TWI414576B - Adhesive composition - Google Patents

Adhesive composition Download PDF

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TWI414576B
TWI414576B TW97121635A TW97121635A TWI414576B TW I414576 B TWI414576 B TW I414576B TW 97121635 A TW97121635 A TW 97121635A TW 97121635 A TW97121635 A TW 97121635A TW I414576 B TWI414576 B TW I414576B
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adhesive composition
group
urethane
mass
acrylate
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TW97121635A
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TW200904929A (en
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Yasushi Akutsu
Yasunobu Yamada
Kouichi Miyauchi
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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    • C08F290/065—Polyamides; Polyesteramides; Polyimides
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1345—Conductors connecting electrodes to cell terminals
    • G02F1/13452—Conductors connecting driver circuitry and terminals of panels
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00013—Fully indexed content
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • 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
    • H05K3/36—Assembling printed circuits with other printed circuits
    • H05K3/361—Assembling flexible printed circuits with other printed circuits
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/901—Printed circuit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/2857—Adhesive compositions including metal or compound thereof or natural rubber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]
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Description

接著劑組成物
本發明係關於一種含有熱塑性樹脂、單官能丙烯酸酯及自由基聚合起始劑之接著劑組成物。
液晶顯示裝置、電漿顯示裝置、有機EL顯示裝置等顯示裝置中之顯示面板之絕大部分，係經由異向性導電膜藉由熱壓接而與可撓性配線基板進行異向性導電連接。作為此種異向性導電膜，先前係使用對於以熱塑性樹脂、環氧系樹脂及胺系硬化劑作為主要成分的黏合劑組成物中分散導電性粒子再製成膜而獲得者，其熱壓接條件通常為180℃、7秒。
