四甲基哌啶基酯、甲基丙烯酸五甲基哌啶基酯、丙烯酸五甲基哌啶基酯、丙烯酸十八烷基酯、N-第三丁基丙烯醯胺、二丙酮丙烯醯胺、N-(羥基甲基)丙烯醯胺、下述通式(E)~通式(N)所表示的化合物等。
[式(E)中，h表示1~10的整數。]
[化12]
[式(G)中，R12 及R13 分別獨立地表示氫原子或者甲基，i表示15~30的整數。]
[式(H)中，R14 及R15 分別獨立地表示氫原子或者甲基，j表示15~30的整數。]
[化15]
[式(I)中，R16 表示氫原子或者甲基。]
[式(J)中，R17 表示氫原子或者甲基，k表示1~10的整數。]
[式(K)中，R18 表示氫原子或者下述通式(i)或通式(ii)所表示的有機基，l表示1~10的整數。]
[式(L)中，R19 表示氫原子或者下述通式(iii)或通式(iv)所表示的有機基，m表示1~10的整數。]
[式(M)中，R20 表示氫原子或者甲基。]
[式(N)中，R21 表示氫原子或者甲基。]
另外，可將屬於(b)自由基聚合性化合物的化合物即含磷酸基的乙烯基化合物、或選自由N-乙烯基化合物及N,N-二烷基乙烯基化合物所組成組群中的N-乙烯基系化合物，與該些化合物以外的(b)自由基聚合性化合物併用。藉由併用含磷酸基的乙烯基化合物，可提高黏著劑組成物對金屬基材的黏著性。另外，藉由併用N-乙烯基系化合物，可提高黏著劑組成物的交聯率。
含磷酸基的乙烯基化合物若為具有磷酸基及乙烯基的化合物，則並無特別限制，較佳為下述通式(O)~通式(Q)所表示的化合物。
[式(O)中，R22 表示(甲基)丙烯醯基氧基，R23 表示氫原子或者甲基，n及o分別獨立地表示1~8的整數；此外，式中，R22 彼此、R23 彼此、n彼此以及o彼此分別可相同，亦可不同。]
[式(P)中，R24 表示(甲基)丙烯醯基氧基，p及q分別獨立地表示1~8的整數；此外，式中，R24 彼此、p彼此以及q彼此分別可相同，亦可不同。]
[化27]
[式(Q)中，R25 表示(甲基)丙烯醯基氧基，R26 表示氫原子或者甲基，r及s分別獨立地表示1~8的整數；此外，式中，R26 彼此以及r彼此分別可相同，亦可不同。]
含磷酸基的乙烯基化合物具體而言可列舉：甲基丙烯酸酸式磷氧基乙酯(acid phosphoxy ethyl methacrylate)、丙烯酸酸式磷氧基乙酯、甲基丙烯酸酸式磷氧基丙酯、酸式磷氧基聚氧乙二醇單甲基丙烯酸酯、酸式磷氧基聚氧丙二醇單甲基丙烯酸酯、磷酸2,2'-二(甲基)丙烯醯氧基二乙酯、環氧乙烷(ethylene oxide，EO)改質磷酸二甲基丙烯酸酯、磷酸改質環氧丙烯酸酯、磷酸乙烯基酯等。
含磷酸基的乙烯基化合物的調配量較佳為與含磷酸基的乙烯基化合物以外的(b)自由基聚合性化合物的調配量獨立地相對於(a)熱塑性樹脂100質量份，設為0.2質量份~300質量份，更佳為設為1質量份~200質量份，尤佳為設為1質量份~50質量份，特佳為設為1質量份~15質量份。若將含磷酸基的乙烯基化合物的調配量設為小於0.2質量份，則存在難以獲得高黏著強度的傾向，若超過300質量份，則存在硬化後的黏著劑組成物的物性容易下降，變得難以確保可靠性的傾向。
另一方面，N-乙烯基系化合物具體而言可列舉：N-乙 烯基咪唑(N-vinyl imidazole)、N-乙烯基吡啶(N-vinyl pyridine)、N-乙烯基吡咯啶酮(N-vinyl pyrrolidone)、N-乙烯基甲醯胺(N-vinyl formamide)、N-乙烯基己內醯胺(N-vinyl caprolactam)、4,4'-亞乙烯基雙(N,N-二甲基苯胺)(4,4'-vinylidene bis(N,N-dimethyl aniline))、N-乙烯基乙醯胺(N-vinyl acetamide)、N,N-二甲基丙烯醯胺(N,N-dimethyl acrylamide)、N,N-二乙基丙烯醯胺(N,N-diethyl acrylamide)等。
相對於(a)熱塑性樹脂100質量份，除上述符合含磷酸基的乙烯基化合物的化合物以外的(b)自由基聚合性化合物的調配量較佳為50質量份~250質量份，更佳為60質量份~150質量份。若上述調配量小於50質量份，則存在硬化後難以獲得充分的耐熱性的傾向，另外，若超過250質量份，則於作為膜來使用的情況，存在難以獲得良好的膜形成性的傾向。
作為必需成分，本實施形態的黏著劑組成物含有滿足臨界表面張力為25mN/m~40mN/m的胺基甲酸酯(甲基)丙烯酸酯、及下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯中的一種或兩種條件的胺基甲酸酯(甲基)丙烯酸酯作為(b)自由基聚合性化合物。其中，本實施形態中，更適宜使用滿足上述條件的胺基甲酸酯丙烯酸酯。此處，下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯可藉由脂肪族系二異氰酸酯及聚酯二醇的縮合反應而獲得。
[化28]
[式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯的開環化合物所衍生的基團、或者下述通式(B)所表示的基團，R4 表示下述通式(B)所表示的基團，R5 表示飽和脂肪族基或者飽和脂環基，a表示1~40的整數。]
[式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同。]
構成上述胺基甲酸酯(甲基)丙烯酸酯的脂肪族系二異氰酸酯是選自以下化合物中：四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、離胺酸二異氰酸酯、2-甲基戊烷-1,5-二異氰酸酯、3-甲基戊烷-1,5-二異氰酸酯、2,2,4-三甲基六亞甲基-1,6-二異氰酸酯、2,4,4-三甲基六亞甲基-1,6-二異氰酸酯、異佛爾酮二異氰酸酯、二異氰酸環己酯、氫化苯二甲 基二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化三甲基苯二甲基二異氰酸酯等。
