TWI528383B - Conductive material and connecting structure - Google Patents

Conductive material and connecting structure Download PDF

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Publication number
TWI528383B
TWI528383B TW101128104A TW101128104A TWI528383B TW I528383 B TWI528383 B TW I528383B TW 101128104 A TW101128104 A TW 101128104A TW 101128104 A TW101128104 A TW 101128104A TW I528383 B TWI528383 B TW I528383B
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Taiwan
Prior art keywords
conductive material
conductive
weight
electrode
particles
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TW101128104A
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Chinese (zh)
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TW201314707A (en
Inventor
Akira Yuuki
Junichi Shimaoka
Hiroshi Kobayashi
Hideaki Ishizawa
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Sekisui Chemical Co Ltd
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Publication of TW201314707A publication Critical patent/TW201314707A/en
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Publication of TWI528383B publication Critical patent/TWI528383B/en

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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
    • H—ELECTRICITY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • 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
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15788—Glasses, e.g. amorphous oxides, nitrides or fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
    • H01R12/50—Fixed connections
    • H01R12/51—Fixed connections for rigid printed circuits or like structures
    • H01R12/52—Fixed connections for rigid printed circuits or like structures connecting to other rigid printed circuits or like structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0221—Insulating particles having an electrically conductive coating
    • 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
    • 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

Description

導電材料及連接結構體 Conductive material and connecting structure

本發明係關於一種包含複數個導電性粒子之導電材料，係關於一種可用於將例如可撓性印刷基板、玻璃基板、環氧玻璃基板、半導體晶片及有機電致發光顯示元件用基板等各種連接對象構件之電極間電性連接的導電材料。又，本發明係關於一種使用上述導電材料之連接結構體。 The present invention relates to a conductive material comprising a plurality of conductive particles, which is useful for connecting various substrates such as a flexible printed circuit board, a glass substrate, a glass epoxy substrate, a semiconductor wafer, and an organic electroluminescence display element. A conductive material electrically connected between the electrodes of the object member. Further, the present invention relates to a bonded structure using the above conductive material.

膏狀或膜狀之各向異性導電材料已廣為人知。該各向異性導電材料係於黏合劑樹脂等中分散有複數個導電性粒子。 Paste or film-like anisotropic conductive materials are well known. The anisotropic conductive material is obtained by dispersing a plurality of conductive particles in a binder resin or the like.

業界將上述各向異性導電材料使用於例如可撓性印刷基板與玻璃基板之連接(FOG(Film on Glass))、半導體晶片與可撓性印刷基板之連接(COF(Chip on Film))、半導體晶片與玻璃基板之連接(COG(Chip on Glass))、及可撓性印刷基板與環氧玻璃基板之連接(FOB(Film on Board))等，以獲得各種連接結構體。 In the industry, the anisotropic conductive material is used for, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass), a connection between a semiconductor wafer and a flexible printed circuit board (COF (Chip on Film)), and a semiconductor. The connection between the wafer and the glass substrate (COG (Chip on Glass)), and the connection between the flexible printed circuit board and the epoxy glass substrate (FOB (Film on Board)), etc., to obtain various connection structures.

作為上述各向異性導電材料之一例，於下述之專利文獻1中，揭示有包含以熱硬化性樹脂為主成分之樹脂成分、捕捉自電極解離之金屬離子之金屬離子捕捉劑、及導電性粒子的各向異性導電材料。上述金屬離子捕捉劑具有小於導電性粒子之粒徑。 As an example of the above-mentioned anisotropic conductive material, Patent Document 1 listed below discloses a metal ion trapping agent containing a thermosetting resin as a main component, a metal ion trapping agent for capturing metal ions dissociated from the electrode, and conductivity. An anisotropic conductive material of particles. The metal ion scavenger has a particle diameter smaller than that of the conductive particles.

於下述之專利文獻2中，揭示有包含絕緣性接著劑、導電性粒子、及無機離子交換體之各向異性導電材料。 Patent Document 2 listed below discloses an anisotropic conductive material including an insulating adhesive, conductive particles, and an inorganic ion exchanger.

又，於下述之專利文獻3中，揭示有包含脂環式環氧樹脂、二醇類、具有環氧基之苯乙烯系熱塑性彈性體、紫外線活性型陽離子聚合觸媒、及導電性粒子的各向異性導電材料。 Further, Patent Document 3 listed below discloses an alicyclic epoxy resin, a glycol, a styrene-based thermoplastic elastomer having an epoxy group, an ultraviolet-active cationic polymerization catalyst, and conductive particles. Anisotropic conductive material.

於下述之專利文獻4中，揭示有包含硬化劑、硬化性之絕緣性樹脂、導電性粒子、及離子捕捉劑粒子的各向異性導電性接著片材。於專利文獻4中，關於離子捕捉劑粒子可交換之離子之類型，記載有陽離子型、陰離子型及兩性離子型。又，專利文獻4中記載，兩性離子型由於可將成為電極端子產生離子遷移之直接原因的金屬離子(陽離子)、與成為使導電率上升而生成金屬離子之原因的陰離子兩者均交換，故而較佳。 Patent Document 4 listed below discloses an anisotropically conductive adhesive sheet comprising a curing agent, a curable insulating resin, conductive particles, and ion scavenger particles. Patent Document 4 describes cationic, anionic, and zwitterionic types for the types of ions that can be exchanged for ion scavenger particles. Further, Patent Document 4 discloses that the zwitterionic type can exchange both metal ions (cations) which are the direct cause of ion migration in the electrode terminals, and anions which cause the formation of metal ions by increasing the conductivity. Preferably.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2001-237006號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-237006

[專利文獻2]日本專利特開平10-245528號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 10-245528

[專利文獻3]日本專利特開平11-060899號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 11-060899

[專利文獻4]日本專利特開2007-16088號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-16088

藉由上述各向異性導電材料將例如半導體晶片之電極與玻璃基板之電極電性連接時，係於玻璃基板上配置包含導電性粒子之各向異性導電材料。其次，將半導體晶片積層，進行加熱及加壓。藉此，使各向異性導電材料硬化， 且經由導電性粒子將電極間電性連接，獲得連接結構體。 When the electrode of the semiconductor wafer and the electrode of the glass substrate are electrically connected by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is disposed on the glass substrate. Next, the semiconductor wafer is laminated and heated and pressurized. Thereby, the anisotropic conductive material is hardened, Further, the electrodes are electrically connected via conductive particles to obtain a bonded structure.

若使用如專利文獻1~4記載的先前之各向異性導電材料製作連接結構體，則當於高濕下以通電狀態使用所獲得之連接結構體時，存在產生遷移之情況。因此，存在上述連接結構體之絕緣可靠性較低之情況。 When the bonded structure is produced using the previously anisotropic conductive material described in Patent Documents 1 to 4, when the obtained bonded structure is used in an energized state under high humidity, migration may occur. Therefore, there is a case where the insulation reliability of the above-mentioned connection structure is low.

尤其是使用如專利文獻3記載之包含陽離子產生劑的先前之各向異性導電材料的連接結構體存在於高濕下以通電狀態使用時，容易產生遷移之問題。 In particular, when a bonded structure using a conventional anisotropic conductive material containing a cation generating agent as described in Patent Document 3 is used in a charged state under high humidity, there is a problem that migration occurs easily.

又，若如專利文獻4記載般僅使用離子捕捉劑，有時無法充分地抑制遷移。進而，於專利文獻4之實施例中，僅係使用陽離子型之離子捕捉劑粒子、陰離子型之離子捕捉劑粒子中之任一者。專利文獻4之實施例中所使用之陽離子型之離子捕捉劑粒子及陰離子型之離子捕捉劑粒子、以及專利文獻4中所列舉之兩性離子型之離子捕捉劑粒子會因其他調配成分之種類之不同，而存在無法充分抑制遷移之情況。 Further, when only the ion scavenger is used as described in Patent Document 4, migration may not be sufficiently suppressed. Further, in the examples of Patent Document 4, only one of the cationic ion trapping agent particles and the anionic ion trapping agent particles is used. The cationic ion trapping agent particles and the anionic ion trapping agent particles used in the examples of Patent Document 4 and the zwitterionic ion trapping agent particles described in Patent Document 4 are different in the type of other compounding components. Different, but there is a situation where migration cannot be sufficiently suppressed.

又，近年來，上述連接結構體中之電極寬度/電極間寬度即L/S(線/間隙，line/space)不斷地進一步變小。上述連接結構體中之電極之L/S越小，存在產生遷移時越容易產生絕緣故障的問題。 Moreover, in recent years, the electrode width/interelectrode width in the above-mentioned connection structure, that is, L/S (line/space) is continually further reduced. The smaller the L/S of the electrode in the above-mentioned bonded structure, the more likely the problem of insulation failure occurs when migration occurs.

本發明之目的係提供一種儘管使用有陽離子產生劑，但將連接對象構件之電極間電性連接時，可提高所獲得之連接結構體之導通可靠性及絕緣可靠性的導電材料，以及使用該導電材料之連接結構體。 An object of the present invention is to provide a conductive material which can improve the conduction reliability and insulation reliability of the obtained connecting structure when the electrodes of the connecting member are electrically connected to each other despite the use of the cation generating agent, and A bonded structure of conductive material.

根據本發明之廣泛之態樣，係提供一種導電材料，其包含硬化性成分、陽離子交換體、陰離子交換體及導電性粒子，且上述硬化性成分含有硬化性化合物及陽離子產生劑。 According to a broad aspect of the present invention, there is provided a conductive material comprising a curable component, a cation exchanger, an anion exchanger, and conductive particles, wherein the curable component contains a curable compound and a cation generator.

於本發明之導電材料之某一特定態樣中，上述陽離子交換體之中***換容量為2 meq/g以上，且上述陰離子交換體之中***換容量為1 meq/g以上。 In a specific aspect of the conductive material of the present invention, the cation exchanger has a neutral exchange capacity of 2 meq/g or more, and the anion exchanger has a neutral exchange capacity of 1 meq/g or more.

上述陽離子交換體較佳為包含鋯原子。上述陰離子交換體較佳為包含鎂原子及鋁原子。 The above cation exchanger preferably contains a zirconium atom. The anion exchanger preferably contains a magnesium atom and an aluminum atom.

於本發明之導電材料之另一特定態樣中，相對於上述硬化性化合物100重量份，上述陽離子交換體之含量為0.01重量份以上、5重量份以下，且上述陰離子交換體之含量為0.01重量份以上、5重量份以下。 In another specific aspect of the conductive material of the present invention, the content of the cation exchanger is 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the curable compound, and the content of the anion exchanger is 0.01. It is more than 5 parts by weight or less.

於本發明之導電材料之另一特定態樣中，上述導電性粒子包含樹脂粒子、及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熔點為450℃以下之低熔點金屬層。 In another specific aspect of the conductive material of the present invention, the conductive particles include resin particles and a conductive layer disposed on a surface of the resin particles, and at least the outer surface of the conductive layer has a melting point of 450 ° C or less. a low melting point metal layer.

於本發明之導電材料之另一特定態樣中，其進而包含助焊劑(flux)。 In another particular aspect of the electrically conductive material of the present invention, it further comprises a flux.

本發明之導電材料較佳為用以連接具有銅電極之連接對象構件之導電材料。 The conductive material of the present invention is preferably a conductive material for connecting a member to be connected having a copper electrode.

本發明之導電材料較佳為各向異性導電材料。 The conductive material of the present invention is preferably an anisotropic conductive material.

本發明之連接結構體包含第1連接對象構件、第2連接對 象構件、將該第1、第2連接對象構件電性連接之連接部，且該連接部係藉由上述之導電材料而形成。 The connection structure of the present invention includes the first connection object member and the second connection pair The image forming member and the connecting portion for electrically connecting the first and second connecting target members are formed of the conductive material described above.

於本發明之連接結構體之某一特定態樣中，上述第1連接對象構件於表面具有第1電極，上述第2連接對象構件於表面具有第2電極，上述第1電極與上述第2電極藉由上述導電性粒子而電性連接，上述第1電極及上述第2電極中之至少一者為銅電極。 In a specific aspect of the connection structure of the present invention, the first connection target member has a first electrode on a surface thereof, and the second connection target member has a second electrode on a surface thereof, and the first electrode and the second electrode At least one of the first electrode and the second electrode is a copper electrode electrically connected by the conductive particles.

本發明之導電材料包含含有硬化性化合物及陽離子產生劑之硬化性成分以及導電性粒子，且進而包含陽離子交換體與陰離子交換體兩者，故而儘管使用有陽離子產生劑，但將連接對象構件之電極間電性連接時，可提高所獲得之連接結構體之導通可靠性及絕緣可靠性。 The conductive material of the present invention contains a curable component containing a curable compound and a cation generating agent, and conductive particles, and further includes both a cation exchanger and an anion exchanger. Therefore, although a cation generating agent is used, the member to be connected is connected. When the electrodes are electrically connected, the conduction reliability and insulation reliability of the obtained connection structure can be improved.

以下，詳細地說明本發明。 Hereinafter, the present invention will be described in detail.

本發明之導電材料包含硬化性成分、陽離子交換體、陰離子交換體及導電性粒子。上述硬化性成分含有硬化性化合物及陽離子產生劑。 The conductive material of the present invention contains a curable component, a cation exchanger, an anion exchanger, and conductive particles. The curable component contains a curable compound and a cation generating agent.

藉由使本發明之導電材料具有上述之組成，尤其是藉由使用陽離子交換體與陰離子交換體兩者，則儘管使用有陽離子產生劑，但將連接對象構件之電極間電性連接時，可提高所獲得之連接結構體之導通可靠性及絕緣可靠性。尤其是即便於高濕下以通電狀態使用該連接結構體，於導電性粒子之導電部及電極亦難以產生遷移，可充分確保較高 之絕緣可靠性。 By making the conductive material of the present invention have the above-described composition, in particular, by using both a cation exchanger and an anion exchanger, although a cation generating agent is used, when the electrodes of the connecting member are electrically connected to each other, Improve the conduction reliability and insulation reliability of the obtained connection structure. In particular, even when the connection structure is used in an energized state under high humidity, it is difficult to cause migration of the conductive portion and the electrode of the conductive particles, and it is possible to sufficiently ensure high Insulation reliability.