然而，近年來因顯示面板向大畫面方面發展，故而在使用異向性導電膜進行熱壓接時不可忽視熱應力對顯示面板的影響，為了儘量排除其影響，一般要求將熱壓接條件由180℃、7秒之條件變更為160℃±20℃、4秒之條件。因此，作為能夠在相對低的溫度下進行壓接之異向性導電膜，目前開始使用對於以熱塑性樹脂及多官能丙烯酸酯及過氧化物為主要成分的黏合劑中分散導電性粒子再進行成膜而成的自由基聚合性異向性導電膜。又，於此種自由基聚合性異向性導電膜之熱硬化過程中，可增加對顯示面板或可撓性配線基板的接著性之羥基的生成卻無法實現。因此，為了改善接著性，而將極性較高且對聚醯亞胺或金屬 表面表現出親和性之分子內具有2個以上胺基甲酸酯鍵之丙烯酸胺基甲酸酯配合於黏合劑中(專利文獻1)。
專利文獻1：日本專利特開2006－257208號公報
然而，於顯示面板或可撓性配線基板之用以進行異向性導電連接的表面，為了提高與異向性導電膜的接著性，而在熱壓接之前以化學藥品進行粗面化處理，但隨著近期之配線的進一步細間距化，若以與先前同樣之方式使用化學藥品對可撓性配線基板的配線金屬表面或在配線間露出的聚醯亞胺表面進行粗面化處理，則會產生配線金屬變細等弊病，因此難以進行與先前相同水準之粗面化處理。
因此，在未對其等表面進行充分粗面化處理之比較平滑的狀態下，必須經由異向性導電膜而進行熱壓接，即便使用配合有丙烯酸胺基甲酸酯之專利文獻1之異向性導電膜，亦存在在顯示面板與可撓性配線基板之間無法確保充分之接著強度的問題。
本發明係欲解決以上所說明之先前技術之問題者，其目的在於：使含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之接著劑組成物，對於可撓性配線基板的配線金屬表面或在配線間露出的聚醯亞胺表面即使在比較平滑之狀態下亦可表現出良好之接著強度。
本發明者發現，於含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之接著劑組成物中所配合之先前的丙 烯酸胺基甲酸酯，在比較平滑的顯示面板與可撓性配線基板之間無法確保充分之接著強度，其原因在於：專利文獻1中所使用之丙烯酸胺基甲酸酯之胺基甲酸酯鍵並不存在於分子末端而是存在於分子內部，因此對於可撓性配線基板的配線金屬表面或在配線間露出的聚醯亞胺表面之作用由於受到立體阻礙等的影響而被抑制；且發現可藉由使用末端具有胺基甲酸酯殘基之單官能丙烯酸胺基甲酸酯，來代替分子內具有2個以上胺基甲酸酯鍵之丙烯酸胺基甲酸酯，而實現上述目的，從而完成本發明。
即，本發明提供一種接著劑組成物，其特徵在於：於含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之接著劑組成物中，含有以式(1)所表示之末端具有胺基甲酸酯殘基之單官能丙烯酸胺基甲酸酯。
CH2 ＝CR0 －COO－R1 －NHCOO－R2 (1)
式(1)中，R0 為氫原子或甲基，R1 為二價之烴基，R2 為可被取代之低級烷基。
又，本發明提供一種連接構造體，係相對向之電極經由於該電極間所挾持的含有異向性導電連接用導電粒子之上述接著劑組成物做電氣性連接而成者。
含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之本發明之接著劑組成物中，含有胺基甲酸酯殘基存在於末端之丙烯酸胺基甲酸酯。在此情形下，丙烯酸酯殘基係聚合部位，因期望丙烯酸酯殘基存在於分子末端，故胺基甲酸酯殘基存在於末端之丙烯酸胺基甲酸酯必然為單官 能。因此，胺基甲酸酯殘基存在於末端之單官能丙烯酸胺基甲酸酯，與分子內具有2個以上胺基甲酸酯鍵之丙烯酸胺基甲酸酯相比，可減小其自身的分子構造，可充分發揮對可撓性配線基板的配線金屬表面或在配線間露出的聚醯亞胺表面之胺基甲酸酯鍵的親和作用，其結果即使在其等表面為比較平滑的狀態下亦可表現出良好之接著強度。
本發明之接著劑組成物係含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之接著劑組成物，其特徵在於：含有以式(1)所表示之末端具有胺基甲酸酯殘基之單官能丙烯酸胺基甲酸酯。
CH2 ＝CR0 COO－R1 －NHCOO－R2 (1)
於式(1)中，R0 為氫原子或甲基。此處，在R0 為氫原子之情形下，式(1)之單官能丙烯酸胺基甲酸酯，於末端具有相對而言反應性高於甲基丙烯酸酯之丙烯酸酯殘基；在R0 為甲基之情形下，式(1)之單官能丙烯酸胺基甲酸酯，於末端具有甲基丙烯酸酯殘基。因此，在利用接著劑組成物來謀求更快之反應性之情況下，R0 較佳為氫原子，於謀求更慢之反應性之情況下，R0 較佳為甲基。