另外，構成上述胺基甲酸酯(甲基)丙烯酸酯的聚酯二醇例如可使用脂肪族系聚酯二醇或芳香族系聚酯二醇，較佳為使用脂肪族系聚酯二醇。脂肪族系聚酯二醇是選自以下化合物中：乙二醇、丙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、1,2-戊二醇、1,4-戊二醇、1,5-戊二醇、2,4-戊二醇、2-甲基-2,4-戊二醇、2,4-二甲基-2,4-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,2-己二醇、1,5-己二醇、1,6-己二醇、2,5-己二醇、2-乙基-1,3-己二醇、2,5-二甲基-2,5-己二醇、1,2-辛二醇、1,8-辛二醇、1,7-庚二醇、1,9-壬二醇、1,2-癸二醇、1,10-癸二醇、1,12-癸二醇、十二烷二醇、頻哪醇(pinacol)、1,4-丁炔二醇、三乙二醇、二乙二醇、二丙二醇、環己烷二甲醇等飽和的低分子二醇類；藉由至少1種以上的上述二醇類與光氣的反應而獲得的聚碳酸酯二醇類；藉由以至少1種以上的上述二醇類作為起始劑，利用公知的方法將環氧乙烷、環氧丙烷、表氯醇(epichlorohydrin)等單體的1種或者其以上進行加成聚合而獲得的聚醚二醇等二醇類；使己二酸、3-甲基己二酸、2,2,5,5-四甲基己二酸、順丁烯二酸、反丁烯二酸、丁二酸、2,2-二甲基丁二酸、2-乙基-2-甲基丁二酸、2,3-二甲基丁二酸、乙二酸、丙二酸、甲基丙二酸、乙基丙二酸、丁基丙二酸、二甲基丙二酸、戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、2,4-二甲基 戊二酸、庚二酸、辛二酸、壬二酸、癸二酸等二元酸或者與該些二元酸對應的酸酐進行脫水縮合而獲得的脂肪族系聚酯二醇類；或將ε-己內酯等環狀酯化合物進行開環聚合而獲得的脂肪族系聚酯系二醇類。上述二醇類及由二羧酸所獲得的聚酯二醇類除了單獨使用以外，亦可將2種以上的聚酯二醇類混合使用。
另外，本實施形態的黏著劑組成物中，就對PET、PC、PEN等基材的黏著強度提高的觀點而言，上述胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量可在8000以上且小於25000的範圍內自由調整而適當使用。若上述胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量在上述範圍內，則可獲得柔軟性及凝集力兩者，與PET、PC、PEN等有機基材的黏著強度提高，可獲得優異的連接可靠性。另外，就更充分地獲得上述效果的觀點而言，上述胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量更佳為10000以上且小於25000。此外，於該重量平均分子量小於8000的情況，存在無法獲得充分的可撓性的傾向，若為25000以上，則存在黏著劑組成物的流動性下降的傾向。
上述胺基甲酸酯(甲基)丙烯酸酯的臨界表面張力較佳為25mN/m~40mN/m，更佳為25mN/m~35mN/m。於胺基甲酸酯(甲基)丙烯酸酯的臨界表面張力為25mN/m~40mN/m的情況，與作為被黏附體的PET、PC、PEN的臨界表面張力接近，潤濕性提高，藉此黏著強度提高，可獲得優異的連接可靠性。另外，若該臨界表面張力小於25 mN/m或者超過40mN/m，則存在對PET、PC、PEN等的潤濕性的降低或相容性惡化的顧慮。一般認為，上述胺基甲酸酯(甲基)丙烯酸酯的臨界表面張力與胺基甲酸酯鍵當量有關，可藉由改變二醇的數量平均分子量來調整。例如，若增大二醇的數量平均分子量，則存在胺基甲酸酯鍵當量減少，臨界表面張力降低的傾向。
另外，以黏著劑組成物總量為基準，上述胺基甲酸酯(甲基)丙烯酸酯的調配量較佳為5質量%~95質量%，更佳為10質量%~80質量%。於調配量小於5質量%的情況，存在耐熱性容易降低的傾向，若超過95質量%，則存在當作為膜來使用時膜形成性容易降低的傾向。
本實施形態的黏著劑組成物中所含有的(c)自由基聚合起始劑可使用自先前以來已知的有機過氧化物或偶氮化合物等藉由賦予來自外部的能量而產生自由基的化合物。就穩定性、反應性、相溶性的觀點而言，(c)自由基聚合起始劑較佳為1分鐘半衰期溫度為90℃~175℃，且分子量為180~1,000的有機過氧化物。藉由1分鐘半衰期溫度在該範圍內，儲存穩定性優異，自由基聚合性亦充分高，可以短時間硬化。
(c)自由基聚合起始劑具體而言可列舉：過氧化新癸酸1,1,3,3-四甲基丁酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二(2-乙基己基)酯、過氧化新癸酸異丙苯基酯、過氧化新癸酸1,1,3,3-四甲基丁酯、二月桂醯基過氧化物、過氧化新癸酸1-環己基-1-甲基乙酯、過氧化新 癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三丁酯、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、2,5-二甲基-2，5-二(2-乙基己醯基過氧化)己烷、過氧化-2-乙基己酸第三己酯、過氧化-2-乙基己酸第三丁酯、過氧化新庚酸第三丁酯、過氧化-2-乙基己酸第三戊酯、過氧化六氫對苯二甲酸二-第三丁酯、過氧化-3,5,5-三甲基己酸第三戊酯、過氧化新癸酸3-羥基-1,1-二甲基丁酯、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、過氧化新癸酸第三戊酯、過氧化-2-乙基己酸第三戊酯、二(3-甲基苯甲醯基)過氧化物、二苯甲醯基過氧化物、二(4-甲基苯甲醯基)過氧化物、過氧化異丙基單碳酸第三己酯、第三丁基過氧化順丁烯二酸、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、2,5-二甲基-2,5-二(3-甲基苯甲醯基過氧化)己烷、過氧化-2-乙基己基單碳酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-二(苯甲醯基過氧化)己烷、過氧化苯甲酸第三丁酯、過氧化三甲基己二酸二丁酯、過氧化正辛酸第三戊酯、過氧化異壬酸第三戊酯、過氧化苯甲酸第三戊酯等有機過氧化物；2,2'-偶氮雙-2,4-二甲基戊腈、1,1'-偶氮雙(1-乙醯氧基-1-苯基乙烷)、2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、二甲基-2,2'-偶氮雙異丁腈、4,4'-偶氮雙(4-氰基戊酸)、1,1'-偶氮雙(1-環己烷甲腈)等偶氮化合物等。