於本發明之導電材料中，上述硬化性成分含有硬化性化合物及硬化劑。上述硬化劑含有陽離子產生劑。由於導電材料含有陽離子產生劑，故而有連接結構體中容易產生遷移之傾向。針對於此，本發明之導電材料包含含有硬化性化合物及陽離子產生劑之硬化性成分以及導電性粒子，且進而包含陽離子交換體與陰離子交換體兩者，故而儘管使用有陽離子產生劑，但可有效地抑制連接結構體中之遷移，可有效地提高絕緣可靠性。 In the conductive material of the present invention, the curable component contains a curable compound and a curing agent. The above hardener contains a cation generating agent. Since the conductive material contains a cation generating agent, there is a tendency that migration occurs easily in the bonded structure. In view of the above, the conductive material of the present invention contains a curable component containing a curable compound and a cation generating agent, and conductive particles, and further includes both a cation exchanger and an anion exchanger, so that although a cation generating agent is used, Effectively suppressing the migration in the bonded structure can effectively improve the insulation reliability.

又，本發明者等人發現，藉由使用陽離子產生劑，與使用陽離子產生劑以外之熱硬化劑(咪唑化合物等)之情形相比，可有效地提高導通可靠性。 Moreover, the inventors of the present invention have found that the use of a cation generating agent can effectively improve the conduction reliability as compared with the case of using a thermal curing agent (imidazole compound or the like) other than the cation generating agent.

又，本發明者等人發現，藉由將陽離子交換體與陰離子交換體兩者併用，與單獨使用陽離子交換體、或單獨使用陰離子交換體、或者單獨使用兩性離子交換體之情形相比，對於包含陽離子產生劑之導電材料，可十分有效地抑制產生遷移，可有效地提高絕緣可靠性。 Further, the inventors of the present invention have found that by using a cation exchanger and an anion exchanger together, as compared with the case of using a cation exchanger alone, or using an anion exchanger alone, or using an amphoteric ion exchanger alone, The conductive material containing the cation generating agent can effectively inhibit migration and effectively improve the insulation reliability.

本發明之導電材料不包括僅含陽離子交換體作為離子交換體之導電材料。本發明之導電材料不包括僅含陰離子交換體作為離子交換體之導電材料。本發明之導電材料不包括含兩性離子交換體作為離子交換體，且不含陽離子交換體與陰離子交換體兩者之導電材料。 The conductive material of the present invention does not include a conductive material containing only a cation exchanger as an ion exchanger. The conductive material of the present invention does not include a conductive material containing only an anion exchanger as an ion exchanger. The conductive material of the present invention does not include a conductive material containing an amphoteric ion exchanger as an ion exchanger and containing no both a cation exchanger and an anion exchanger.

又，為於低溫下快速硬化，較佳為應用陽離子硬化系。由於陽離子產生劑之分子結構中所含之離子性成分容易於 組合物中擴散，及環氧化合物等陽離子硬化性化合物有時含有氯離子等原因，於使用陽離子產生劑之情形時，容易因微量之離子性成分而腐蝕電極。因此，於使用陽離子產生劑之情形時，電極間之連接可靠性存在問題。 Further, in order to rapidly harden at a low temperature, it is preferred to apply a cationic hardening system. Since the ionic component contained in the molecular structure of the cation generating agent is easy The diffusion of the composition and the cationically curable compound such as an epoxy compound may cause chlorine ions or the like. When a cation generating agent is used, the electrode is likely to be corroded by a trace amount of ionic components. Therefore, in the case of using a cation generating agent, there is a problem in connection reliability between electrodes.

另一方面，應用離子交換體對於上述問題可獲得效果，但存在其效果並不充分之情況。本發明者等人發現，藉由使用陽離子交換體與陰離子交換體兩者而並非僅使用陽離子交換體與陰離子交換體中之任一種離子交換體，可針對上述問題獲得顯著之效果。認為其原因在於，在僅使用陽離子交換體與陰離子交換體中之一者之情形時，由於僅將其中一種離子捕捉，故而陽離子產生劑等之解離平衡之平衡性受到破壞，其結果抗衡離子成為游離之狀態且繼續存在，因此無法充分降低組合物中之離子成分之不良影響。又，與使用具有陰陽兩性之離子捕捉能力之兩性離子交換體相比，使用陽離子交換體與陰離子交換體兩者對於上述問題更有效果。其理由並不明確，但可認為具有陰陽兩性之離子捕捉能力之化合物會因具有陰/陽性捕捉能力之部位靠近而使捕捉能力相互抵消從而使效果降低。 On the other hand, the application of the ion exchanger has an effect on the above problems, but the effect is not sufficient. The inventors of the present invention have found that a remarkable effect can be obtained in view of the above problems by using both a cation exchanger and an anion exchanger without using only one of a cation exchanger and an anion exchanger. The reason is considered to be that, in the case where only one of the cation exchanger and the anion exchanger is used, since only one of the ions is trapped, the balance of the dissociation balance of the cation generator or the like is deteriorated, and as a result, the counter ion becomes It is in a free state and continues to exist, so that the adverse effects of the ionic components in the composition cannot be sufficiently reduced. Further, the use of both the cation exchanger and the anion exchanger is more effective for the above problems than the use of the amphoteric ion exchanger having the ion-capturing ability of both yin and yang. The reason for this is not clear, but it is considered that a compound having an ion-capturing ability of both yin and yang can cause the capturing ability to cancel each other due to the proximity of the portion having the yin/positive capturing ability, thereby reducing the effect.

作為使本發明之導電材料硬化之方法，可列舉：對導電材料照射光之方法；加熱導電材料之方法；對導電材料照射光後加熱導電材料之方法；及加熱導電材料後對導電材料照射光之方法。又，於光硬化之速度與熱硬化之速度不同之情形時等，亦可同時進行光照射與加熱。其中，較佳為對導電材料照射光之後加熱導電材料之方法。藉由將光 硬化與熱硬化併用，可於短時間內使導電材料硬化。 As a method of hardening the conductive material of the present invention, a method of irradiating light to a conductive material; a method of heating the conductive material; a method of heating the conductive material after irradiating the conductive material; and irradiating the conductive material with the light after heating the conductive material The method. Further, when the speed of photohardening is different from the speed of thermal curing, light irradiation and heating can be simultaneously performed. Among them, a method of heating the conductive material after irradiating the conductive material with light is preferred. By light Hardening and thermal hardening can be used to harden the conductive material in a short time.

上述硬化性化合物可為藉由加熱可硬化之硬化性化合物(熱硬化性化合物、或者光及熱硬化性化合物)，亦可為藉由光照射可硬化之硬化性化合物(光硬化性化合物、或者光及熱硬化性化合物)。上述硬化性化合物較佳為藉由加熱可硬化之硬化性化合物(熱硬化性化合物、或光及熱硬化性化合物)。 The curable compound may be a curable compound (a thermosetting compound or a photocurable compound) which is curable by heating, or a curable compound which is curable by light irradiation (photocurable compound, or Light and thermosetting compounds). The curable compound is preferably a curable compound (thermosetting compound or light and thermosetting compound) which is curable by heating.

上述導電材料為藉由加熱可硬化之導電材料，可包含藉由加熱可硬化之硬化性化合物(熱硬化性化合物、或者光及熱硬化性化合物)。該藉由加熱可硬化之硬化性化合物可為藉由光照射無法硬化之硬化性化合物(熱硬化性化合物)，亦可為藉由光照射與加熱兩者而可硬化之硬化性化合物(光及熱硬化性化合物)。 The conductive material is a conductive material that can be cured by heating, and may include a curable compound (thermosetting compound or light and thermosetting compound) which is curable by heating. The curable compound which can be hardened by heating can be a curable compound (thermosetting compound) which cannot be cured by light irradiation, or a curable compound which can be hardened by both light irradiation and heating (light and Thermosetting compound).

又，較佳為上述導電材料為藉由光照射與加熱兩者而可硬化之導電材料，且進而包含藉由光照射可硬化之硬化性化合物(光硬化性化合物、或者光及熱硬化性化合物)作為上述硬化性化合物。於此情形時，可藉由光照射使導電材料半硬化(B階段化)而降低導電材料之流動性之後，藉由加熱使導電材料硬化。上述藉由光照射可硬化之硬化性化合物可為藉由加熱無法硬化之硬化性化合物(光硬化性化合物)，亦可為藉由光照射與加熱兩者而可硬化之硬化性化合物(光及熱硬化性化合物)。 Further, it is preferable that the conductive material is a conductive material curable by both light irradiation and heating, and further includes a curable compound (photocurable compound, or light and thermosetting compound) which is hardenable by light irradiation. ) as the above curable compound. In this case, after the conductive material is semi-hardened (B-staged) by light irradiation to reduce the fluidity of the conductive material, the conductive material is hardened by heating. The curable compound which is hardenable by light irradiation may be a curable compound (photocurable compound) which cannot be cured by heating, or a curable compound which can be hardened by both light irradiation and heating (light and Thermosetting compound).

本發明之導電材料包含硬化劑。本發明之導電材料係包含陽離子產生劑作為上述硬化劑。上述陽離子產生劑可為 藉由而加熱產生陽離子之陽離子產生劑(熱陽離子產生劑、或者光及熱陽離子產生劑)，亦可為藉由光照射而產生陽離子之陽離子產生劑(光陽離子產生劑、或者光及熱陽離子產生劑)。對於上述硬化性化合物而言，較佳為藉由加熱而產生陽離子之陽離子產生劑(熱陽離子產生劑、或者光及熱陽離子產生劑)。 The electrically conductive material of the present invention comprises a hardener. The conductive material of the present invention contains a cation generating agent as the above-mentioned hardener. The above cation generating agent can be A cation generating agent (a thermal cation generating agent or a photo and a thermal cation generating agent) which generates a cation by heating, and may also be a cation generating agent (photo cation generating agent, or light and thermal cation) which generates a cation by light irradiation. Producer). The above-mentioned curable compound is preferably a cation generating agent (thermal cation generating agent or light and thermal cation generating agent) which generates a cation by heating.

本發明之導電材料亦可包含光硬化起始劑。本發明之導電材料較佳為包含光自由基產生劑作為上述光硬化起始劑。 The electrically conductive material of the present invention may also comprise a photohardening initiator. The conductive material of the present invention preferably contains a photo radical generating agent as the photohardening initiator.

上述導電材料較佳為包含熱硬化性化合物，且進而包含光硬化性化合物、或者光及熱硬化性化合物作為上述硬化性化合物。上述導電材料較佳為包含熱硬化性化合物與光硬化性化合物作為上述硬化性化合物。 The conductive material preferably contains a thermosetting compound, and further contains a photocurable compound or a light and thermosetting compound as the curable compound. The conductive material preferably contains a thermosetting compound and a photocurable compound as the curable compound.

以下，首先對可較佳地用於本發明之導電材料的各成分進行詳細說明。 Hereinafter, each component which can be preferably used in the conductive material of the present invention will be described in detail first.

(硬化性化合物) (hardening compound)

上述導電材料中所含之硬化性化合物並無特別限定。可使用先前公知之硬化性化合物作為上述硬化性化合物。上述硬化性化合物可僅使用1種，亦可併用2種以上。 The curable compound contained in the above conductive material is not particularly limited. A previously known curable compound can be used as the above curable compound. The curable compound may be used alone or in combination of two or more.

上述硬化性化合物較佳為含有具有環氧基之硬化性化合物。具有環氧基之硬化性化合物為環氧化合物。上述具有環氧基之硬化性化合物可僅使用1種，亦可併用2種以上。 The curable compound preferably contains a curable compound having an epoxy group. The curable compound having an epoxy group is an epoxy compound. The curable compound having an epoxy group may be used alone or in combination of two or more.

上述具有環氧基之硬化性化合物較佳為具有芳香族環。作為上述芳香族環，可列舉：苯環、萘環、蒽環、菲環、 稠四苯環、環、聯三伸苯環、苯并蒽環、芘環、稠五苯環、苉環及苝環等。其中，上述芳香族環較佳為苯環、萘環或蒽環，更佳為苯環或萘環。又，由於萘環具有平面結構，因此可更迅速地硬化，故而較佳。 The above-mentioned curable compound having an epoxy group preferably has an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a thick tetraphenyl ring. Ring, triazole ring, benzofluorene ring, anthracene ring, thick pentacene ring, anthracene ring and anthracene ring. Among them, the aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring, more preferably a benzene ring or a naphthalene ring. Further, since the naphthalene ring has a planar structure, it can be cured more rapidly, which is preferable.

就提高上述導電材料之硬化性之觀點而言，上述硬化性化合物之總體100重量%中，上述具有環氧基之硬化性化合物之含量較佳為10重量%以上，更佳為20重量%以上、100重量%以下。上述硬化性化合物亦可全部為上述具有環氧基之硬化性化合物。於將上述具有環氧基之硬化性化合物、及與該具有環氧基之硬化性化合物不同的其他硬化性化合物併用之情形時，上述硬化性化合物之總體100重量%中，上述具有環氧基之硬化性化合物之含量較佳為99重量%以下，更佳為95重量%以下，進而更佳為90重量%以下，尤佳為80重量%以下。 The content of the curable compound having an epoxy group is preferably 10% by weight or more, and more preferably 20% by weight or more, based on 100% by weight of the total of the curable compound, from the viewpoint of improving the curability of the conductive material. 100% by weight or less. The curable compound may be all of the above-mentioned curable compounds having an epoxy group. In the case where the above-mentioned curable compound having an epoxy group and another curable compound different from the curable compound having an epoxy group are used in combination, the above-mentioned epoxy group has 100% by weight of the total of the curable compound. The content of the curable compound is preferably 99% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less, and still more preferably 80% by weight or less.

上述硬化性化合物亦可進而含有與具有環氧基之硬化性化合物不同的其他硬化性化合物。作為該其他硬化性化合物，可列舉：具有不飽和雙鍵之硬化性化合物、酚硬化性化合物、胺基硬化性化合物、不飽和聚酯硬化性化合物、聚胺基甲酸酯硬化性化合物、聚矽氧硬化性化合物及聚醯亞胺硬化性化合物等。上述其他硬化性化合物可僅使用1種，亦可併用2種以上。 The curable compound may further contain another curable compound different from the curable compound having an epoxy group. Examples of the other curable compound include a curable compound having an unsaturated double bond, a phenol curable compound, an amine curable compound, an unsaturated polyester curable compound, a polyurethane curable compound, and a poly An oxygen curable compound, a polyimine hardening compound, and the like. The other curable compounds may be used alone or in combination of two or more.