R1 為二價之烴基。作為二價之烴基，可舉出：伸甲基、伸乙基、伸丙基、伸丁基、伸環己基等伸烷基；伸苯基、伸萘基等伸芳香基；伸二甲苯基等伸芳烷基等。其中，就提昇接著強度之效果方面而言，較佳為伸烷基，特佳為伸 甲基、伸乙基，最佳為伸乙基。
R2 為可被取代之低級烷基。作為取代基，可舉出：甲氧基、乙氧基等烷氧基；苯基等芳香基。又，作為低級烷基，可舉出：甲基、乙基、異丙基、丙基、丁基、異丁基、戊基、己基、環己基等；作為R2 之較佳具體例，可舉出：甲基、乙基、乙氧基乙基、丁基、己基；其中，就提昇接著強度之效果方面而言，更佳為甲基或乙基。
因此，作為式(1)之單官能丙烯酸胺基甲酸酯之較佳具體例，可舉出：N－(甲基丙烯醯氧基乙基)胺基甲酸甲酯、N－(甲基丙烯醯氧基乙基)胺基甲酸乙酯、N－(甲基丙烯醯氧基乙基)胺基甲酸乙氧基乙酯、N－(甲基丙烯醯氧基乙基)胺基甲酸丁酯、N－(甲基丙烯醯氧基乙基)胺基甲酸己酯等。特佳為N－(甲基丙烯醯氧基乙基)胺基甲酸甲酯或N－(甲基丙烯醯氧基乙基)胺基甲酸乙酯。
若單官能丙烯酸胺基甲酸酯在接著劑組成物中之含量過少，則會導致接著力下降，若過多則會導致凝集力下降，而有產生導通不良之傾向，因此，於樹脂固體成分(熱塑性樹脂、多官能丙烯酸酯、自由基聚合起始劑及單官能丙烯酸胺基甲酸酯之合計)中，單官能丙烯酸胺基甲酸酯之含量，較佳為2~20質量%，更佳為5~10質量%。
再者，作為單官能丙烯酸胺基甲酸酯，可使用市售品，亦可如日本專利特開昭54－005921號公報中所揭示般，使醇類與具有甲基丙烯醯氧基及末端異氰酸酯基之化合物反應，而加以合成。
構成本發明之接著劑組成物之熱塑性樹脂，係膜形成用成分，可自先前用於異向性導電接著劑或絕緣性接著劑等領域中之熱塑性樹脂中適當選擇使用。作為熱塑性樹脂之具體例，可舉出：苯氧基樹脂、聚胺基甲酸酯樹脂酯、聚醯亞胺、聚醯胺、聚(甲基)丙烯酸酯、聚醚聚胺基甲酸酯、NBR樹脂等。該等熱塑性樹脂之重量平均分子量，就確保成膜性且確保與其他成分之相溶性方面而言，通常為5000~150000。
若熱塑性樹脂在接著劑組成物中之含量過少，則難以製成膜，若過多，則於連接時無法除去樹脂而有導致導通不良之傾向，因此，於樹脂固體成分(熱塑性樹脂、多官能丙烯酸酯、自由基聚合起始劑及單官能丙烯酸胺基甲酸酯之合計)中，熱塑性樹脂之含量較佳為10~60質量%，更佳為20~50質量%。
構成本發明接著劑組成物之多官能丙烯酸酯，係於接著劑組成物膜中導入三維網狀構造，且提高其凝集力之成分。作為此種多官能丙烯酸酯，係分子中具有2以上的丙烯酸酯殘基或甲基丙烯酸酯殘基之聚合性化合物，可自先前用於異向性導電接著劑或絕緣性接著劑等領域中之多官能丙烯酸酯中適當選擇使用。作為多官能丙烯酸酯之具體例，可舉出：三羥甲基丙烷三(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚烷二醇二(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯、新戊二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、 異三聚氰酸改質2官能(甲基)丙烯酸酯、異三聚氰酸改質3官能(甲基)丙烯酸酯等。
若多官能丙烯酸酯在接著劑組成物中之含量過小，則會凝集力不足且連接可靠性下降，若或多，則會變硬且降低應力緩和效果而有接著力下降之傾向，因此，於樹脂固體成分(熱塑性樹脂、多官能丙烯酸酯、自由基聚合起始劑及單官能丙烯酸胺基甲酸酯之合計)中，多官能丙烯酸酯之含量較佳為10~60質量%，更佳為20~50質量%。
構成本發明接著劑組成物之自由基聚合起始劑，係用以使多官能丙烯酸酯以及單官能丙烯酸胺基甲酸酯產生自由基聚合之起始劑，先前係用於異向性導電接著劑或絕緣性接著劑等領域中，可自於聚合時不易產生氣體之自由基聚合起始劑中適當選擇使用。作為自由基聚合起始劑之具體例，就穩定性、反應性、相溶性之觀點而言，可較佳地使用1分鐘半衰期溫度為90~175℃、分子量為180~1000之有機過氧化物。作為此種有機過氧化物之具體例，可舉出：過氧化苯甲醯、過氧化新癸酸異丙苯酯(cumyl peroxyneodecanoate)、過氧化新癸酸1,1,3,3－四甲基丁酯、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、過氧化三甲基乙酸第三丁酯、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 三丁基)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、過氧化新癸酸第三戊酯、過氧化2－乙基己酸第三戊酯、過氧化異丙基單碳酸第三己酯、過氧化馬來酸第三丁酯、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－甲基過氧化苯甲醯基)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(過氧化苯甲醯基)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。該等化合物，亦可將2種以上化合物混合使用。