該些化合物除了單獨使用以外，亦可將2種以上的化合物混合使用。
另外，(c)自由基聚合起始劑可使用藉由150nm~750 nm的光照射而產生自由基的化合物。作為如上所述的化合物，例如Photoinitiation,Photopolymerization and Photocuring,J.-P.Fouassier,Hanser Publishers(1995年，p17~p35)中記載的α-乙醯胺基苯酮(α-acetaminophenone)衍生物或膦氧化物衍生物對光照射的感度高，故而更佳。
該些化合物除了單獨使用以外，亦可與上述有機過氧化物或偶氮化合物混合使用。
相對於(a)熱塑性樹脂100質量份，上述(c)自由基聚合起始劑的調配量較佳為0.1質量份~500質量份，更佳為1質量份~300質量份，尤佳為5質量份~50質量份，特佳為10質量份~30質量份。若(c)自由基聚合起始劑的調配量小於0.1質量份，則存在黏著劑組成物變得難以充分硬化的傾向，若超過500質量份，則存在儲存穩定性惡化的傾向。
本實施形態的黏著劑組成物中所含有的(d)導電性粒子若為於其整體或者表面具有導電性的粒子即可，但於用於具有連接端子的電路構件的連接的情況，較佳為平均粒徑小於連接端子間距離。
(d)導電性粒子可列舉Au、Ag、Ni、Cu、焊料等金屬粒子或碳等。另外，亦可為以非導電性的玻璃、陶瓷、塑膠等為核，且於該核上包覆有上述金屬、金屬粒子或碳的導電性粒子。於(d)導電性粒子為以塑膠為核且於該核上包覆有上述金屬、金屬粒子或碳的導電性粒子或熱熔融金屬粒子的情況，由於藉由加熱加壓而具有變形性，因此 連接時與電極的接觸面積增加，可靠性提高，因此較佳。
另外，將該些(d)導電性粒子的表面進而以高分子樹脂等包覆的微粒子抑制於增加導電性粒子的調配量時的由粒子彼此的接觸引起的短路，可提高電極電路間的絕緣性，因此亦可適宜將其單獨或者與(d)導電性粒子混合使用。
就分散性、導電性的方面而言，該(d)導電性粒子的平均粒徑較佳為1μm~18μm。於含有如上所述的(d)導電性粒子的情況，黏著劑組成物可適宜作為異向導電性黏著劑來使用。
(d)導電性粒子的使用量不受特別限制，但相對於黏著劑組成物總體積，較佳為設為0.1體積百分比(vol%)~30vol%，更佳為設為0.1vol%~10vol%。若該值小於0.1vol%，則存在導電性變低的傾向，若超過30vol%，則存在變得容易產生電路的短路的傾向。此外，體積百分比是基於23℃的硬化前的各成分的體積而決定，各成分的體積可利用比重，由重量換算為體積。另外，亦可將向在量筒等中加入有不使該成分溶解或膨潤而使該成分充分潤濕的適當溶劑(水、醇等)者中投入該成分而增加的體積作為該成分的體積來求出。
另外，本實施形態的黏著劑組成物中，為了控制硬化速度或賦予儲存穩定性，可添加穩定劑。如上所述的穩定劑並無特別限制，可使用公知的化合物，較佳為苯醌(benzoquinone)或對苯二酚(hydroquinone)等醌衍生物； 4-甲氧基苯酚(4-methoxy phenol)或4-第三丁基鄰苯二酚(4-t-butyl catechol)等酚衍生物；2,2,6,6-四甲基哌啶-1-氧(2,2,6,6-tetramethyl piperidine-1-oxyl)或4-羥基-2,2,6,6-四甲基哌啶-1-氧等胺基氧(aminoxyl)衍生物；甲基丙烯酸四甲基哌啶基酯等受阻胺衍生物等。
相對於黏著劑組成物100質量份，穩定劑的調配量較佳為0.01質量份~30質量份，更佳為0.05質量份~10質量份。於調配量小於0.01質量份的情況，變得難以控制硬化速度或賦予儲存穩定性，於超過30質量份的情況，變得容易對與其他成分的相溶性造成不良影響。
另外，本實施形態的黏著劑組成物中，可適宜添加烷氧基矽烷(alkoxysilane)衍生物或矽氮烷(silazane)衍生物所代表的偶合劑、密著提高劑及調平劑等黏著助劑。偶合劑具體而言較佳為下述通式(R)所表示的化合物，除了單獨使用以外，亦可將2種以上的化合物混合使用。
[式(R)中，R27 、R28 及R29 分別獨立地表示氫原子、碳數1~5的烷基、碳數1~5的烷氧基、碳數1~5的烷氧基羰基或者芳基，R30 表示(甲基)丙烯醯基、乙烯基、異氰 酸酯基、咪唑基、巰基、胺基、甲基胺基、二甲基胺基、苄基胺基、苯基胺基、環己基胺基、嗎啉基、哌嗪基、脲基或者縮水甘油基，t表示1~10的整數。]
本實施形態的黏著劑組成物亦可以應力緩和及黏著性提高為目的而併用橡膠成分。所謂橡膠成分，是指在其原本的狀態下表現出橡膠彈性(JIS K6200)的成分或者藉由反應而表現出橡膠彈性的成分。橡膠成分於室溫(25℃)下可為固形亦可為液狀，但就流動性提高的觀點而言，較佳為液狀。橡膠成分較佳為具有聚丁二烯骨架的化合物。橡膠成分可具有氰基、羧基、羥基、(甲基)丙烯醯基或者嗎啉基。另外，就黏著性提高的觀點而言，較佳為於側鏈或者末端含有作為高極性基的氰基、羧基的橡膠成分。此外，即便具有聚丁二烯骨架，亦於表現出熱塑性的情況分類為(a)熱塑性樹脂，於表現出自由基聚合性的情況分類為(b)自由基聚合性化合物。
橡膠成分具體而言可列舉：聚異戊二烯、聚丁二烯、羧基末端聚丁二烯、羥基末端聚丁二烯、1,2-聚丁二烯、羧基末端1,2-聚丁二烯、羥基末端1,2-聚丁二烯、丙烯酸橡膠、苯乙烯-丁二烯橡膠、羥基末端苯乙烯-丁二烯橡膠、丙烯腈-丁二烯橡膠，於聚合物末端含有羧基、羥基、(甲基)丙烯醯基或者嗎啉基的丙烯腈-丁二烯橡膠，羧基化腈橡膠、羥基末端聚(氧丙烯)、烷氧基矽烷基末端聚(氧丙烯)、聚(氧四亞甲基)二醇、聚烯烴二醇等。