就使得可容易地控制上述導電材料之硬化，或者進一步提高連接結構體之導通可靠性之觀點而言，上述硬化性化合物較佳為含有具有不飽和雙鍵之硬化性化合物。就使得 可容易地控制上述導電材料之硬化，或者更進一步提高連接結構體之導通可靠性之觀點而言，上述具有不飽和雙鍵之硬化性化合物較佳為具有(甲基)丙烯醯基之硬化性化合物。藉由使用上述具有(甲基)丙烯醯基之硬化性化合物，可容易地對B階段化之導電材料整體(包含光直接照射之部分與光未直接照射之部分)將硬化率控制為較佳之範圍，所獲得之連接結構體之導通可靠性進一步提高。 The curable compound preferably contains a curable compound having an unsaturated double bond, from the viewpoint of easily controlling the hardening of the above-mentioned conductive material or further improving the conduction reliability of the bonded structure. Just make The curable compound having an unsaturated double bond preferably has a sclerosing property of a (meth) acryl oxime group from the viewpoint of easily controlling the hardening of the above-mentioned conductive material or further improving the conduction reliability of the bonded structure. Compound. By using the above-mentioned curable compound having a (meth)acryl fluorenyl group, it is possible to easily control the B-staged conductive material as a whole (including a portion directly irradiated with light and a portion not directly irradiated with light) to control the hardening rate to be preferable. In the range, the conduction reliability of the obtained connection structure is further improved.

就可容易地控制B階段化之導電材料層之硬化率，進而使所獲得之連接結構體之導通可靠性進一步提高之觀點而言，上述具有(甲基)丙烯醯基之硬化性化合物較佳為具有1個或2個(甲基)丙烯醯基。 The above-mentioned hardening compound having a (meth)acryl fluorene group is preferable from the viewpoint of easily controlling the hardening rate of the B-staged conductive material layer and further improving the conduction reliability of the obtained bonded structure. It has one or two (meth) acrylonitrile groups.

就可容易地控制B階段化之導電材料層之硬化率，進而使所獲得之連接結構體之導通可靠性進一步提高之觀點而言，上述具有(甲基)丙烯醯基之硬化性化合物較佳為具有1個或2個(甲基)丙烯醯基。 The above-mentioned hardening compound having a (meth)acryl fluorene group is preferable from the viewpoint of easily controlling the hardening rate of the B-staged conductive material layer and further improving the conduction reliability of the obtained bonded structure. It has one or two (meth) acrylonitrile groups.

作為上述具有(甲基)丙烯醯基之硬化性化合物，可列舉不具有環氧基且具有(甲基)丙烯醯基之硬化性化合物，及具有環氧基且具有(甲基)丙烯醯基之硬化性化合物。 The curable compound having a (meth) acrylonitrile group may, for example, be a curable compound having an epoxy group and having a (meth) acryl fluorenyl group, and having an epoxy group and having a (meth) acrylonitrile group. a hardening compound.

作為上述具有(甲基)丙烯醯基之硬化性化合物，可較佳地使用：使(甲基)丙烯酸與具有羥基之化合物反應而獲得之酯化合物、使(甲基)丙烯酸與環氧化合物反應而獲得之環氧(甲基)丙烯酸酯、或使異氰酸酯與具有羥基之(甲基)丙烯酸衍生物反應而獲得之(甲基)丙烯酸胺基甲酸酯等。上述「(甲基)丙烯醯基」表示丙烯醯基及甲基丙烯醯基。 上述「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸。上述「(甲基)丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯。 As the curable compound having a (meth)acryl fluorenyl group, an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, and reacting (meth)acrylic acid with an epoxy compound can be preferably used. The obtained epoxy (meth) acrylate or a (meth)acrylic acid urethane obtained by reacting an isocyanate with a (meth)acrylic acid derivative having a hydroxyl group. The above "(meth)acryloyl group" means an acryloyl group and a methacryloyl group. The above "(meth)acrylic acid" means acrylic acid and methacrylic acid. The above "(meth) acrylate" means acrylate and methacrylate.

上述使(甲基)丙烯酸與具有羥基之化合物反應而獲得之酯化合物並無特別限定。作為該酯化合物，可使用單官能之酯化合物、雙官能之酯化合物及三官能以上之酯化合物中之任一者。 The ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group is not particularly limited. As the ester compound, any of a monofunctional ester compound, a difunctional ester compound, and a trifunctional or higher ester compound can be used.

上述具有環氧基且具有(甲基)丙烯醯基之硬化性化合物較佳為藉由將具有2個以上環氧基之化合物的一部分環氧基轉換成(甲基)丙烯醯基而獲得之硬化性化合物。該硬化性化合物為部分(甲基)丙烯酸酯化環氧化合物。 The above-mentioned curable compound having an epoxy group and having a (meth)acryl fluorenyl group is preferably obtained by converting a part of an epoxy group of a compound having two or more epoxy groups into a (meth) acryl fluorenyl group. A hardening compound. The curable compound is a partially (meth)acrylated epoxy compound.

上述硬化性化合物較佳為含有具有2個以上環氧基之化合物與(甲基)丙烯酸之反應產物。該反應產物可藉由依照常用方法，於酸性觸媒等觸媒之存在下使具有2個以上環氧基之化合物與(甲基)丙烯酸反應而獲得。較佳為環氧基之20%以上轉換(轉化率)成(甲基)丙烯醯基。轉化率更佳為30%以上，且較佳為80%以下，更佳為70%以下。尤佳為環氧基之40%以上、60%以下轉換成(甲基)丙烯醯基。 The curable compound is preferably a reaction product containing a compound having two or more epoxy groups and (meth)acrylic acid. The reaction product can be obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid in the presence of a catalyst such as an acid catalyst according to a usual method. It is preferred that 20% or more of the epoxy group is converted (conversion ratio) to a (meth) acrylonitrile group. The conversion ratio is more preferably 30% or more, and is preferably 80% or less, more preferably 70% or less. More preferably, 40% or more and 60% or less of the epoxy group are converted into a (meth) acrylonitrile group.

作為上述部分(甲基)丙烯酸酯化環氧化合物，可列舉：雙酚型環氧(甲基)丙烯酸酯、甲酚酚醛清漆型環氧(甲基)丙烯酸酯、羧酸酐改性環氧(甲基)丙烯酸酯、及苯酚酚醛清漆型環氧(甲基)丙烯酸酯等。 Examples of the partial (meth)acrylated epoxy compound include bisphenol epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and carboxylic anhydride modified epoxy ( Methyl) acrylate, and phenol novolac type epoxy (meth) acrylate.

上述硬化性化合物亦可使用將具有2個以上環氧基之苯氧基樹脂之一部分環氧基轉換成(甲基)丙烯醯基所得的改性苯氧基樹脂。即，亦可使用具有環氧基與(甲基)丙烯醯 基之改性苯氧基樹脂。 The curable compound may be a modified phenoxy resin obtained by converting a partial epoxy group of a phenoxy resin having two or more epoxy groups to a (meth) acrylonitrile group. That is, it is also possible to use an epoxy group and (meth) acrylonitrile. Modified phenoxy resin.

又，上述硬化性化合物可為交聯性化合物，亦可為非交聯性化合物。 Further, the curable compound may be a crosslinkable compound or a non-crosslinkable compound.

作為上述交聯性化合物之具體例，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、丙三醇甲基丙烯酸酯丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯、二乙烯苯、聚酯(甲基)丙烯酸酯、及(甲基)丙烯酸胺基甲酸酯等。 Specific examples of the crosslinkable compound include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-fluorene. Alcohol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di Methyl) acrylate, glycerol methacrylate acrylate, pentaerythritol tri(meth) acrylate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, (meth) acrylate Vinyl ester, divinylbenzene, polyester (meth) acrylate, and (meth) acrylate urethane.

作為上述非交聯性化合物之具體例，可列舉：(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯及(甲基)丙烯酸十四烷基酯等。 Specific examples of the non-crosslinkable compound include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl methacrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid-2- Ethylhexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, Dodecyl (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (meth)acrylate.

於將熱硬化性化合物與光硬化性化合物併用之情形時，光硬化性化合物與熱硬化性化合物之調配比可根據光硬化性化合物與熱硬化性化合物之種類而適當調整。對於上述 導電材料而言，較佳為以重量比1：99~90：10而包含光硬化性化合物與熱硬化性化合物，更佳為以5：95~60：40而包含，進而更佳為以10：90~40：60而包含。 When the thermosetting compound and the photocurable compound are used in combination, the compounding ratio of the photocurable compound to the thermosetting compound can be appropriately adjusted depending on the type of the photocurable compound and the thermosetting compound. For the above The conductive material preferably contains a photocurable compound and a thermosetting compound in a weight ratio of 1:99 to 90:10, more preferably 5:95 to 60:40, and even more preferably 10 :90~40:60 and included.

(硬化劑) (hardener)

上述導電材料包含硬化劑。該硬化劑可為熱硬化劑，亦可為光硬化起始劑。該硬化劑含有陽離子產生劑。該陽離子產生劑可使用先前公知之陽離子產生劑。又，於本發明中，陽離子產生劑較佳為並非作為僅用以使導電材料光硬化之光陽離子產生劑而使用，而作為用以使導電材料至少熱硬化之熱陽離子產生劑而使用。進而，於本發明中，陽離子產生劑較佳為並非作為用以使導電材料光硬化之光陽離子產生劑而使用，而作為用以使導電材料熱硬化之熱陽離子產生劑而使用。上述陽離子產生劑可僅使用1種，亦可併用2種以上。 The above conductive material contains a hardener. The hardener may be a heat hardener or a photohardening initiator. The hardener contains a cation generator. As the cation generating agent, a previously known cation generating agent can be used. Further, in the present invention, the cation generating agent is preferably used not as a photocation generating agent for photohardening only a conductive material, but as a thermal cation generating agent for thermally hardening at least a conductive material. Further, in the present invention, the cation generating agent is preferably used not as a photocation generating agent for photocuring a conductive material, but as a thermal cation generating agent for thermally hardening a conductive material. The cation generating agent may be used alone or in combination of two or more.

上述陽離子產生劑可較佳地使用錪鹽及鋶鹽。例如，作為上述陽離子產生劑之市售品，可列舉：三新化學公司製造之San-Aid SI-45L、San-Aid SI-60L、San-Aid SI-80L、San-Aid SI-100L、San-Aid SI-110L、San-Aid SI-150L；楠本化成公司製造之K-PURE；及ADEKA公司製造之Adeka Optomer SP-150、Adeka Optomer SP-170等。 As the above cationic generating agent, a phosphonium salt and a phosphonium salt can be preferably used. For example, as a commercial product of the above-mentioned cation generating agent, San-Aid SI-45L, San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San manufactured by Sanshin Chemical Co., Ltd. -Aid SI-110L, San-Aid SI-150L; K-PURE manufactured by Nanben Chemical Co., Ltd.; and Adeka Optomer SP-150, Adeka Optomer SP-170 manufactured by ADEKA Corporation.

作為較佳之陽離子產生劑之陰離子部分，可列舉PF6、BF4、及B(C6F5)4。 Preferred examples of the anion portion of the cation generating agent include PF 6 , BF 4 and B(C 6 F 5 ) 4 .