若自由基聚合起始劑在接著劑組成物中之含量過少，則會硬化不足，若過多，則在進行加熱加壓時樹脂排除性會下降，且有連接阻力增高之傾向，因此，樹脂固體成分(熱塑性樹脂、多官能丙烯酸酯、自由基聚合起始劑及單官能丙烯酸胺基甲酸酯之合計)中，自由基聚合起始劑之含量較佳為1~10質量%，更佳為2~8質量%。
本發明之接著劑組成物，可視需要而含有粒徑為0.1~10 μm之鎳粒子等導電粒子，粒徑為2~10 μm之樹脂包覆鎳粒子等異向性導電粒子、粒徑為0.01~1 μm之二氧化矽等絕緣填充劑等。若含有導電粒子，則可用作導電性接著劑組成物。若含有異向性導電粒子，則可用作異向性導電接著劑。在此情況下，於樹脂固體成分(熱塑性樹脂、多官能丙烯酸酯、自由基聚合起始劑及單官能丙烯 酸胺基甲酸酯之合計)中配合1~50質量%、較佳為1~40質量%之異向性導電粒子。又，若含有填充劑，則可提昇其硬化物之機械強度。又，為了緩和硬化時之應力，可含有各種橡膠材料。進一步，可視需要而適當配合甲醇、乙醇、丁醇等醇類，乙酸乙酯等酯類，丙酮、甲基乙基酮等酮類等通用溶劑。在將接著劑組成物製成膜之情況下，較佳為含有該等溶劑。
本發明之接著劑組成物，可將熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑及以式(1)所表示之於末端具有胺基甲酸酯殘基之單官能丙烯酸胺基甲酸酯，進一步視需要之其他添加成分或溶劑，藉由常法均勻混合進行製備。
本發明之接著劑組成物，可依照公知之方法作為糊狀物或膜而加以使用。例如，藉由將本發明之接著劑組成物作為糊狀物或膜，再將其夾持於相對向之電極之間進行熱壓接，而獲得將電極彼此之間電氣性連接之連接構造體。作為相對向之電極，可舉出顯示面板之電極與可撓性配線基板的電極之組合，但並不限定於該等。又，作為較佳態樣，可舉出相對向之電極中的一個為半導體元件的電極墊之態樣。
作為熱壓接條件，可舉出：通常為100~200℃、3~10秒，較佳為130~200℃、3~6秒之於比較低的溫度下且為短時間之硬化條件。如此，可實現較廣之壓接溫度範圍。
[實施例]
以下，根據實施例對說明本發明進行具體說明。
實施例1
於甲基丙烯酸異氰基乙酯10質量份中添加甲醇100質量份，於60℃下攪拌10小時，藉此獲得N－(甲基丙烯醯氧基乙基)胺基甲酸甲酯之甲醇溶液。於所含有之N－(甲基丙烯醯氧基乙基)胺基甲酸甲酯為10質量份的量之甲醇溶液中，將苯氧基樹脂(YP50，東都化成公司)40質量份、二丙烯酸酯(Light Ester 3EG，共榮社化學公司)40質量份、聚酯系聚胺基甲酸酯(Nipporan 3113、日本聚胺酯工業公司)10質量份及過氧化苯甲醯(日本油脂公司)3質量份，與樹脂固體含量為50質量%之量的乙酸乙酯與甲苯之混合溶劑(1：1(容量比))均勻混合，而獲得接著劑組成物。
實施例2
除了使用乙醇100質量份來代替甲醇100質量份以外，其餘重複進行與實施例1同樣的操作，藉此製備N－(甲基丙烯醯氧基乙基)胺基甲酸乙酯之乙醇溶液，進而獲得接著劑組成物。
實施例3
除了使用乙氧基乙醇100質量份來代替甲醇100質量份以外，其餘重複進行與實施例1同樣的操作，藉此製備N－(甲基丙烯醯氧基乙基)胺基甲酸乙氧基乙酯之乙氧基乙醇溶液，進而獲得接著劑組成物。
實施例4
除了使用丁醇100質量份來代替甲醇100質量份以外， 其餘重複進行與實施例1同樣的操作，藉此製備N－(甲基丙烯醯氧基乙基)胺基甲酸丁酯之丁醇溶液，進而獲得接著劑組成物。
實施例5
除了使用己醇100質量份來代替甲醇100質量份以外，重複進行與實施例1同樣的操作，藉此製備N－(甲基丙烯醯氧基乙基)胺基甲酸己酯之己醇溶液，進而獲得接著劑組成物。
比較例1
除了使用苯酚100質量份來代替甲醇100質量份以外，其餘重複進行與實施例1同樣的操作，藉此製備N－(甲基丙烯醯氧基乙基)胺基甲酸苯酯之苯酚溶液，進而獲得接著劑組成物。
比較例2