另外，上述具有高極性基且於室溫下為液狀的橡膠成 分具體而言可列舉：液狀丙烯腈-丁二烯橡膠，於聚合物末端含有羧基、羥基、(甲基)丙烯醯基或者嗎啉基的液狀丙烯腈-丁二烯橡膠、液狀羧基化腈橡膠等；作為極性基的丙烯腈含量較佳為10質量%~60質量%。
該些化合物除了單獨使用以外，亦可將2種以上的化合物混合使用。
另外，本實施形態的黏著劑組成物中，以應力緩和及黏著性提高為目的，亦可添加有機微粒子。有機微粒子的平均粒徑較佳為0.05μm~1.0μm。此外，於有機微粒子包含上述橡膠成分的情況，分類為橡膠成分而並非有機微粒子，於有機微粒子包含上述(a)熱塑性樹脂的情況，分類為(a)熱塑性樹脂而並非有機微粒子。
有機微粒子具體而言可列舉包含以下化合物的有機微粒子：聚異戊二烯、聚丁二烯、羧基末端聚丁二烯、羥基末端聚丁二烯、1,2-聚丁二烯、羧基末端1,2-聚丁二烯、丙烯酸橡膠、苯乙烯-丁二烯橡膠、丙烯腈-丁二烯橡膠，於聚合物末端含有羧基、羥基、(甲基)丙烯醯基或者嗎啉基的丙烯腈-丁二烯橡膠，羧基化腈橡膠、羥基末端聚(氧丙烯)、烷氧基矽烷基末端聚(氧丙烯)、聚(氧四亞甲基)二醇、聚烯烴二醇(甲基)丙烯酸烷基酯-丁二烯-苯乙烯共聚物、(甲基)丙烯酸烷基酯-聚矽氧共聚物或者聚矽氧(甲基)丙烯酸共聚物或者複合物。
該些有機微粒子除了單獨使用以外，亦可將2種以上的化合物併用來使用。
本實施形態的黏著劑組成物於在常溫下為液狀的情況可以漿料狀來使用。於在室溫下為固體的情況，除了加熱而使用以外，亦可使用溶劑而漿料化。可使用的溶劑較佳為與黏著劑組成物及添加劑並無反應性且表現出充分的溶解性的溶劑，較佳為常壓下的沸點為50℃~150℃的溶劑。於沸點小於50℃的情況，若於室溫下放置，則存在揮發的顧慮增多，而變得難以於開放系統中使用的傾向。另外，若沸點超過150℃，則存在難以使溶劑揮發，對黏著後的可靠性造成不良影響的情況增多的傾向。
另外，本實施形態的黏著劑組成物亦可製成膜狀而使用。可將向黏著劑組成物中視需要添加溶劑等而成的溶液塗佈於氟樹脂膜、聚對苯二甲酸乙二酯膜、脫模紙等剝離性基材上，或者使不織布等基材含浸上述溶液而載置於剝離性基材上，去除溶劑等而製成膜來使用。若以膜的形狀使用，則就操作性等方面而言更便利。
本實施形態的黏著劑組成物可將加熱及加壓併用而黏著。加熱溫度較佳為100℃~200℃的溫度。壓力較佳為不對被黏附體造成損傷的範圍，通常較佳為0.1MPa~10MPa。該些加熱及加壓較佳為於0.5秒~120秒的範圍內進行，於120℃~190℃、3MPa、10秒的加熱下亦可使其黏著。
本實施形態的黏著劑組成物可作為熱膨脹係數不同的異種被黏附體的黏著劑來使用。具體而言，可作為異向導電黏著劑、銀漿料、銀膜等所代表的電路連接材料，晶片 尺寸封裝(chip scale package，CSP)用彈性體、CSP用底部填充材料、引線覆蓋晶片封裝(lead on chip，LOC)帶等所代表的半導體元件黏著材料來使用。
本實施形態的黏著劑組成物是作為用於將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件連接的黏著劑組成物來使用。此處，上述第一電路構件及/或上述第二電路構件是由包含玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成。玻璃轉移溫度為200℃以下的熱塑性樹脂並無特別限定，例如可列舉聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯等。
接著，對使用上述本實施形態的黏著劑組成物的電路構件的連接結構體進行說明。圖1是表示使用本實施形態的黏著劑組成物的電路構件的連接結構體的一實施形態的示意剖面圖。圖2是表示製作圖1所示的電路構件的連接結構體之前的第一電路構件、第二電路構件及黏著劑組成物的示意剖面圖。
圖1所示的電路構件的連接結構體100包括：於第一電路基板31的主面31a上具有第一連接端子32的第一電路構件30、於第二電路基板41的主面41a上具有第二連接端子42的第二電路構件40、以及以第一連接端子32與第二連接端子42對向的方式將第一電路基板31的主面31a與第二電路基板41的主面41a連接的連接構件10C。第一連接端子32與第二連接端子42是藉由相互接觸而電 性連接。另外，連接構件10C包含本實施形態的黏著劑組成物10的硬化物。
圖1所示的電路構件的連接結構體100例如可以如下方式來製造。
首先，如圖2所示，準備第一電路構件30、第二電路構件40及成形為膜狀的黏著劑組成物10。接著，將黏著劑組成物10載置於第二電路構件40的形成有第二連接端子42的主面41a上，進而於黏著劑組成物10上以第一連接端子32與第二連接端子42對向的方式載置第一電路構件30。然後，經由第一電路構件30及第二電路構件40，一邊將黏著劑組成物10加熱一邊使其硬化，同時對主面31a、41a向垂直方向加壓，於第一電路構件30及第二電路構件40之間形成連接構件10C，獲得圖1的電路構件的連接結構體100。
圖3是表示使用含有(d)導電性粒子的本實施形態的黏著劑組成物的電路構件的連接結構體的一實施形態的示意剖面圖。圖4是表示製作圖3所示的電路構件的連接結構體之前的第一電路構件、第二電路構件及黏著劑組成物(含有導電性粒子)的示意剖面圖。
圖3所示的電路構件的連接結構體200包括：於第一電路基板31的主面31a上具有第一連接端子32的第一電路構件30、於第二電路基板41的主面41a上具有第二連接端子42的第二電路構件40、以及以第一連接端子32與第二連接端子42相對向的方式將第一電路基板31的主面 31a與第二電路基板41的主面41a連接的連接構件20C。此外，連接構件20C是於黏著劑組成物的導電性粒子以外的成分21中分散有導電性粒子22的黏著劑組成物20的硬化物(即，於黏著劑組成物的導電性粒子以外的成分的硬化物21C中分散有導電性粒子22的硬化物)，於對向的第一連接端子32與第二連接端子42之間，導電性粒子22與兩連接端子接觸，藉此經由導電性粒子22而使兩連接端子電性連接。