又，作為上述陽離子產生劑之其他具體例，可列舉：四(五氟苯基)硼酸-2-丁烯基二甲基鋶、四氟硼酸-2-丁烯基二 甲基鋶、六氟磷酸-2-丁烯基二甲基鋶、四(五氟苯基)硼酸-2-丁烯基四亞甲基鋶、四氟硼酸-2-丁烯基四亞甲基鋶、六氟磷酸-2-丁烯基四亞甲基鋶、四(五氟苯基)硼酸-3-甲基-2-丁烯基二甲基鋶、四氟硼酸-3-甲基-2-丁烯基二甲基鋶、六氟磷酸-3-甲基-2-丁烯基二甲基鋶、四(五氟苯基)硼酸-3-甲基-2-丁烯基四亞甲基鋶、四氟硼酸-3-甲基-2-丁烯基四亞甲基鋶、六氟磷酸-3-甲基-2-丁烯基四亞甲基鋶、四(五氟苯基)硼酸-4-羥基苯基肉桂基甲基鋶、四氟硼酸-4-羥基苯基肉桂基甲基鋶、六氟磷酸-4-羥基苯基肉桂基甲基鋶、四(五氟苯基)硼酸-α-萘基甲基四亞甲基鋶、四氟硼酸-α-萘基甲基四亞甲基鋶、六氟磷酸-α-萘基甲基四亞甲基鋶、四(五氟苯基)硼酸肉桂基二甲基鋶、四氟硼酸肉桂基二甲基鋶、六氟磷酸肉桂基二甲基鋶、四(五氟苯基)硼酸肉桂基四亞甲基鋶、四氟硼酸肉桂基四亞甲基鋶、六氟磷酸肉桂基四亞甲基鋶、四(五氟苯基)硼酸聯苯基甲基二甲基鋶、四氟硼酸聯苯基甲基二甲基鋶、六氟磷酸聯苯基甲基二甲基鋶、四(五氟苯基)硼酸聯苯基甲基四亞甲基鋶、四氟硼酸聯苯基甲基四亞甲基鋶、六氟磷酸聯苯基甲基四亞甲基鋶、四(五氟苯基)硼酸苯基甲基二甲基鋶、四氟硼酸苯基甲基二甲基鋶、六氟磷酸苯基甲基二甲基鋶、四(五氟苯基)硼酸苯基甲基四亞甲基鋶、四氟硼酸苯基甲基四亞甲基鋶、六氟磷酸苯基甲基四亞甲基鋶、四(五氟苯基)硼酸茀基甲基二甲基鋶、四氟硼酸茀基甲基二甲基鋶、六氟磷酸茀基甲基二甲基鋶、四(五氟苯基)硼酸 茀基甲基四亞甲基鋶、四氟硼酸茀基甲基四亞甲基鋶、及六氟磷酸茀基甲基四亞甲基鋶等。 Further, as another specific example of the above cation generating agent, 4-(pentafluorophenyl)borate-2-butenyldimethylhydrazine and tetrafluoroboric acid-2-butenyl 2 may be mentioned. Methyl hydrazine, 2-butenyl dimethyl sulfonium hexafluorophosphate, 2-butenyl tetramethylene fluorene tetrakis(pentafluorophenyl)borate, 2-butenyl tetramethylene tetrafluoroborate Base, hexafluorophosphate-2-butenyltetramethylene fluorene, tetrakis(pentafluorophenyl)borate-3-methyl-2-butenyl dimethyl hydrazine, tetrafluoroborate-3-methyl 2-butenyl dimethyl hydrazine, hexafluorophosphate-3-methyl-2-butenyl dimethyl hydrazine, tetrakis(pentafluorophenyl)borate-3-methyl-2-butenyl four Methylene hydrazine, tetramethylborate tetramethylammonium tetrafluoroborate, 3-methyl-2-butenyltetramethylene hexafluorophosphate, tetrakis(pentafluorobenzene) Boric acid 4-hydroxyphenyl cinnamylmethyl hydrazine, tetrafluoroboric acid-4-hydroxyphenyl cinnamylmethyl hydrazine, hexafluorophosphate-4-hydroxyphenyl cinnamylmethyl hydrazine, tetrakis(pentafluorobenzene) Boric acid-α-naphthylmethyltetramethylene fluorene, tetrafluoroboric acid-α-naphthylmethyltetramethylene fluorene, hexafluorophosphate-α-naphthylmethyltetramethylene fluorene, tetra Pentafluorophenyl)boronic acid cinnamyl dimethyl hydrazine, tetrafluoroboric acid cinnamyl dimethyl hydrazine, hexyl fluorophosphate cinnamyl dimethyl hydrazine, tetrakis(pentafluorophenyl)boronic acid cinnamyl tetramethylene fluorene, four Cinnamon fluoroborate Tetramethyl hydrazine, hexyl fluorophosphate cinnamyltetramethylene fluorene, tetrakis(pentafluorophenyl)borate biphenylmethyl dimethyl hydrazine, tetrafluoroborate biphenylmethyl dimethyl hydrazine, hexafluoro Biphenylmethyldimethylphosphonium phosphate, biphenylmethyltetramethylenesulfonium tetrakis(pentafluorophenyl)borate, biphenylmethyltetramethylenetetrafluoroborate, biphenylphosphonium hexafluorophosphate Methyltetramethylene fluorene, tetrakis(pentafluorophenyl)boronic acid phenylmethyl dimethyl hydrazine, tetrafluoroboric acid phenylmethyl dimethyl hydrazine, hexafluorophosphate phenylmethyl dimethyl hydrazine, four (pentafluorophenyl)boronic acid phenylmethyltetramethylene fluorene, tetrafluoroboric acid phenylmethyltetramethylene fluorene, hexafluorophosphate phenylmethyltetramethylene fluorene, tetrakis(pentafluorophenyl) Methyl dimethyl hydrazine borate, decyl methyl dimethyl hydrazine tetrafluoroborate, decyl methyl dimethyl hydrazine hexafluorophosphate, tetrakis(pentafluorophenyl) boric acid Mercaptomethyltetramethylenesulfonium, decylmethyltetramethylenesulfonium tetrafluoroborate, and mercaptomethyltetramethylenephosphonium hexafluorophosphate.

上述陽離子產生劑較佳為藉由加熱而釋出無機酸離子，或者藉由加熱而釋出含硼原子之有機酸離子。上述陽離子產生劑較佳為藉由加熱而釋出無機酸離子之成分，且藉由加熱而釋出含硼原子之有機酸離子之成分亦較佳。 The above cation generating agent preferably releases inorganic acid ions by heating, or releases organic acid ions containing boron atoms by heating. The above cation generating agent is preferably a component which releases inorganic acid ions by heating, and a component which releases organic acid ions containing a boron atom by heating is also preferable.

藉由加熱而釋出無機酸離子之陽離子產生劑較佳為具有SbF6-或PF6-作為陰離子部分之化合物。上述陽離子產生劑較佳為具有SbF6-作為陰離子部分之化合物，具有PF6-作為陰離子部分之化合物亦較佳。 The cation generating agent which releases inorganic acid ions by heating is preferably a compound having SbF 6- or PF 6- as an anion moiety. The above cationic generator is preferably a compound having SbF 6- as an anion moiety, and a compound having PF 6- as an anion moiety is also preferred.

上述陽離子產生劑之陰離子部分較佳為以B(C6X5)4 -表示。釋出含硼原子之有機酸離子之陽離子產生劑較佳為具有下述式(1)所示之陰離子部分之化合物。 The anion portion of the above cationic generating agent is preferably represented by B(C 6 X 5 ) 4 - . The cation generating agent which releases the organic acid ion of a boron atom is preferably a compound having an anion moiety represented by the following formula (1).

上述式(1)中，X表示鹵素原子。上述式(1)中之X較佳為氯原子、溴原子或氟原子，更佳為氟原子。 In the above formula (1), X represents a halogen atom. X in the above formula (1) is preferably a chlorine atom, a bromine atom or a fluorine atom, more preferably a fluorine atom.

上述陽離子產生劑之陰離子部分較佳為以B(C6F5)4 -表示。上述釋出含硼原子之有機酸離子之陽離子產生劑更佳為具有下述式(1A)所示之陰離子部分之化合物。 The anion portion of the above cationic generating agent is preferably represented by B(C 6 F 5 ) 4 - . The cation generating agent which releases the organic acid ion containing a boron atom is more preferably a compound having an anion moiety represented by the following formula (1A).

[化2] [Chemical 2]

上述陽離子產生劑之含量並無特別限定。相對於上述硬化性化合物100重量份，上述陽離子產生劑之含量較佳為0.01重量份以上，更佳為0.05重量份以上，進而更佳為5重量份以上，尤佳為10重量份以上，且較佳為40重量份以下，更佳為30重量份以下，進而更佳為20重量份以下。若上述陽離子產生劑相對於上述硬化性化合物之含量為上述下限以上且上述上限以下，則導電材料可充分地硬化。 The content of the above cation generating agent is not particularly limited. The content of the cation generating agent is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, and still more preferably 10 parts by weight or more, based on 100 parts by weight of the curable compound. It is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. When the content of the cation generating agent with respect to the curable compound is not less than the above lower limit and not more than the above upper limit, the conductive material can be sufficiently cured.

相對於上述藉由加熱可硬化之硬化性化合物100重量份，上述陽離子產生劑之含量較佳為0.01重量份以上，更佳為0.05重量份以上，進而更佳為5重量份以上，尤佳為10重量份以上，且較佳為40重量份以下，更佳為30重量份以下，進而更佳為20重量份以下。若上述陽離子產生劑相對於上述藉由加熱可硬化之硬化性化合物之含量為上述下限以上且上述上限以下，則導電材料可充分地熱硬化。 The content of the above cationic generating agent is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more, and particularly preferably 100 parts by weight of the hardenable curable compound. 10 parts by weight or more, and preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. When the content of the cation generating agent with respect to the hardenable curable compound by heating is not less than the above lower limit and not more than the above upper limit, the conductive material can be sufficiently thermally cured.

就進一步提高電極間之導通可靠性及連接結構體於高濕下之連接可靠性的觀點而言，上述導電材料較佳為包含上述陽離子產生劑與熱自由基產生劑兩者。上述熱自由基產生劑並無特別限定。可使用先前公知之熱自由基產生劑作為上述熱自由基產生劑。上述熱自由基產生劑可僅使用1種，亦可併用2種以上。此處，所謂「熱自由基產生劑」，係表示藉由加熱而生成自由基種之化合物。 The conductive material preferably contains both the cation generating agent and the thermal radical generating agent from the viewpoint of further improving the conduction reliability between the electrodes and the connection reliability of the bonded structure under high humidity. The above thermal radical generating agent is not particularly limited. A previously known thermal radical generator can be used as the above thermal radical generator. The above-mentioned thermal radical generating agent may be used alone or in combination of two or more. Here, the "thermal radical generating agent" means a compound which generates a radical species by heating.

上述熱自由基產生劑並無特別限定，可列舉偶氮化合物及過氧化物等。作為上述過氧化物，可列舉：過氧化二醯化合物、過氧酯化合物、過氧化氫化合物、過氧化二碳酸酯化合物、過氧縮酮化合物、過氧化二烷基化合物、及過氧化酮化合物等。 The thermal radical generating agent is not particularly limited, and examples thereof include an azo compound and a peroxide. Examples of the peroxide include a dioxane compound, a peroxyester compound, a hydrogen peroxide compound, a peroxydicarbonate compound, a peroxyketal compound, a dialkyl peroxide compound, and a ketone peroxide compound. Wait.

作為上述偶氮化合物，例如可列舉：2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、1,1'-偶氮雙-1-環己腈、2,2'-偶氮雙異丁酸二甲酯、2,2'-偶氮雙(2-甲基丙酸甲酯)、1,1'-偶氮雙(1-環己甲酸甲酯)、4,4'-偶氮雙(4-氰基戊酸)、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2-第三丁基偶氮-2-氰基丙烷、2,2'-偶氮雙(2-甲基丙醯胺)二水合物、及2,2'-偶氮雙(2,4,4-三甲基戊烷)等。 Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis (2, 4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis(2- Methyl methacrylate), 1,1'-azobis(methyl 1-cyclohexanoate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azo Bis(2-amidinopropane) dihydrochloride, 2-t-butylazo-2-cyanopropane, 2,2'-azobis(2-methylpropionamide) dihydrate, and 2,2'-azobis(2,4,4-trimethylpentane) and the like.

作為上述過氧化二醯化合物，可列舉：過氧化苯甲醯、過氧化二異丁醯、過氧化二(3,5,5-三甲基己醯)、過氧化二月桂醯、及過氧化二琥珀醯(Disuccinic acid peroxide)等。作為上述過氧酯化合物，可列舉：過氧化新癸酸異丙苯酯、過氧化新癸酸-1,1,3,3-四甲基丁酯、過氧化新癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化新庚酸第三丁酯、過氧化三甲基乙酸第三己酯、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-乙基己醯基過氧基)己烷、過氧化-2-乙基己酸第三己酯、過氧化三甲基乙酸第三丁酯、過氧化-2-乙基己酸第三丁酯、過氧化異丁酸第三丁酯、過氧化月桂酸第三丁酯、過氧化間苯二甲酸第 三丁酯、過氧化乙酸第三丁酯、過氧化辛酸第三丁酯及過氧化苯甲酸第三丁酯等。作為上述過氧化氫化合物，可列舉：氫過氧化異丙苯、氫過氧化對薄荷烷等。作為上述過氧化二碳酸酯化合物，可列舉：過氧化二碳酸二-第二丁酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二正丙酯、過氧化碳酸二異丙酯、及過氧化碳酸二(2-乙基己基)酯等。又，作為上述過氧化物之其他例，可列舉：過氧化甲基乙基酮、過氧硫酸鉀、及1,1-雙(第三丁基過氧基)-3,3,5-三甲基環己烷等。 Examples of the above-mentioned dioxonium peroxide compound include benzammonium peroxide, diisobutylphosphonium peroxide, bis(3,5,5-trimethylhexyl peroxide), dilaurin peroxide, and peroxidation. Disuccinic acid peroxide and the like. Examples of the peroxyester compound include cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, and trihexyl peroxy neodecanoate. Peroxidic neodecanoic acid tert-butyl ester, peroxy neoheptanoic acid tert-butyl ester, trimethyl acetoxyacetate trihexyl ester, peroxy-2-ethylhexanoic acid-1,1,3,3-tetra Methyl butyl ester, 2,5-dimethyl-2,5-di(2-ethylhexylperoxy)hexane, perhexyl peroxy-2-ethylhexanoate, peroxidation Tert-butyl methacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, third butyl laurate, peroxyisophthalic acid Tributyl ester, tert-butyl peroxyacetate, tert-butyl peroxyoctanoate and tert-butyl peroxybenzoate. Examples of the hydrogen peroxide compound include cumene hydroperoxide, hydroperoxide, and menthane. Examples of the peroxydicarbonate compound include di-second butyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, and di-n-propyl peroxydicarbonate. Diisopropyl carbonate, and di(2-ethylhexyl)peroxycarbonate. Further, examples of the other examples of the peroxide include methyl ethyl ketone peroxide, potassium peroxy potassium sulfate, and 1,1-bis(t-butylperoxy)-3,3,5-three. Methylcyclohexane and the like.

用以獲得上述熱自由基產生劑之10小時半衰期之分解溫度較佳為30℃以上，更佳為40℃以上，且較佳為90℃以下，更佳為80℃以下，進而更佳為70℃以下。若用以獲得上述熱自由基產生劑之10小時半衰期之分解溫度未達30℃，則存在導電材料之儲存穩定性降低之傾向，若超過90℃，則存在藉由上述熱自由基產生劑之作用難以使導電材料充分地熱硬化之傾向。 The decomposition temperature for obtaining the 10-hour half-life of the above thermal radical generator is preferably 30 ° C or more, more preferably 40 ° C or more, and is preferably 90 ° C or less, more preferably 80 ° C or less, and still more preferably 70 Below °C. If the decomposition temperature for obtaining the 10-hour half-life of the above thermal radical generator is less than 30 ° C, the storage stability of the conductive material tends to decrease, and if it exceeds 90 ° C, the thermal radical generating agent is present. It is difficult to make the conductive material sufficiently thermally hardened.