將2官能丙烯酸胺基甲酸酯(U－ZPPA，新中村化學公司)10質量份，與苯氧基樹脂(YP50，東都化成公司)40質量份、二丙烯酸酯(Light Ester 3EG，共榮社化學公司)40質量份、聚酯系聚胺基甲酸酯(Nipporan 3113，日本聚胺酯工業公司)10質量份及過氧化苯甲醯(日本油脂公司)3質量份，及樹脂固體含量為50質量%之量的乙酸乙酯與甲苯之混合溶劑(1：1(容量比))均勻混合，而獲得接著劑組成物。
比較例3
將苯酚樹脂(YP50，東都化成公司社)40質量份、二 丙烯酸酯(Light Ester 3EG，共榮社化學公司)40質量份、聚酯系聚胺基甲酸酯(Nipporan 3113，日本聚胺酯工業公司)10質量份及過氧化苯甲醯(日本油脂公司)3質量份，與樹脂固體含量為50質量%之量的乙酸乙酯和甲苯之混合溶劑(1：1(容量比))均勻混合，而獲得接著劑組成物。
評價 將實施例及比較例之接著劑組成物以乾燥厚度達到50 μm之方式，塗佈於厚度為50 μm之經剝離處理之聚對苯二甲酸乙二酯膜上，於80℃之烘箱中乾燥5分鐘，而製作接著膜。使用所獲得之接著膜，以如下說明之方式測定接著強度。
(接著強度試驗：參照圖1) 準備於0.7 mm厚之玻璃基板上形成有ITO膜之ITO玻璃基板、及50 μm間距(銅配線寬度為25 μm，銅配線厚度為8 μm)之聚醯亞胺可撓性配線基板(帶寬為40 mm)，使各配線之電極相對向，並將接著膜夾持於其間，於160℃、4 Mpa、4秒之條件下進行熱壓接。於熱壓接後，以10 mm寬，將接著膜嵌入聚醯亞胺可撓性配線基板中，於拉伸試驗裝置(TENSILON，OLIENTEC公司製)中以50 mm/min之速度進行90度剝離。將此時所獲得之接著強度值示於表1。再者，於實用方面期望接著強度為5 N/cm以上。
如表1所示，實施例1~5之接著劑組成物的接著強度，為實用方面較佳之5 N/cm以上，特別是在R2 為甲基、乙基之情況下，尤其是接著強度有變高。
另一方面，在R2 為苯基之比較例1之情況下、在使用2官能丙烯酸胺基甲酸酯之比較例2之情況下、在未使用丙烯酸胺基甲酸酯之比較例3之情況下，接著強度均未達到5 N/cm以上。
產業上之可利用性
含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之本發明之接著劑組成物，含有胺基甲酸酯殘基存在於末端之單官能丙烯酸胺基甲酸酯。因此，可充分發揮胺基甲酸酯鍵對可撓性配線基板的配線金屬表面或在配線間露出的聚醯亞胺表面之親和作用，結果即使在其等表面為比較平滑的狀態下亦可表現出良好之接著強度。因此，可實現細間距化，且可用於連接被黏著表面為比較圓滑之電子材料。
圖1係接著強度試驗之說明圖(圖中，FPC為可撓性配線板(flexible printed circuit)之縮寫，TAB為帶狀自動化黏合構裝(tape automated bonding)之縮寫，ACF為異向性導電膜(anisotropic conductive film)之縮寫)。

Claims (10)

  1. 一種接著劑組成物，其特徵在於：於含有熱塑性樹脂、多官能丙烯酸酯及自由基聚合起始劑之接著劑組成物中含有以式(1)所表示之末端具有胺基甲酸酯殘基之單官能丙烯酸胺基甲酸酯CH2 =CR0 -COO-R1 -NHCOO-R2 (1)(R0 為氫原子或甲基，R1 為二價之烴基，R2 為可被取代之低級烷基)；該接著劑組成物中該單官能丙烯酸胺基甲酸酯含量為2~20質量%；該熱塑性樹脂之重量平均分子量為5000~150000。
  2. 如申請專利範圍第1項之接著劑組成物，其中R1 為伸烷基。
  3. 如申請專利範圍第2項之接著劑組成物，其中伸烷基為伸乙基。
  4. 如申請專利範圍第1~3項中任一項之接著劑組成物，其中R2 為甲基、乙基、乙氧基乙基、丁基或己基。
  5. 如申請專利範圍第4項之接著劑組成物，其中R2 為甲基或乙基。
  6. 如申請專利範圍第1~3項中任一項之接著劑組成物，係含有異向性導電連接用導電粒子。
  7. 如申請專利範圍第4項之接著劑組成物，其中含有異向性導電連接用導電粒子。
  8. 如申請專利範圍第5項之接著劑組成物，其中含有異 向性導電連接用導電粒子。
  9. 一種連接構造體，係相對向之電極經由其間所挾持的申請專利範圍第6~8項中任一項之接著劑組成物做電氣性連接而成者。
  10. 如申請專利範圍第9項之連接構造體，其中相對向之電極中的一者為半導體元件之電極墊。
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