圖3所示的電路構件的連接結構體200例如可如圖4所示，準備第一電路構件30、第二電路構件40及成形為膜狀的黏著劑組成物20，利用與獲得上述電路構件的連接結構體100的方法相同的方法來製造。
此處，第一電路構件30及第二電路構件40中的至少一者是由含有玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成。即，第一電路基板31及第二電路基板41中的至少一者含有玻璃轉移溫度為200℃以下的熱塑性樹脂。此處，玻璃轉移溫度為200℃以下的熱塑性樹脂較佳為選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種。若第一電路構件30及第二電路構件40中的至少一者為由含有選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種的基材所構成的電路構件，則與黏著劑組成物的潤濕性提高，黏著強度進一步提高。因此，此種電路構件的連接結構體可獲得更優異的連接可靠性。
此外，第一電路構件30及第二電路構件40中的一者可由不含選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種的基材所構成。形成此種電路構件的基材可使用：半導體、玻璃、陶瓷等包含無機物的基材，聚醯亞胺等包含有機物的基材，玻璃/環氧等組合有無機物與有機物的基材等。
另外，第一連接端子32及第二連接端子42中的至少一者較佳為由選自由ITO及IZO所組成組群中的至少1種所構成。ITO及IZO由於容易進行蝕刻，圖案加工性優異，故而適宜作為連接端子。並且，藉由使用本實施形態的黏著劑組成物，可充分抑制由ITO及/或IZO構成的連接端子的腐蝕。
此外，第一連接端子32及第二連接端子42中的一者或兩者可由ITO及IZO以外的材料所構成。如上所述的連接端子可使用包含銅、銀、鋁、金、鈀、鎳及該些金屬的合金等金屬的連接端子。
此外，作為連接構件來使用的本實施形態的黏著劑組成物無需完全硬化(於規定硬化條件下可達成的最高度的硬化)，只要產生上述特性，則亦可為部分硬化的狀態。
實例
以下，基於實例對本實施形態進行具體說明，但本實施形態並不限定於此。
〈熱塑性樹脂〉
(苯氧基樹脂的製備)
將苯氧基樹脂(東都化成股份有限公司製造，YP-50(商品名))40質量份溶解於甲基乙基酮60質量份中，製成固體成分為40質量%的溶液。
(聚酯胺基甲酸酯樹脂的準備)
聚酯胺基甲酸酯樹脂(東洋紡股份有限公司製造，UR-1400(商品名))是使用樹脂成分為30質量%的甲基乙基酮與甲苯的1：1混合溶劑溶解品。
(胺基甲酸酯樹脂的合成)
於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，將重量平均分子量為2000的聚己二酸丁二酯二醇450質量份、重量平均分子量為2000的聚氧四亞甲基二醇450質量份、及1,4-丁二醇100質量份於甲基乙基酮4000質量份中均勻混合，添加二苯基甲烷二異氰酸酯390質量份，於70℃下反應，獲得重量平均分子量為35萬的胺基甲酸酯樹脂。
〈自由基聚合性化合物〉
(胺基甲酸酯丙烯酸酯(L-1600S)的準備)
準備重量平均分子量為15000且臨界表面張力為15mN/m的胺基甲酸酯丙烯酸酯(Mitsui Polyurethane股份有限公司製造，L-1600S(商品名))。另外，L-1600S為使用醚系二醇的化合物，並不滿足上述通式(A)。
(胺基甲酸酯丙烯酸酯(PE-UA1)的合成)
於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，投入數量平均分子量 為2000的聚(3-甲基戊烷己二酸酯)二醇(脂肪族聚酯二醇，Kuraray股份有限公司製造，Kurapol P-2010(商品名))2000質量份(1.00莫耳)、二月桂酸二丁基錫(Aldrich股份有限公司製造)5.53質量份。充分導入氮氣後，加熱至70℃~75℃，然後以3小時均勻滴加二環己基甲烷4,4'-二異氰酸酯(脂肪族二異氰酸酯，Evonik Degussa公司製造，VESTANAT H12 DMI(商品名))787質量份(3.00莫耳)，使其反應。滴加完畢後繼續反應約10小時。接著向其中投入丙烯酸2-羥基乙酯(Aldrich股份有限公司製造)238質量份(2.05莫耳)、對苯二酚單甲醚(Aldrich股份有限公司製造)0.53質量份，進而反應10小時，藉由紅外線(infrared，IR)測定來確認異氰酸酯消失而結束反應，獲得胺基甲酸酯丙烯酸酯。所得的胺基甲酸酯丙烯酸酯(PE-UA1)的臨界表面張力為30mN/m，重量平均分子量為15300。另外，PE-UA1是使用聚酯二醇的化合物，滿足上述通式(A)。
(胺基甲酸酯丙烯酸酯(PE-UA2)的合成)
於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，投入數量平均分子量為2000的聚己內酯二醇(脂肪族聚酯二醇，商品名：Placcel 220EB，Daicel化學工業股份有限公司製造)2000質量份(1.00莫耳)、二月桂酸二丁基錫(Aldrich股份有限公司製造)5.53質量份。充分導入氮氣後，加熱至70℃~75℃，然後以3小時均勻滴加異佛爾酮二異氰酸酯(脂肪族二異 氰酸酯，Aldrich股份有限公司製造)666質量份(3.00莫耳)，使其反應。滴加完畢後繼續反應約10小時。接著向其中投入丙烯酸2-羥基乙酯(Aldrich股份有限公司製造)238質量份(2.05莫耳)、對苯二酚單甲醚(Aldrich股份有限公司製造)0.53質量份，進而反應10小時，藉由IR測定來確認異氰酸酯消失而結束反應，獲得胺基甲酸酯丙烯酸酯。所得的胺基甲酸酯丙烯酸酯(PE-UA2)的臨界表面張力為25mN/m，重量平均分子量為13500。另外，PE-UA2是使用聚酯二醇的化合物，滿足上述通式(A)。
(胺基甲酸酯丙烯酸酯(PE-UA3)的合成)