上述熱硬化劑之含量並無特別限定。相對於上述硬化性化合物中之上述藉由加熱可硬化之硬化性化合物100重量份，上述熱硬化劑之含量較佳為0.01重量份以上，更佳為0.05重量份以上，進而更佳為5重量份以上，尤佳為10重量份以上，且較佳為40重量份以下，更佳為30重量份以下，進而更佳為20重量份以下。若上述熱硬化劑之含量為上述下限以上且上述上限以下，則可使導電材料充分地熱硬化。關於上述熱硬化劑之含量，於上述熱硬化劑僅為陽 離子產生劑之情形時，係表示陽離子產生劑之含量，於上述熱硬化劑包含陽離子產生劑與其他熱硬化劑(熱自由基產生劑等)兩者之情形時，係表示陽離子產生劑與其他熱硬化劑之合計含量。 The content of the above-mentioned thermosetting agent is not particularly limited. The content of the above-mentioned heat curing agent is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and still more preferably 5 parts by weight based on 100 parts by weight of the above-mentioned curable compound which is hardenable by heating. The amount is preferably 10 parts by weight or more, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. When the content of the above-mentioned thermosetting agent is not less than the above lower limit and not more than the above upper limit, the conductive material can be sufficiently thermally cured. Regarding the content of the above thermal hardener, the above heat hardener is only positive In the case of an ion generator, it means the content of a cation generating agent, and when the above-mentioned thermosetting agent contains both a cation generating agent and another thermosetting agent (thermal radical generating agent, etc.), it means a cation generating agent and others. The total content of the heat hardener.

於上述硬化劑包含熱自由基產生劑之情形時，相對於上述硬化性化合物中之上述藉由加熱可硬化之硬化性化合物100重量份，上述熱自由基產生劑之含量較佳為0.01重量份以上，更佳為0.05重量份以上，且較佳為10重量份以下，更佳為5重量份以下。若上述熱自由基產生劑之含量為上述下限以上且上述上限以下，則可使導電材料充分地熱硬化。 When the curing agent contains a thermal radical generating agent, the content of the thermal radical generating agent is preferably 0.01 parts by weight based on 100 parts by weight of the hardenable curable compound in the curable compound. The above is more preferably 0.05 parts by weight or more, and is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the thermal radical generator is not less than the above lower limit and not more than the above upper limit, the conductive material can be sufficiently thermally cured.

上述導電材料亦可包含光硬化起始劑作為上述硬化劑。光硬化起始劑包括上述之光陽離子產生劑(光陽離子產生劑、或者光及熱陽離子產生劑)。上述光硬化起始劑並無特別限定。可使用先前公知之光硬化起始劑作為上述光硬化起始劑。就進一步提高電極間之導通可靠性及連接結構體之連接可靠性的觀點而言，上述導電材料較佳為包含光自由基產生劑。上述光硬化起始劑可僅使用1種，亦可併用2種以上。 The above conductive material may also contain a photohardening initiator as the above-mentioned hardener. The photohardening initiator includes the above photocation generator (photocation generator, or photo and thermal cation generator). The photohardening initiator is not particularly limited. A previously known photohardening initiator can be used as the above photohardening initiator. The conductive material preferably contains a photo radical generating agent from the viewpoint of further improving the conduction reliability between the electrodes and the connection reliability of the connection structure. The photohardening initiator may be used alone or in combination of two or more.

作為上述陽離子產生劑以外之其他光硬化起始劑，並無特別限定，可列舉：苯乙酮光硬化起始劑(苯乙酮光自由基產生劑)、二苯甲酮光硬化起始劑(二苯甲酮光自由基產生劑)、9-氧硫、縮酮光硬化起始劑(縮酮光自由基產生劑)、鹵代酮、醯基氧化膦及醯基磷酸酯等。 The photocuring initiator other than the above-mentioned cation generating agent is not particularly limited, and examples thereof include an acetophenone photohardening initiator (acetophenone photoradical generator) and a benzophenone photocuring initiator. (benzophenone photoradical generator), 9-oxosulfur , a ketal photohardening initiator (ketal photoradical generator), a halogenated ketone, a fluorenylphosphine oxide, a decyl phosphate, and the like.

作為上述苯乙酮光硬化起始劑之具體例，可列舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、甲氧基苯乙酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、及2-羥基-2-環己基苯乙酮等。作為上述縮酮光硬化起始劑之具體例，可列舉苯偶醯二甲基縮酮等。 Specific examples of the acetophenone photohardening initiator include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone and 2-hydroxy-2-methyl- 1-phenylpropan-1-one, methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylbenzene Ethyl ketone and the like. Specific examples of the ketal photohardening initiator include benzoin dimethyl ketal and the like.

上述光硬化起始劑之含量並無特別限定。相對於上述硬化性化合物中之上述藉由光照射可硬化之硬化性化合物100重量份，上述光硬化起始劑之含量較佳為0.1重量份以上，更佳為0.2重量份以上，且較佳為2重量份以下，更佳為1重量份以下。若上述光硬化起始劑之含量為上述下限以上且上述上限以下，則可使導電材料適度地光硬化。藉由對導電材料照射光而進行B階段化，可抑制導電材料之流動。關於上述光硬化起始劑之含量，於上述光硬化起始劑僅為陽離子產生劑之情形時，表示陽離子產生劑之含量，於上述光硬化起始劑包含陽離子產生劑與其他光硬化起始劑兩者之情形時，表示陽離子產生劑與其他光硬化起始劑之合計含量。 The content of the photohardening initiator is not particularly limited. The content of the photohardening initiator is preferably 0.1 part by weight or more, more preferably 0.2 part by weight or more, and more preferably 100 parts by weight of the curable compound which is hardenable by light irradiation in the curable compound. It is 2 parts by weight or less, more preferably 1 part by weight or less. When the content of the photohardening initiator is not less than the above lower limit and not more than the above upper limit, the conductive material can be appropriately photocured. By performing B-stage formation by irradiating light to the conductive material, the flow of the conductive material can be suppressed. The content of the photohardening initiator in the case where the photohardening initiator is only a cation generator, indicating the content of the cation generator, and the photohardening initiator comprises a cation generator and other photohardening initiators. In the case of both agents, the total content of the cationic generator and other photohardening initiators is indicated.

(離子交換體) (ion exchanger)

上述導電材料中所含之陽離子交換體及陰離子交換體並無特別限定。上述陽離子交換體可僅使用1種，亦可併用2種以上。上述陰離子交換體可僅使用1種，亦可併用2種以上。 The cation exchanger and the anion exchanger contained in the conductive material are not particularly limited. The cation exchanger may be used alone or in combination of two or more. The anion exchanger may be used alone or in combination of two or more.

作為上述陽離子交換體，可列舉Zr系陽離子交換體及Sb系陽離子交換體等。就進一步抑制連接結構體中之遷移， 進一步提高絕緣可靠性之觀點而言，上述陽離子交換體較佳為Zr系陽離子交換體，較佳為包含鋯原子。 Examples of the cation exchanger include a Zr-based cation exchanger and an Sb-based cation exchanger. Further inhibiting migration in the joined structure, From the viewpoint of further improving the insulation reliability, the cation exchanger is preferably a Zr-based cation exchanger, and preferably contains a zirconium atom.

作為上述陽離子交換體之市售品，可列舉IXE-100及IXE-300(以上均為東亞合成公司製造)等。 Examples of the commercially available product of the cation exchanger include IXE-100 and IXE-300 (all of which are manufactured by Toagosei Co., Ltd.).

作為上述陰離子交換體，可列舉Bi系陰離子交換體、Mg-Al系陰離子交換體及Zr系陰離子交換體等。就進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性之觀點而言，上述陽離子交換體較佳為Mg-Al系陰離子交換體，較佳為包含鎂原子及鋁原子。 Examples of the anion exchanger include a Bi-based anion exchanger, a Mg-Al anion exchanger, and a Zr-based anion exchanger. The cation exchanger is preferably a Mg-Al anion exchanger, and preferably contains a magnesium atom and an aluminum atom, from the viewpoint of further suppressing migration in the bonded structure and further improving insulation reliability.

作為上述陰離子交換體之市售品，可列舉IXE-500、IXE-530及IXE-550、IXE-700F及IXE-800(以上均為東亞合成公司製造)等。 Examples of commercially available products of the anion exchanger include IXE-500, IXE-530, and IXE-550, IXE-700F, and IXE-800 (all of which are manufactured by Toagosei Co., Ltd.).

上述陽離子交換體之中***換容量較佳為1 meq/g以上，更佳為2 meq/g以上，且較佳為10 meq/g以下，更佳為4 meq/g以下。若上述陽離子交換體之中***換容量為上述下限以上且上述上限以下，則可進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性。 The intermediate exchange capacity of the cation exchanger is preferably 1 meq/g or more, more preferably 2 meq/g or more, and is preferably 10 meq/g or less, more preferably 4 meq/g or less. When the neutral exchange capacity of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the bonded structure can be further suppressed, and insulation reliability can be further improved.

上述陰離子交換體之中***換容量較佳為0.1 meq/g以上，更佳為1 meq/g以上，且較佳為10 meq/g以下，更佳為5 meq/g以下。若上述陰離子交換體之中***換容量為上述下限以上且上述上限以下，則可進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性。 The intermediate exchange capacity of the anion exchanger is preferably 0.1 meq/g or more, more preferably 1 meq/g or more, and is preferably 10 meq/g or less, more preferably 5 meq/g or less. When the neutral exchange capacity of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the bonded structure can be further suppressed, and insulation reliability can be further improved.

上述陽離子交換體之中值粒徑較佳為0.1 μm以上，更佳為0.5 μm以上，且較佳為10 μm以下，更佳為3 μm以下。 若上述陽離子交換體之中值粒徑為上述下限以上且上述上限以下，則可進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性。 The median diameter of the cation exchanger is preferably 0.1 μm or more, more preferably 0.5 μm or more, and is preferably 10 μm or less, more preferably 3 μm or less. When the median diameter of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the bonded structure can be further suppressed, and insulation reliability can be further improved.

上述陰離子交換體之中值粒徑較佳為0.1 μm以上，更佳為0.5 μm以上，且較佳為10 μm以下，更佳為3 μm以下。若上述陰離子交換體之中值粒徑為上述下限以上且上述上限以下，則可進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性。 The median diameter of the anion exchanger is preferably 0.1 μm or more, more preferably 0.5 μm or more, and is preferably 10 μm or less, and more preferably 3 μm or less. When the median diameter of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the bonded structure can be further suppressed, and insulation reliability can be further improved.

相對於上述硬化性化合物100重量份，上述陽離子交換體之含量較佳為0.01重量份以上，更佳為0.1重量份以上，且較佳為5重量份以下，更佳為4重量份以下。若上述陽離子交換體之含量為上述下限以上且上述上限以下，則可進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性。 The content of the cation exchanger is preferably 0.01 parts by weight or more, more preferably 0.1 part by weight or more, and preferably 5 parts by weight or less, more preferably 4 parts by weight or less based on 100 parts by weight of the curable compound. When the content of the cation exchanger is not less than the above lower limit and not more than the above upper limit, migration in the bonded structure can be further suppressed, and insulation reliability can be further improved.

相對於上述硬化性化合物100重量份，上述陰離子交換體之含量較佳為0.01重量份以上，更佳為0.1重量份以上，且較佳為5重量份以下，更佳為4重量份以下。若上述陰離子交換體之含量為上述下限以上且上述上限以下，則可進一步抑制連接結構體中之遷移，進一步提高絕緣可靠性。 The content of the anion exchanger is preferably 0.01 parts by weight or more, more preferably 0.1 part by weight or more, and preferably 5 parts by weight or less, more preferably 4 parts by weight or less based on 100 parts by weight of the curable compound. When the content of the anion exchanger is not less than the above lower limit and not more than the above upper limit, migration in the bonded structure can be further suppressed, and insulation reliability can be further improved.

上述導電材料較佳為以重量比9：1~1：9而包含上述陽離子交換體與陰離子交換體，更佳為以8：2~2：8而包含，進而更佳為以6：4~4：6而包含。 Preferably, the conductive material comprises the cation exchanger and the anion exchanger at a weight ratio of 9:1 to 1:9, more preferably 8:2 to 2:8, and even more preferably 6:4~ Included in 4:6.

(導電性粒子) (conductive particles)

上述導電材料中所含之導電性粒子例如將第1、第2連接對象構件之電極間電性連接。上述導電性粒子只要為具有 導電性之粒子，則並無特別限定。上述導電性粒子只要於導電性之表面具有導電部即可。導電性粒子之導電部之表面可由絕緣層被覆。導電性粒子之導電部之表面亦可由絕緣性粒子被覆。於該等情形時，將連接對象構件連接時，需將導電部與電極之間之絕緣層或絕緣性粒子排除。 The conductive particles contained in the conductive material are electrically connected between the electrodes of the first and second connection members, for example. The above conductive particles are only required to have The conductive particles are not particularly limited. The conductive particles may have a conductive portion on the surface of the conductive material. The surface of the conductive portion of the conductive particles may be covered with an insulating layer. The surface of the conductive portion of the conductive particles may be covered with insulating particles. In such cases, when the connection member is connected, the insulating layer or the insulating particles between the conductive portion and the electrode are excluded.

作為上述導電性粒子，例如可列舉：將有機粒子、除金屬粒子以外之無機粒子、有機無機混成粒子或金屬粒子等之表面以導電層(金屬層)被覆而成之導電性粒子，及實質上僅由金屬所構成之金屬粒子等。上述導電性粒子較佳為將有機粒子、除金屬粒子以外之無機粒子、或有機無機混成粒子之表面以導電層被覆而成之導電性粒子。 Examples of the conductive particles include conductive particles obtained by coating a surface of an organic particle, inorganic particles other than metal particles, organic-inorganic mixed particles, or metal particles with a conductive layer (metal layer), and substantially Metal particles composed only of metal. The conductive particles are preferably conductive particles obtained by coating the surface of the organic particles, inorganic particles other than the metal particles, or the organic-inorganic mixed particles with a conductive layer.

上述導電部及上述金屬層並無特別限定。作為構成上述導電部之金屬，可列舉金、銀、銅、鎳、鈀及錫等。作為上述金屬層，可列舉金層、銀層、銅層、鎳層、鈀層及含有錫之金屬層等。 The conductive portion and the metal layer are not particularly limited. Examples of the metal constituting the conductive portion include gold, silver, copper, nickel, palladium, tin, and the like. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, and a metal layer containing tin.

就擴大電極與導電性粒子之接觸面積，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包含樹脂粒子、及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的導電性粒子。上述導電性粒子更佳為包含樹脂粒子、及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。 The conductive particles preferably include a resin particle and a conductive layer disposed on the surface of the resin particle from the viewpoint of increasing the contact area between the electrode and the conductive particle and further improving the conduction reliability between the electrodes (first Conductive layer). From the viewpoint of further improving the conduction reliability between the electrodes, the conductive particles are preferably conductive particles having a surface of at least the outer side of the conductive material being a low melting point metal. More preferably, the conductive particles include a resin particle and a conductive layer disposed on a surface of the resin particle, and at least the outer surface of the conductive layer is a low-melting metal layer.

上述低熔點金屬層係包含低熔點金屬之層。該所謂低熔 點金屬，係表示熔點為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包含錫。於低熔點金屬或低熔點金屬層中所含之金屬100重量%中，錫之含量較佳為30重量%以上，更佳為40重量%以上，進而更佳為70重量%以上，尤佳為90重量%以上。若上述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提高。再者，上述錫之含量可使用高頻感應耦合電漿發光光譜分析裝置(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」)等而測定。 The low melting point metal layer is a layer containing a low melting point metal. The so-called low melting A point metal is a metal having a melting point of 450 ° C or less. The melting point of the low melting point metal is preferably 300 ° C or lower, more preferably 160 ° C or lower. Further, the low melting point metal preferably contains tin. The content of tin in the 100% by weight of the metal contained in the low melting point metal or the low melting point metal layer is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. When the content of the tin is at least the above lower limit, the connection reliability between the low melting point metal and the electrode is further improved. In addition, the high-frequency inductively coupled plasma luminescence spectrum analyzer ("ICP-AES" manufactured by Horiba, Ltd.) or the fluorescent X-ray analyzer (EDX-800HS manufactured by Shimadzu Corporation) can be used. ) and measured.

於導電部之外側之表面為低熔點金屬之情形時，低熔點金屬熔融而接合於電極，藉此低熔點金屬使電極間導通。例如，低熔點金屬與電極容易面接觸而並非點接觸，故而連接電阻降低。並且，藉由使用至少導電性之外側之表面為低熔點金屬的導電性粒子，低熔點金屬與電極之接合強度升高，結果低熔點金屬與電極更不容易產生剝離，耐濕熱性進一步提高。 When the surface on the outer side of the conductive portion is a low melting point metal, the low melting point metal is melted and bonded to the electrode, whereby the low melting point metal conducts the electrodes. For example, the low melting point metal is easily in surface contact with the electrode and is not in point contact, so the connection resistance is lowered. Further, by using conductive particles having a surface of at least the outer side of the conductive material as a low melting point metal, the bonding strength between the low melting point metal and the electrode is increased, and as a result, the low melting point metal and the electrode are less likely to be peeled off, and the moist heat resistance is further improved.

構成上述低熔點金屬層之低熔點金屬並無特別限定。該低熔點金屬較佳為錫、或包含錫之合金。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。其中，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，原因在於對於電極之潤濕性優異。 The low melting point metal constituting the low melting point metal layer is not particularly limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy. Wherein, the low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, tin-indium alloy, more preferably tin-bismuth alloy, tin-indium alloy, because of the electrode Excellent wettability.

又，上述低熔點金屬較佳為焊料。上述低熔點金屬層較佳為焊料層。構成該焊料之材料並無特別限定，較佳為根據JIS Z3001：焊接用語，液相線為450℃以下之熔填材料(filler material)。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，焊料較佳為不含鉛，較佳為含錫及銦之焊料、或含錫及鉍之焊料。 Further, the low melting point metal is preferably a solder. The low melting point metal layer is preferably a solder layer. The material constituting the solder is not particularly limited, and is preferably a filler material having a liquidus of 450 ° C or less in accordance with JIS Z3001: Welding Word. Examples of the composition of the solder include a metal composition containing zinc, gold, lead, copper, tin, antimony, indium, or the like. Among them, a tin-indium-based (117 ° C eutectic) or a tin-lanthanide (139 ° C eutectic) having a low melting point and no lead is preferable. That is, the solder is preferably free of lead, preferably a solder containing tin and indium, or a solder containing tin and antimony.

為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包含：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包含鎳、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或低熔點金屬層所含之金屬100重量%中較佳為0.0001重量%以上，且較佳為1重量%以下。 In order to further improve the bonding strength between the low melting point metal and the electrode, the low melting point metal may further comprise: nickel, copper, lanthanum, aluminum, zinc, iron, gold, titanium, phosphorus, lanthanum, cerium, cobalt, lanthanum, manganese, chromium. , molybdenum, palladium and other metals. From the viewpoint of further improving the bonding strength between the low melting point metal and the electrode, the low melting point metal preferably contains nickel, copper, ruthenium, aluminum or zinc. The content of the metals for improving the bonding strength is preferably 0.0001% by weight based on 100% by weight of the metal contained in the low melting point metal or the low melting point metal layer from the viewpoint of further improving the bonding strength between the low melting point metal and the electrode. The above is preferably 1% by weight or less.

上述導電性粒子較佳為包含樹脂粒子、及配置於該樹脂粒子之表面上之導電層，該導電層之外側之表面為低熔點金屬層，且於上述樹脂粒子與上述低熔點金屬層(焊料層等)之間，包含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，上述第2導電層為上述導電層整體之一部分。於使用該導電性粒子之情形時，較佳為使第2導電層接觸電極。 Preferably, the conductive particles include a resin particle and a conductive layer disposed on a surface of the resin particle, and a surface on the outer side of the conductive layer is a low melting point metal layer, and the resin particle and the low melting point metal layer (solder) Between the layers and the like, a second conductive layer different from the above-described low melting point metal layer is included. In this case, the low-melting-point metal layer is a part of the entire conductive layer, and the second conductive layer is a part of the entire conductive layer. In the case of using the conductive particles, it is preferred that the second conductive layer is in contact with the electrode.

與上述低熔點金屬層不同之上述第2導電層較佳為包含金屬。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，上述金屬亦可使用摻錫氧化銦(ITO)。上述金屬可僅使用1種，亦可併用2種以上。 The second conductive layer different from the low melting point metal layer preferably contains a metal. The metal constituting the second conductive layer is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, ruthenium, osmium, iridium, and cadmium, and the like. Further, tin-doped indium oxide (ITO) may be used as the above metal. These metals may be used alone or in combination of two or more.

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，進而更佳為銅層。導電性粒子較佳為包含鎳層、鈀層、銅層或金層，更佳為包含鎳層或金層，進而更佳為包含銅層。藉由將包含該等較佳之導電層的導電性粒子使用於電極間之連接，電極間之連接電阻進一步降低。又，於該等較佳之導電層之表面可更容易地形成低熔點金屬層。再者，上述第2導電層亦可為焊料層等低熔點金屬層。導電性粒子可包含複數層之低熔點金屬層。 The second conductive layer is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and still more preferably a copper layer. The conductive particles preferably comprise a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and more preferably a copper layer. By using the conductive particles containing the preferred conductive layers for the connection between the electrodes, the connection resistance between the electrodes is further lowered. Further, a low melting point metal layer can be formed more easily on the surface of the preferred conductive layers. Further, the second conductive layer may be a low melting point metal layer such as a solder layer. The conductive particles may comprise a plurality of layers of a low melting point metal layer.

上述低熔點金屬層之厚度較佳為0.1 μm以上，更佳為0.5 μm以上，進而更佳為1 μm以上，且較佳為50 μm以下，更佳為10 μm以下，進而更佳為5 μm以下，尤佳為3 μm以下。若上述低熔點金屬層之厚度為上述下限以上，則導電性充分地升高。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，低熔點金屬層不易產生剝離。 The thickness of the low-melting-point metal layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, and more preferably 50 μm or less, more preferably 10 μm or less, and still more preferably 5 μm. The following is particularly preferably 3 μm or less. When the thickness of the low-melting-point metal layer is at least the above lower limit, the electrical conductivity is sufficiently increased. When the thickness of the low-melting-point metal layer is less than or equal to the above upper limit, the difference in thermal expansion coefficient between the resin particles and the low-melting-point metal layer is small, and the low-melting-point metal layer is less likely to be peeled off.

於導電層為低熔點金屬層以外之導電層之情形時，或者導電層具有多層結構之情形時，導電層之整體厚度較佳為0.1 μm以上，更佳為0.5 μm以上，進而更佳為1 μm以上， 且較佳為50 μm以下，更佳為10 μm以下，進而更佳為5 μm以下，尤佳為3 μm以下。 In the case where the conductive layer is a conductive layer other than the low melting point metal layer, or when the conductive layer has a multilayer structure, the overall thickness of the conductive layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 1 Above μm, It is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less.

上述導電性粒子之平均粒徑較佳為0.5 μm以上，更佳為1 μm以上，且較佳為100 μm以下，更佳為20 μm以下，進而更佳為15 μm以下，尤佳為10 μm以下，最佳為未達5 μm，其原因在於上述粒徑為適合於各向異性導電材料中之導電性粒子的尺寸，且可進一步縮小電極間之間隔。 The average particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, and is preferably 100 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm. Hereinafter, it is preferably less than 5 μm because the above-mentioned particle diameter is a size suitable for the conductive particles in the anisotropic conductive material, and the interval between the electrodes can be further reduced.

上述導電性粒子之平均粒徑最佳為1 μm以上且未達5 μm。藉由使用本發明之導電材料，即便導電性粒子之平均粒徑未達5 μm而導電性粒子較小，亦可充分地提高連接結構體之連接可靠性。 The average particle diameter of the above conductive particles is preferably 1 μm or more and less than 5 μm. By using the conductive material of the present invention, even if the average particle diameter of the conductive particles is less than 5 μm and the conductive particles are small, the connection reliability of the bonded structure can be sufficiently improved.

又，上述樹脂粒子可根據所安裝之基板之電極尺寸或焊墊直徑而區分使用。 Further, the resin particles may be used in accordance with the electrode size of the substrate to be mounted or the diameter of the pad.

就將上下之電極間進一步確實地連接，且進一步抑制於橫方向上鄰接之電極間之短路的觀點而言，導電性粒子之平均粒徑C相對於樹脂粒子之平均粒徑A的比(C/A)超過1.0，較佳為3.0以下。又，於在上述樹脂粒子與上述焊料層之間存在上述第2導電層之情形時，焊料層除外之導電性粒子部分之平均粒徑B相對於樹脂粒子之平均粒徑A的比(B/A)超過1.0，較佳為2.0以下。進而，於在上述樹脂粒子與上述焊料層之間存在上述第2導電層之情形時，包含焊料層在內之導電性粒子之平均粒徑C相對於焊料層除外之導電性粒子部分之平均粒徑B的比(C/B)超過1.0，較佳為2.0以下。若上述比(B/A)在上述範圍內，或者上述比 (C/B)在上述範圍內，則可將上下之電極間進一步確實地連接，且可進一步抑制於橫方向上鄰接之電極間之短路。 The ratio of the average particle diameter C of the conductive particles to the average particle diameter A of the resin particles is from the viewpoint of further reliably connecting the electrodes between the upper and lower electrodes and further suppressing the short circuit between the electrodes adjacent in the lateral direction. /A) is more than 1.0, preferably 3.0 or less. Further, in the case where the second conductive layer is present between the resin particles and the solder layer, the ratio of the average particle diameter B of the conductive particle portion excluding the solder layer to the average particle diameter A of the resin particles (B/ A) exceeds 1.0, preferably 2.0 or less. Further, when the second conductive layer is present between the resin particles and the solder layer, the average particle diameter of the conductive particles including the solder layer is equal to the average particle size of the conductive particle portion excluding the solder layer. The ratio of the diameter B (C/B) exceeds 1.0, preferably 2.0 or less. If the above ratio (B/A) is within the above range, or the above ratio When (C/B) is within the above range, the electrodes between the upper and lower electrodes can be further reliably connected, and the short circuit between the adjacent electrodes in the lateral direction can be further suppressed.

面向FOB及FOF用途之導電材料(各向異性導電材料)：上述導電材料可較佳地使用於可撓性印刷基板與環氧玻璃基板之連接(FOB(Film on Board))、或可撓性印刷基板與可撓性印刷基板之連接(FOF(Film on Film))。 Conductive material for an FOB and FOF use (anisotropic conductive material): The above conductive material can be preferably used for connection between a flexible printed substrate and a glass epoxy substrate (FOB (Film on Board)), or flexibility The connection between the printed substrate and the flexible printed substrate (FOF (Film on Film)).

於FOB及FOF用途中，存在電極之部分(線)與無電極之部分(間隙)的尺寸即L & S通常為100~500 μm。FOB及FOF用途中所使用之樹脂粒子之平均粒徑較佳為10~100 μm。若樹脂粒子之平均粒徑為10 μm以上，則配置於電極間之導電材料及連接部之厚度為充分厚，接著力進一步提高。若樹脂粒子之平均粒徑為100 μm以下，則鄰接之電極間更難產生短路。 For FOB and FOF applications, the size of the electrode portion (line) and the electrodeless portion (gap), that is, L & S is usually 100 to 500 μm. The average particle diameter of the resin particles used in the FOB and FOF applications is preferably from 10 to 100 μm. When the average particle diameter of the resin particles is 10 μm or more, the thickness of the conductive material and the connecting portion disposed between the electrodes is sufficiently thick, and the force is further improved. When the average particle diameter of the resin particles is 100 μm or less, it is more difficult to cause a short circuit between adjacent electrodes.

面向倒裝晶片用途之導電材料(各向異性導電材料)： Conductive materials for flip chip applications (anisotropic conductive materials):

上述導電材料可較佳地使用於倒裝晶片用途中。 The above conductive materials are preferably used in flip chip applications.

於倒裝晶片用途中，通常焊墊直徑為15~80 μm。倒裝晶片用途中所使用之樹脂粒子之平均粒徑較佳為1~15 μm。若樹脂粒子之平均粒徑為1 μm以上，則可將配置於該樹脂粒子之表面上之焊料層的厚度設為充分厚，可將電極間進一步確實地電性連接。若樹脂粒子之平均粒徑為10 μm以下，則鄰接之電極間更難產生短路。 In flip chip applications, solder pads are typically 15 to 80 μm in diameter. The average particle diameter of the resin particles used in the flip chip application is preferably from 1 to 15 μm. When the average particle diameter of the resin particles is 1 μm or more, the thickness of the solder layer disposed on the surface of the resin particles can be made sufficiently thick, and the electrodes can be electrically connected to each other more reliably. When the average particle diameter of the resin particles is 10 μm or less, it is more difficult to cause a short circuit between adjacent electrodes.