於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，投入丙烯酸2-羥基乙酯(Aldrich股份有限公司製造)238質量份(2.05莫耳)、對苯二酚單甲醚(Aldrich股份有限公司製造)0.53質量份、數量平均分子量為1000的聚己內酯二醇(脂肪族聚酯二醇，商品名：Placcel 210N，Daicel化學工業股份有限公司製造)2000質量份(2.00莫耳)、二月桂酸二丁基錫(Aldrich股份有限公司製造)5.53質量份。充分導入氮氣後，加熱至70℃~75℃，然後以3小時均勻滴加異佛爾酮二異氰酸酯(脂肪族二異氰酸酯，Aldrich股份有限公司製造)666質量份(3.00莫耳)，使其反應。滴加完畢後繼續反應約10小時，藉由IR測定來確認異氰酸酯消失而結束反應，獲得胺基甲酸酯丙烯酸酯。所得的胺基甲酸酯丙烯酸酯(PE-UA3)的臨界表面張力為28mN/m，重量平均分 子量為14500。另外，PE-UA3是使用聚酯二醇的化合物，滿足上述通式(A)。
(胺基甲酸酯丙烯酸酯(PE-UA4)的合成)
於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，加入3-甲基-1,5-戊二醇1650質量份(14莫耳)及間苯二甲酸1660質量份(10莫耳)，於常壓下充分導入氮氣後，一邊將在約170℃下生成的水蒸餾去除至系統外，一邊進行酯化反應。於聚酯的酸值成為0.3mgKOH/g以下的時刻利用真空泵緩緩提高真空度，使反應完結。以上述方式獲得的芳香族聚酯二醇(ED-1)的數量平均分子量為2000。
進而，於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，投入所得的芳香族聚酯二醇(ED-1)2000質量份(1.00莫耳)、二月桂酸二丁基錫(Aldrich股份有限公司製造)5.53質量份。充分導入氮氣後，加熱至70℃~75℃，然後以3小時均勻滴加異佛爾酮二異氰酸酯(脂肪族二異氰酸酯，Aldrich股份有限公司製造)666質量份(3.00莫耳)，使其反應。滴加完畢後，繼續反應約15小時。接著向其中投入丙烯酸2-羥基乙酯(Aldrich股份有限公司製造)238質量份(2.05莫耳)、對苯二酚單甲醚(Aldrich股份有限公司製造)0.53質量份，進而反應7小時，藉由IR測定來確認異氰酸酯消失而結束反應，獲得胺基甲酸酯丙烯酸酯。所得的胺基甲酸酯丙烯酸酯(PE-UA4)的臨界表面張力為42mN/m，重 量平均分子量為11500。另外，PE-UA4是使用聚酯二醇的化合物，滿足上述通式(A)。
(胺基甲酸酯丙烯酸酯(PE-UA5)的合成)
於具備攪拌機、溫度計、安裝有氯化鈣乾燥管的回流冷卻管、氮氣導入管的反應容器中，投入數量平均分子量為2000的聚(1,6-己二醇碳酸酯)二醇(脂肪族聚碳酸酯二醇，旭化成化學股份有限公司製造，PCDL T5652(商品名))4000質量份(2.00莫耳)、二月桂酸二丁基錫(Aldrich股份有限公司製造)5.53質量份。充分導入氮氣後，加熱至70℃~75℃，然後以3小時均勻滴加異佛爾酮二異氰酸酯(脂肪族二異氰酸酯，Aldrich股份有限公司製造)666質量份(3.00莫耳)，使其反應。滴加完畢後，繼續反應約15小時。接著向其中投入丙烯酸2-羥基乙酯(Aldrich股份有限公司製造)238質量份(2.05莫耳)、對苯二酚單甲醚(Aldrich股份有限公司製造)0.53質量份，進而反應10小時，藉由IR測定來確認異氰酸酯消失而結束反應，獲得胺基甲酸酯丙烯酸酯。所得的胺基甲酸酯丙烯酸酯(PE-UA5)的臨界表面張力為21mN/m，重量平均分子量為30000。另外，PE-UA5為使用聚碳酸酯二醇的化合物，並不滿足上述通式(A)。
(異三聚氰酸改質2官能丙烯酸酯(M-215)的準備)
準備異三聚氰酸改質2官能丙烯酸酯(東亞合成股份有限公司製造，M-215(商品名))。
(具有磷酸基的乙烯基化合物(P-2M)的準備)
準備磷酸2-(甲基)丙烯醯氧基乙酯(商品名：Light Ester P-2M，共榮社化學股份有限公司製造)。
〈自由基聚合起始劑〉
準備過氧化二苯甲醯(商品名：Nyper BW，日油股份有限公司製造)作為自由基聚合起始劑。
〈導電性粒子〉
(導電性粒子的製作)
於以聚苯乙烯為核的粒子的表面設置厚度0.2μm的鎳層，且於該鎳層的外側設置厚度0.02μm的金層，製作平均粒徑為10μm、比重為2.5的導電性粒子。
[實例1~實例10及比較例1~比較例5]
以固體重量比計如表2所示來調配熱塑性樹脂、自由基聚合性化合物及自由基聚合起始劑，進而調配分散1.5vol%的導電性粒子，獲得黏著劑組成物。使用塗佈裝置，將所得的黏著劑組成物塗佈於厚度80μm的氟樹脂膜上，藉由70℃、10分鐘的熱風乾燥而獲得黏著劑層的厚度為20μm的膜狀黏著劑組成物。
[連接電阻、黏著強度的測定]
使實例1~實例10以及比較例1~比較例5的膜狀黏著劑組成物，介隔存在於在聚醯亞胺膜(Tg為350℃)上具有80根線寬為150μm、間距為300μm、厚度為8μm的銅電路的可撓性電路板(flexible printed circuit，FPC)與形成有厚度5μm的Ag漿料薄層的PET基板(厚度為0.1mm)之間。另外，使實例1~實例10以及比較例1~比較例5的膜狀黏著劑組成物，介隔存在於在聚醯亞胺膜 上具有80根線寬為150μm、間距為300μm、厚度為18μm的銅電路的FPC與在PET(厚度為0.1mm)膜上形成有線寬為150μm、間距為300μm、厚度為10μm的Ag漿料電路的基板之間。對該些分別使用熱壓接裝置(加熱方式：恆溫型，Toray Engineering公司製造)，於150℃、2MPa下加熱加壓10秒，遍及寬度2mm而連接，製作連接體。於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，利用萬用表來測定該些連接體的鄰接電路間的電阻值。電阻值是以鄰接電路間的電阻37點的平均值表示。
另外，依據JIS-Z0237，利用90度剝離法來測定各個連接體的黏著強度，進行評價。此處，黏著強度的測定裝置是使用Toyo Baldwin股份有限公司製造的Tensilon UTM-4(剝離速度為50mm/min，25℃)。將以上述方式進行的膜狀黏著劑組成物的連接電阻及黏著強度的測定的結果示於下述表3。
實例1~實例7的黏著劑組成物於加熱溫度150℃下，於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，表現出約1.2Ω以下的良好連接電阻及600N/m以上的良好黏著強度。
相對於該些實例，比較例1及比較例3的黏著劑組成物於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，雖表現出良好的連接電阻，但黏著強度變低。另外，比較例2、比較例4及比較例5的黏著劑組成物於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)的連接電阻高，黏著強度亦與實例1~實例7相比較而變低。
另一方面，實例8~實例10的黏著劑組成物於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，表現出約1.2Ω以下的良好連接電阻，且與比較例1及比較例3相比，黏著強度優異。
[實例11~實例13以及比較例6及比較例7]
另外，使實例3、實例4及實例7以及比較例3及比較例4的膜狀黏著劑組成物，分別介隔存在於在聚醯亞胺膜上具有80根線寬為150μm、間距為300μm、厚度為8μm的銅電路的可撓性電路板(FPC)與PET膜(厚度為0.1mm，Tg為120℃)、PC膜(厚度為0.1mm，Tg為150℃)及PEN膜(厚度為0.1mm，Tg為160℃)之間。對該些分別使用熱壓接裝置(加熱方式：恆溫型，Toray Engineering公司製造)，於150℃、2MPa下加熱加壓10秒，遍及寬度2mm而壓接，製作連接體。
另外，各個連接體的黏著強度是以與上述方法相同的方式測定。將以上述方式進行的膜狀黏著劑組成物的黏著強度的測定結果示於下述表4。
實例11~實例13中使用的黏著劑組成物對於任一種基材，均於加熱溫度150℃下，於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，表現出600N/m以上的良好黏著強度。相對於該些實例，比較例6及比較例7中使用的黏著劑組成物於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，黏著強度變低。
[參考例1~參考例6]
作為參考例，使實例3、實例4、實例6及實例7以及比較例1及比較例3的膜狀黏著劑組成物，介隔存在於在聚醯亞胺膜上具有500根線寬為25μm、間距為50μm、厚度為8μm的銅電路的可撓性電路板(FPC)與形成有 0.2μm的ITO薄層的玻璃(厚度為1.1mm，表面電阻為20Ω/□)之間。對其使用熱壓接裝置(加熱方式：恆溫型，Toray Engineering公司製造)，於150℃、2MPa下加熱加壓10秒，遍及寬度2mm而連接，製作連接體。於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，利用萬用表來測定該連接體的鄰接電路間的電阻值。電阻值是以鄰接電路間的電阻37點的平均值表示。
另外，依據JIS-Z0237，利用90度剝離法來測定該連接體的黏著強度，進行評價。此處，黏著強度的測定裝置是使用Toyo Baldwin股份有限公司製造的Tensilon UTM-4(剝離速度為50mm/min，25℃)。將以上述方式進行的膜狀黏著劑組成物的連接電阻及黏著強度的測定的結果示於下述表5。
如上所示，比較例的黏著劑組成物於被黏附體為PET膜、PC膜及PEN膜的情況，連接電阻或黏著強度差。但是，如表5所示，於被黏附體為附有ITO的玻璃的情況，包括使用比較例的黏著劑組成物的情況的參考例1~參考例6的所有例子中，於剛黏著後及在85℃、85%RH的高溫高濕槽中保持240小時後(試驗後)，確認獲得2.5Ω以下的良好連接電阻及680N/m以上的良好黏著強度。
[產業上之可利用性]
依據本實施形態，可提供一種對於聚對苯二甲酸乙二酯、聚碳酸酯、聚萘二甲酸乙二酯等有機基材，即便於低溫的硬化條件下亦可獲得優異的黏著強度，且於長時間的可靠性試驗(高溫高濕試驗)後亦可維持穩定的性能(黏著強度或連接電阻)的黏著劑組成物，使用該黏著劑組成物的電路構件的連接結構體，連接結構體的製造方法以及黏著劑組成物的應用。
10、20‧‧‧黏著劑組成物
10C、20C‧‧‧連接構件
21‧‧‧不含導電性粒子的黏著劑組成物
22‧‧‧導電性粒子
21C‧‧‧不含導電性粒子的黏著劑組成物的硬化物
30‧‧‧第一電路構件
31‧‧‧第一電路基板
31a‧‧‧主面
32‧‧‧第一連接端子
40‧‧‧第二電路構件
41‧‧‧第二電路基板
41a‧‧‧主面
42‧‧‧第二連接端子
100、200‧‧‧電路構件的連接結構體
圖1是表示使用本實施形態的黏著劑組成物的電路構件的連接結構體的一實施形態的示意剖面圖。
圖2是表示製作圖1所示的電路構件的連接結構體之前的第一電路構件、第二電路構件及黏著劑組成物的示意剖面圖。
圖3是表示使用本實施形態的黏著劑組成物(含有導電性粒子)的電路構件的連接結構體的一實施形態的示意剖面圖。
圖4是表示製作圖3所示的電路構件的連接結構體之前的第一電路構件、第二電路構件及黏著劑組成物(含有導電性粒子)的示意剖面圖。
10C‧‧‧連接構件
30‧‧‧第一電路構件
31‧‧‧第一電路基板
31a‧‧‧主面
32‧‧‧第一連接端子
40‧‧‧第二電路構件
41‧‧‧第二電路基板
41a‧‧‧主面
42‧‧‧第二連接端子
100‧‧‧電路構件的連接結構體

Claims (14)