面向COF之導電材料(各向異性導電材料)：上述導電材料可較佳地使用於半導體晶片與可撓性印刷基板之連接(COF(Chip on Film))。 Conductive material for COF (anisotropic conductive material): The above conductive material can be preferably used for connection of a semiconductor wafer to a flexible printed substrate (COF (Chip on Film)).

於COF用途中，存在電極之部分(線)與無電極之部分(間隙)的尺寸即L & S通常為10~50 μm。COF用途中所使用之樹脂粒子之平均粒徑較佳為1~10 μm。若樹脂粒子之平均粒徑為1 μm以上，則可將配置於該樹脂粒子之表面上之焊料層之厚度設為充分厚，可將電極間進一步確實地電性連接。若樹脂粒子之平均粒徑為10 μm以下，則鄰接之電極間更難產生短路。 In COF applications, the size of the electrode (line) and the electrodeless portion (gap), that is, L & S is usually 10 to 50 μm. The average particle diameter of the resin particles used in the COF application is preferably from 1 to 10 μm. When the average particle diameter of the resin particles is 1 μm or more, the thickness of the solder layer disposed on the surface of the resin particles can be made sufficiently thick, and the electrodes can be electrically connected to each other more reliably. When the average particle diameter of the resin particles is 10 μm or less, it is more difficult to cause a short circuit between adjacent electrodes.

上述導電性粒子及上述樹脂粒子之「平均粒徑」係表示數量平均粒徑。導電性粒子之平均粒徑可藉由利用電子顯微鏡或光學顯微鏡觀察任意50個導電性粒子，算出平均值而求出。 The "average particle diameter" of the conductive particles and the resin particles means a number average particle diameter. The average particle diameter of the conductive particles can be determined by observing an arbitrary number of 50 conductive particles by an electron microscope or an optical microscope and calculating an average value.

上述導電性粒子之導電部之表面亦可經絕緣性材料、絕緣性粒子、助焊劑等進行絕緣處理。絕緣性材料、絕緣性粒子、助焊劑等較佳為可藉由連接時之熱而軟化、流動從而自連接部排除。藉此，可抑制電極間之短路。 The surface of the conductive portion of the conductive particles may be insulated by an insulating material, insulating particles, a flux, or the like. The insulating material, the insulating particles, the flux, and the like are preferably softened and flowed by the heat at the time of connection, and are removed from the joint portion. Thereby, the short circuit between the electrodes can be suppressed.

上述導電性粒子之含量並無特別限定。於上述導電材料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，進而更佳為1重量%以上，且較佳為40重量%以下，更佳為30重量%以下，進而更佳為19重量%以下。若上述導電性粒子之含量為上述下限以上且上述上限以下，則可將導電性粒子容易地配置於所應連接的上下之電極間。進而，不允許連接之鄰接之電極間不容易經由複數個導電性粒子而電性連接。即，可進一步防止相鄰之電極間之短路。 The content of the above conductive particles is not particularly limited. The content of the conductive particles is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, and preferably 40% by weight or less, based on 100% by weight of the conductive material. It is preferably 30% by weight or less, and more preferably 19% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be easily disposed between the upper and lower electrodes to be connected. Further, it is not allowed to electrically connect the electrodes adjacent to each other via the plurality of conductive particles. That is, the short circuit between adjacent electrodes can be further prevented.

(助焊劑) (flux)

上述導電材料亦可包含助焊劑。藉由使用該助焊劑，可有效果地除去電極表面所形成之氧化膜。其結果，連接結構體之導通可靠性進一步提高。再者，上述導電材料亦非必需包含助焊劑。 The above conductive material may also contain a flux. By using the flux, the oxide film formed on the surface of the electrode can be effectively removed. As a result, the conduction reliability of the connection structure is further improved. Furthermore, the above conductive material does not necessarily need to contain a flux.

上述助焊劑並無特別限定。可使用焊料接合等中通常使用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、熔融鹽、磷酸、磷酸之衍生物、有機鹵化物、肼、有機酸及松脂等。上述助焊劑可僅使用1種，亦可併用2種以上。 The flux is not particularly limited. A flux which is usually used in solder bonding or the like can be used as the flux. Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, a phosphoric acid, a derivative of phosphoric acid, an organic halide, an anthracene, and an organic acid. And turpentine and so on. The flux may be used alone or in combination of two or more.

作為上述熔融鹽，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，電極間之連接電阻進一步降低。 Examples of the molten salt include ammonium chloride and the like. Examples of the organic acid include lactic acid, citric acid, stearic acid, and glutamic acid. Examples of the rosin include activated rosin and non-activated rosin. The above flux is preferably rosin. By using turpentine, the connection resistance between the electrodes is further lowered.

上述松脂係以松脂酸為主成分之松香類。上述助焊劑較佳為松香類，更佳為松脂酸。藉由使用該較佳之助焊劑，電極間之連接電阻進一步降低。 The above rosin is a rosin mainly composed of rosin acid. The above flux is preferably rosin, more preferably rosin. By using the preferred flux, the connection resistance between the electrodes is further reduced.

上述助焊劑可分散於黏合劑樹脂中，亦可附著於上述導電性粒子之表面上。 The flux may be dispersed in the binder resin or may be attached to the surface of the conductive particles.

於上述導電材料100重量%中，上述助焊劑之含量較佳為0.5重量%以上，且較佳為30重量%以下，更佳為25重量%以下。若上述助焊劑之含量為上述下限以上且上述上限以下，則可更有效果地除去電極表面所形成之氧化膜。 又，若上述助焊劑之含量為上述下限以上，則可更有效果地顯現助焊劑之添加效果。若上述助焊劑之含量為上述上限以下，則硬化物之吸濕性進一步降低，連接結構體之可靠性進一步提高。 The content of the flux is preferably 0.5% by weight or more, and preferably 30% by weight or less, and more preferably 25% by weight or less, based on 100% by weight of the conductive material. When the content of the flux is not less than the above lower limit and not more than the above upper limit, the oxide film formed on the surface of the electrode can be removed more effectively. Moreover, when the content of the flux is at least the above lower limit, the effect of adding the flux can be more effectively exhibited. When the content of the flux is less than or equal to the above upper limit, the hygroscopicity of the cured product is further lowered, and the reliability of the bonded structure is further improved.

(其他成分) (other ingredients)

上述導電材料較佳為包含填料。藉由使用填料，可抑制導電材料之硬化物之熱線膨脹率。作為上述填料之具體例，可列舉：二氧化矽、氮化鋁、氧化鋁、玻璃、氮化硼、氮化矽、聚矽氧、碳、石墨(graphite)、石墨烯(graphene)及滑石等。填料可僅使用1種，亦可將2種以上併用。若使用熱導率較高之填料，則正式硬化時間縮短。 The above conductive material preferably contains a filler. By using the filler, the rate of thermal linear expansion of the cured material of the conductive material can be suppressed. Specific examples of the filler include cerium oxide, aluminum nitride, aluminum oxide, glass, boron nitride, cerium nitride, polyfluorene oxide, carbon, graphite, graphene, talc, and the like. . The filler may be used alone or in combination of two or more. If a filler with a high thermal conductivity is used, the actual hardening time is shortened.

上述導電材料亦可包含溶劑。藉由使用該溶劑，可容易地調整導電材料之黏度。作為上述溶劑，例如可列舉：乙酸乙酯、甲基賽路蘇、甲苯、丙酮、甲基乙基酮、環己烷、正己烷、四氫呋喃及二***等。 The above conductive material may also contain a solvent. The viscosity of the conductive material can be easily adjusted by using the solvent. Examples of the solvent include ethyl acetate, methyl sarbuta, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether.

(導電材料之詳細說明及用途) (Detailed description and use of conductive materials)

本發明之導電材料較佳為各向異性導電材料。本發明之導電材料較佳為將電極電性連接所使用之導電材料。本發明之導電材料為將有機電致發光顯示元件之電極電性連接所使用的導電材料亦較佳。本發明之導電材料為膏狀或膜狀之導電材料，較佳為膏狀之導電材料。膏狀之導電材料即導電膏。膜狀之導電材料即導電膜。於導電材料為導電膜之情形時，亦可於包含該導電性粒子之導電膜上積層不含導電性粒子之膜。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。 The conductive material of the present invention is preferably an anisotropic conductive material. The conductive material of the present invention is preferably a conductive material used for electrically connecting the electrodes. The conductive material of the present invention is also preferably a conductive material used for electrically connecting electrodes of an organic electroluminescence display element. The conductive material of the present invention is a paste or film-like conductive material, preferably a paste-like conductive material. The paste-like conductive material is a conductive paste. The film-shaped conductive material is a conductive film. When the conductive material is a conductive film, a film containing no conductive particles may be laminated on the conductive film containing the conductive particles. The above conductive paste is preferably an anisotropic conductive paste. The above conductive film is preferably an anisotropic conductive film.

本發明之導電材料較佳為係導電膏，且係可以膏狀之狀態塗佈於連接對象構件上之導電膏。 The conductive material of the present invention is preferably a conductive paste, and is a conductive paste which is applied to the member to be connected in a paste state.

上述導電膏於25℃下之黏度較佳為20 Pa．s以上，更佳為100 Pa．s以上，且較佳為1000 Pa．s以下，更佳為700 Pa．s以下，進而更佳為600 Pa．s以下。若上述黏度為上述下限以上，則可抑制導電膏中之導電性粒子沈澱。若上述黏度為上述上限以下，則導電性粒子之分散性進一步提高。只要塗佈前之上述導電膏之上述黏度在上述範圍內，則於第1連接對象構件上塗佈導電膏之後，可進一步抑制硬化前之導電膏之流動，進而更難以產生孔隙(void)。上述導電膏於25℃下之黏度亦可為300 Pa．s以下。再者，膏狀亦包括液狀。 The viscosity of the above conductive paste at 25 ° C is preferably 20 Pa. Above s, more preferably 100 Pa. Above s, and preferably 1000 Pa. Below s, more preferably 700 Pa. s below, and more preferably 600 Pa. s below. When the viscosity is at least the above lower limit, precipitation of conductive particles in the conductive paste can be suppressed. When the viscosity is not more than the above upper limit, the dispersibility of the conductive particles is further improved. When the viscosity of the conductive paste before coating is within the above range, the conductive paste is applied to the first connection member, and the flow of the conductive paste before curing can be further suppressed, and voids are more likely to be generated. The above conductive paste may have a viscosity of 300 Pa at 25 ° C. s below. Furthermore, the paste also includes liquid.

本發明之導電材料較佳為用以將具有銅電極之連接對象構件連接之導電材料。於使用導電材料將具有銅電極之連接對象構件連接之情形時，存在連接結構體中之銅電極容易引起產生遷移之問題。相對於此，藉由使用本發明之導電材料，則即便將具有銅電極之連接對象構件連接，亦可有效果地抑制連接結構體中之遷移，可有效地提高絕緣可靠性。 The conductive material of the present invention is preferably a conductive material for connecting a connection member having a copper electrode. In the case where a connection member having a copper electrode is connected using a conductive material, there is a problem in that the copper electrode in the connection structure is liable to cause migration. On the other hand, by using the conductive material of the present invention, even if the connection target member having the copper electrode is connected, the migration in the bonded structure can be effectively suppressed, and the insulation reliability can be effectively improved.

本發明之導電材料可用於將各種連接對象構件接著。上述導電材料可較佳地用於獲得第1、第2連接對象構件經電性連接的連接結構體。上述導電材料可更佳地用於獲得第1、第2連接對象構件之電極間經電性連接的連接結構體。 The electrically conductive material of the present invention can be used to join various connecting object members. The conductive material can be preferably used to obtain a bonded structure in which the first and second connection members are electrically connected. The conductive material can be more preferably used for obtaining a connection structure in which electrodes of the first and second connection members are electrically connected to each other.

圖1係以正面剖面圖模式性地表示使用本發明之一實施形態之導電材料的連接結構體之一例。 Fig. 1 is a front cross-sectional view schematically showing an example of a bonded structure using a conductive material according to an embodiment of the present invention.

圖1所示之連接結構體1包含第1連接對象構件2、第2連接對象構件4、及將第1、第2連接對象構件2、4電性連接之連接部3。連接部3為硬化物層，係藉由使包含導電性粒子5之導電材料硬化而形成。連接部3較佳為係藉由使各向異性導電材料硬化而形成。 The connection structure 1 shown in FIG. 1 includes a first connection object member 2, a second connection object member 4, and a connection portion 3 that electrically connects the first and second connection object members 2, 4. The connecting portion 3 is a cured layer formed by curing a conductive material containing the conductive particles 5. The connecting portion 3 is preferably formed by hardening an anisotropic conductive material.

第1連接對象構件2於表面2a(上表面)具有複數個第1電極2b。第2連接對象構件4於表面4a(下表面)具有複數個第2電極4b。第1電極2b與第2電極4b藉由一個或複數個導電性粒子5而電性連接。因此，第1、第2連接對象構件2、4藉由導電性粒子5而電性連接。 The first connection target member 2 has a plurality of first electrodes 2b on the front surface 2a (upper surface). The second connection target member 4 has a plurality of second electrodes 4b on the front surface 4a (lower surface). The first electrode 2b and the second electrode 4b are electrically connected by one or a plurality of conductive particles 5. Therefore, the first and second connection target members 2 and 4 are electrically connected by the conductive particles 5 .

第1、第2電極2b、4b間之連接通常係藉由下述方式而進行：將第1連接對象構件2與第2連接對象構件4經由導電材料，以第1、第2電極2b、4b彼此相對向之方式重疊之後，在使導電材料硬化之時進行加壓。藉由加壓，通常導電性粒子5受到壓縮。 The connection between the first and second electrodes 2b and 4b is usually performed by the first connection member 2 and the second connection member 4 via the conductive material, and the first and second electrodes 2b and 4b. After overlapping each other, the pressure is applied while the conductive material is hardened. The conductive particles 5 are usually compressed by pressurization.