  1. 一種黏著劑組成物，用於將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件連接，上述第一電路構件及/或上述第二電路構件是由包含玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且上述(b)自由基聚合性化合物包含下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯： [式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯的開環化合物所衍生的基團或者下述通式(B)所表示的基團，R4 表示飽和脂肪族基或者飽和脂環基，R5 表示下述通式(B)所表示的基團，a表示1~40的整數] [式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同]。
  2. 一種黏著劑組成物，用於將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件連接，上述第一電路構件及/或上述第二電路構件是由包含選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種的基材所構成，上述黏著劑組成物含有(a)熱塑性樹脂、(b)自由基聚合性化合物及(c)自由基聚合起始劑，且上述(b)自由基聚合性化合物包含下述通式(A)所表示的胺基甲酸酯(甲基)丙烯酸酯： [式(A)中，R1 及R2 分別獨立地表示氫原子或者甲基，R3 表示伸乙基、伸丙基、由ε-己內酯的開環化合物所衍生的基團或者下述通式(B)所表示的基團，R4 表示飽和脂肪族基或者飽和脂環基，R5 表示下述通式(B)所表示的基團，a表示1~40的整數] [式(B)中，R6 及R7 分別獨立地表示碳數2~12的直鏈或者分支鏈的伸烷基，b表示1~10的整數，c表示1~25的整數；此外，式中，R6 彼此、R7 彼此、b彼此以及c彼此分別可相同，亦可不同]。
  3. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中上述胺基甲酸酯(甲基)丙烯酸酯是使用脂肪族聚酯二醇而獲得。
  4. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中上述胺基甲酸酯(甲基)丙烯酸酯的重量平均分子量為8000以上且小於25000。
  5. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中上述(b)自由基聚合性化合物含有1種以上的具有磷酸基的乙烯基化合物、及1種以上的上述具有磷酸基的乙烯基化合物以外的自由基聚合性化合物。
  6. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中上述(a)熱塑性樹脂含有選自由苯氧基樹脂、聚胺基甲酸酯樹脂、聚酯胺基甲酸酯樹脂、丁醛樹脂、丙烯酸樹脂及聚醯亞胺樹脂所組成組群中的至少1種。
  7. 如申請專利範圍第1項或第2項所述之黏著劑組成 物，其中更含有(d)導電性粒子。
  8. 如申請專利範圍第1項或第2項所述之黏著劑組成物，其中所述黏著劑組成物為膜狀。
  9. 一種異向導電性黏著劑，含有如申請專利範圍第7項所述之黏著劑組成物。
  10. 一種電路構件的連接結構體，包括：主面上具有第一連接端子的第一電路構件、主面上具有第二連接端子的第二電路構件及連接構件，以使上述第一連接端子及上述第二連接端子對向的方式配置上述第一電路構件及上述第二電路構件，其中上述連接構件介於上述第一電路構件與上述第二電路構件之間，而且上述第一連接端子及上述第二連接端子電性連接，上述連接構件為如申請專利範圍第1項至第8項中任一項所述之黏著劑組成物或如申請專利範圍第9項所述之異向導電性黏著劑的硬化物，並且上述第一電路構件及/或上述第二電路構件是由含有玻璃轉移溫度為200℃以下的熱塑性樹脂的基材所構成。
  11. 一種電路構件的連接結構體，包括：主面上具有第一連接端子的第一電路構件、主面上具有第二連接端子的第二電路構件及連接構件，以使上述第一連接端子及上述第二連接端子對向的方式配置上述第一電路構件及上述第二電路構件，其中上述連接構件介於上述第一電路構件與上述第二電路構件之間，而且上述第一連接端子及上述第二連接端子電性連接， 上述連接構件為如申請專利範圍第1項至第8項中任一項所述之黏著劑組成物或如申請專利範圍第9項所述之異向導電性黏著劑的硬化物，並且上述第一電路構件及/或上述第二電路構件是由包含選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種的基材所構成。
  12. 一種電路構件的連接結構體，包括：主面上具有第一連接端子的第一電路構件、主面上具有第二連接端子的第二電路構件及連接構件，以使上述第一連接端子及上述第二連接端子對向的方式配置上述第一電路構件及上述第二電路構件，其中上述連接構件介於上述第一電路構件與上述第二電路構件之間，而且上述第一連接端子及上述第二連接端子電性連接，並且上述連接構件為如申請專利範圍第1項至第8項中任一項所述之黏著劑組成物或如申請專利範圍第9項所述之異向導電性黏著劑的硬化物。
  13. 如申請專利範圍第10項至第12項中任一項所述之電路構件的連接結構體，其中上述第一電路構件或者上述第二電路構件中的一方的電路構件是由含有選自由聚對苯二甲酸乙二酯、聚碳酸酯及聚萘二甲酸乙二酯所組成組群中的至少1種的基材所構成，並且上述第一電路構件或第二電路構件中的另一方的電路構件是由含有選自由聚醯亞胺樹脂及聚對苯二甲酸乙二酯 所組成組群中的至少1種的基材所構成。
  14. 一種電路構件的連接結構體的製造方法，包括以下步驟：將主面上具有第一連接端子的第一電路構件、與主面上具有第二連接端子的第二電路構件，以使上述第一連接端子及上述第二連接端子對向的方式配置，其中如申請專利範圍第1項至第8項中任一項所述之黏著劑組成物或如申請專利範圍第9項所述之異向導電性黏著劑介於上述第一電路構件與上述第二電路構件之間；以及將上述黏著劑組成物加熱，使其硬化而將上述第一電路構件與上述第二電路構件連接。
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