第1、第2連接對象構件並無特別限定。作為第1、第2連接對象構件，具體而言可列舉：半導體晶片、電容器及二極體等之電子零件，及印刷基板、可撓性印刷基板及玻璃基板等電路基板等之電子零件等。上述導電材料較佳為用於連接電子零件之導電材料。 The first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include electronic components such as a semiconductor wafer, a capacitor, and a diode, and electronic components such as a printed circuit board, a flexible printed circuit board, and a circuit board such as a glass substrate. The above conductive material is preferably a conductive material for connecting electronic parts.

圖1所示之連接結構體1可經由例如圖2(a)~(c)所示之狀態，以如下之方式而獲得。 The connection structure 1 shown in Fig. 1 can be obtained in the following manner via, for example, the state shown in Figs. 2(a) to (c).

如圖2(a)所示般，準備於表面2a(上表面)具有第1電極2b之第1連接對象構件2。其次，於第1連接對象構件2之表面2a上配置包含複數個導電性粒子5之導電材料，在第1連接對象構件2之表面2a上形成導電材料層3A。此時，較佳為於第1電極2b上配置有一個或複數個導電性粒子5。 As shown in Fig. 2(a), the first connection member 2 having the first electrode 2b on the front surface 2a (upper surface) is prepared. Next, a conductive material including a plurality of conductive particles 5 is placed on the front surface 2a of the first connection member 2, and a conductive material layer 3A is formed on the front surface 2a of the first connection target member 2. In this case, it is preferable that one or a plurality of conductive particles 5 are disposed on the first electrode 2b.

繼而，藉由對導電材料層3A照射光，而進行導電材料層3A之硬化。於圖2(a)~(c)中，係對導電材料層3A照射光，進行導電材料層3A之硬化，而使導電材料層3A進行B階段化。即，如圖2(b)所示，於第1連接對象構件2之表面2a上形成經B階段化之導電材料層3B。藉由B階段化，第1連接對象構件2與經B階段化之導電材料層3B暫時接著。經B階段化之導電材料層3B為處於半硬化狀態之半硬化物。經B階段化之導電材料層3B並未完全硬化，可進而進行熱硬化。但是，亦可不對導電材料層3A進行B階段化，而對導電材料層3A照射光或將導電材料層3A加熱使導電材料層3A一次性硬化。 Then, the conductive material layer 3A is hardened by irradiating light to the conductive material layer 3A. In FIGS. 2(a) to 2(c), the conductive material layer 3A is irradiated with light, and the conductive material layer 3A is cured, and the conductive material layer 3A is B-staged. That is, as shown in FIG. 2(b), the B-staged conductive material layer 3B is formed on the surface 2a of the first connection member 2. By the B-stage, the first connection target member 2 and the B-staged conductive material layer 3B are temporarily followed. The B-staged conductive material layer 3B is a semi-hardened material in a semi-hardened state. The B-staged conductive material layer 3B is not completely cured, and can be further thermally hardened. However, the conductive material layer 3A may not be B-staged, and the conductive material layer 3A may be irradiated with light or the conductive material layer 3A may be heated to harden the conductive material layer 3A at one time.

為有效地進行導電材料層3A之硬化，照射光時之光照射強度較佳為在0.1~8000 mW/cm2之範圍內。累計光量較佳為0.1~20000 J/cm2。照射光時所使用之光源並無特別限定。作為該光源，例如可列舉於波長420 nm以下具有充分之發光分佈的光源等。又，作為光源之具體例，例如可列舉：低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵素燈及LED(Light Emitting Diode，發光二極體)燈等。 In order to effectively harden the conductive material layer 3A, the light irradiation intensity when irradiated with light is preferably in the range of 0.1 to 8000 mW/cm 2 . The cumulative amount of light is preferably from 0.1 to 20,000 J/cm 2 . The light source used when irradiating light is not particularly limited. Examples of the light source include a light source having a sufficient light emission distribution at a wavelength of 420 nm or less. Further, specific examples of the light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light, a microwave excited mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode). ) lights, etc.

繼而，如圖2(c)所示般，於經B階段化之導電材料層3B之上表面3a上積層第2連接對象構件4。以使第1連接對象構件2之表面2a之第1電極2b、與第2連接對象構件4之表面4a之第2電極4b相對向之方式積層第2連接對象構件4。 Then, as shown in FIG. 2(c), the second connection member 4 is laminated on the upper surface 3a of the B-staged conductive material layer 3B. The second connection member 4 is laminated so that the first electrode 2b on the front surface 2a of the first connection member 2 and the second electrode 4b on the surface 4a of the second connection member 4 face each other.

進而，在積層第2連接對象構件4時，對經B階段化之導電材料層3B加熱，藉此使經B階段化之導電材料層3B進一步硬化，形成連接部3。但是，亦可於積層第2連接對象構件4之前對經B階段化之導電材料層3B加熱。另外，亦可於積層第2連接對象構件4之後對經B階段化之導電材料層3B加熱。 Further, when the second connection member 4 is laminated, the B-staged conductive material layer 3B is heated, whereby the B-staged conductive material layer 3B is further cured to form the connection portion 3. However, the B-staged conductive material layer 3B may be heated before the second connection object member 4 is laminated. Further, the B-staged conductive material layer 3B may be heated after the second connection object member 4 is laminated.

藉由加熱而使導電材料層3A或經B階段化之導電材料層3B硬化時之加熱溫度較佳為50℃以上，更佳為80℃以上，進而較佳為100℃以上，進而更佳為140℃以上，尤佳為160℃以上，且較佳為250℃以下，更佳為200℃以下。於將本發明之導電材料使用於有機電致發光顯示元件中之電極之電性連接的情形時，使上述導電材料層3A或經B階段化之導電材料層3B硬化時，加熱溫度亦可為120℃以下。 The heating temperature when the conductive material layer 3A or the B-staged conductive material layer 3B is cured by heating is preferably 50 ° C or higher, more preferably 80 ° C or higher, further preferably 100 ° C or higher, and more preferably It is 140 ° C or more, particularly preferably 160 ° C or more, and preferably 250 ° C or less, more preferably 200 ° C or less. When the conductive material of the present invention is used for electrical connection of electrodes in the organic electroluminescence display device, when the conductive material layer 3A or the B-staged conductive material layer 3B is hardened, the heating temperature may be Below 120 °C.

較佳為於使經B階段化之導電材料層3B硬化時進行加壓。藉由進行加壓而以第1電極2b與第2電極4b壓縮導電性粒子5，可增大第1、第2電極2b、4b與導電性粒子5之接觸面積。因此，可提高導通可靠性。進而，藉由壓縮導電性粒子5，則即便第1、第2電極2b、4b間之距離擴大，導電性粒子5之粒徑亦可追隨該擴大而增大。 It is preferable to pressurize when the B-staged conductive material layer 3B is hardened. When the conductive particles 5 are compressed by the first electrode 2b and the second electrode 4b by pressurization, the contact area between the first and second electrodes 2b and 4b and the conductive particles 5 can be increased. Therefore, the conduction reliability can be improved. Further, by compressing the conductive particles 5, even if the distance between the first and second electrodes 2b and 4b is increased, the particle diameter of the conductive particles 5 can be increased in accordance with the expansion.

藉由使經B階段化之導電材料層3B硬化，第1連接對象 構件2與第2連接對象構件4經由連接部3而連接。又，第1電極2b與第2電極4b經由導電性粒子5而電性連接。如此，可獲得使用導電材料的圖1所示之連接結構體1。此處，由於係併用光硬化與熱硬化，故而可於短時間內使導電材料硬化。 By hardening the B-staged conductive material layer 3B, the first connection object The member 2 and the second connection object member 4 are connected via the connection portion 3 . Further, the first electrode 2b and the second electrode 4b are electrically connected via the conductive particles 5. Thus, the bonded structure 1 shown in Fig. 1 using a conductive material can be obtained. Here, since the photohardening and the thermal hardening are used together, the electrically conductive material can be hardened in a short time.

本發明之導電材料例如可使用於：可撓性印刷基板與玻璃基板之連接(FOG(Film on Glass))、半導體晶片與可撓性印刷基板之連接(COF(Chip on Film))、半導體晶片與玻璃基板之連接(COG(Chip on Glass))、或者可撓性印刷基板與環氧玻璃基板之連接(FOB(Film on Board))等。其中，上述導電材料於FOG用途或COG用途中較佳，於COG用途中更佳。本發明之導電材料較佳為可撓性印刷基板與玻璃基板之連接、或半導體晶片與玻璃基板之連接中所使用之導電材料，更佳為可撓性印刷基板與玻璃基板之連接中所使用之導電材料。 The conductive material of the present invention can be used, for example, for connection between a flexible printed substrate and a glass substrate (FOG (Film on Glass), connection of a semiconductor wafer to a flexible printed substrate (COF (Chip on Film)), and a semiconductor wafer. Connection to a glass substrate (COG (Chip on Glass)), or connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)). Among them, the above conductive material is preferred for FOG use or COG use, and is more preferable for COG use. The conductive material of the present invention is preferably a conductive material used for connection between a flexible printed substrate and a glass substrate, or a connection between a semiconductor wafer and a glass substrate, and more preferably used for connection between a flexible printed substrate and a glass substrate. Conductive material.

於本發明之連接結構體中，較佳為上述第2連接對象構件與上述第1連接對象構件為可撓性印刷基板與玻璃基板、或半導體晶片與玻璃基板，更佳為可撓性印刷基板與玻璃基板。 In the connection structure of the present invention, it is preferable that the second connection target member and the first connection target member are a flexible printed circuit board and a glass substrate, or a semiconductor wafer and a glass substrate, and more preferably a flexible printed circuit board. With a glass substrate.

又，本發明之連接結構體為有機電致發光顯示元件亦較佳。上述有機電致發光顯示元件之電極可由上述導電材料中所含之導電性粒子電性連接。 Further, the connection structure of the present invention is also preferably an organic electroluminescence display element. The electrode of the organic electroluminescence display element may be electrically connected to the conductive particles contained in the conductive material.

較佳為上述第1電極及上述第2電極中之至少一者為銅電極。較佳為上述第1電極及上述第2電極兩者均為銅電極。 於此情形時，可獲得更佳的抑制本發明之導電材料所引起之遷移的效果，連接結構體之絕緣可靠性進一步提高。 Preferably, at least one of the first electrode and the second electrode is a copper electrode. Preferably, both of the first electrode and the second electrode are copper electrodes. In this case, it is possible to obtain a better effect of suppressing the migration caused by the conductive material of the present invention, and the insulation reliability of the bonded structure is further improved.

電極寬度(第1電極寬度及第2電極寬度)較佳為5 μm以上，更佳為10 μm以上，且較佳為500 μm以下，更佳為300 μm以下。電極間寬度(第1電極間寬度及第2電極間寬度)較佳為3 μm以上，更佳為10 μm以上，且較佳為500 μm以下，更佳為300 μm以下。又，電極寬度/電極間寬度即L/S(線/間隙)較佳為5 μm/5 μm以上，更佳為10 μm/10 μm以上，且較佳為500 μm/500 μm以下，更佳為300 μm/300 μm以下。 The electrode width (the first electrode width and the second electrode width) is preferably 5 μm or more, more preferably 10 μm or more, and is preferably 500 μm or less, and more preferably 300 μm or less. The inter-electrode width (the width between the first electrodes and the width between the second electrodes) is preferably 3 μm or more, more preferably 10 μm or more, and is preferably 500 μm or less, and more preferably 300 μm or less. Further, the electrode width/electrode width, that is, L/S (line/gap) is preferably 5 μm/5 μm or more, more preferably 10 μm/10 μm or more, and is preferably 500 μm/500 μm or less, more preferably It is 300 μm/300 μm or less.

再者，近年來，上述連接結構體中之電極寬度/電極間寬度即L/S(線/間隙)不斷地進一步減小。上述連接結構體中之電極之L/S越小，則產生遷移時越容易產生絕緣故障。針對於此，藉由使用本發明之導電材料，則即便連接微細之電極，亦可有效果地抑制絕緣故障之產生，可充分地確保絕緣可靠性。 Further, in recent years, the electrode width/inter-electrode width, that is, L/S (line/gap) in the above-described bonded structure has been continuously reduced. The smaller the L/S of the electrode in the above-mentioned connection structure, the more easily the insulation failure occurs when migration occurs. On the other hand, by using the conductive material of the present invention, even if a fine electrode is connected, the occurrence of insulation failure can be effectively suppressed, and the insulation reliability can be sufficiently ensured.

以下，列舉實施例、比較例及參考例對本發明進行具體說明。本發明並不僅限於以下之實施例。 Hereinafter, the present invention will be specifically described by way of examples, comparative examples and reference examples. The invention is not limited to the following examples.

於實施例及比較例中，係使用以下材料。 In the examples and comparative examples, the following materials were used.

(離子交換體) (ion exchanger)

(1)IXE-100(Zr系陽離子交換體，中***換容量3.3 meq/g，東亞合成公司製造) (1) IXE-100 (Zr-based cation exchanger, neutral exchange capacity 3.3 meq/g, manufactured by Toagosei Co., Ltd.)

(2)IXE-700F(Mg-Al系陰離子交換體，中***換容量4.5 meq/g，東亞合成公司製造) (2) IXE-700F (Mg-Al anion exchanger, neutral exchange capacity 4.5 meq/g, manufactured by Toagosei Co., Ltd.)

(3)IXE-300(Sb系陽離子交換體，中***換容量2.3 meq/g，東亞合成公司製造) (3) IXE-300 (Sb-based cation exchanger, neutral exchange capacity 2.3 meq/g, manufactured by Toagosei Co., Ltd.)

(4)IXE-500(Bi系陰離子交換體，中***換容量1.8 meq/g，東亞合成公司製造) (4) IXE-500 (Bi-based anion exchanger, neutral exchange capacity 1.8 meq/g, manufactured by Toagosei Co., Ltd.)

(5)IXE-530(Bi系陰離子交換體，中***換容量1.8 meq/g，東亞合成公司製造) (5) IXE-530 (Bi-based anion exchanger, neutral exchange capacity 1.8 meq/g, manufactured by Toagosei Co., Ltd.)

(6)IXE-633(Sb、Bi系兩性離子交換體，中***換容量1.8 meq/g，東亞合成公司製造) (6) IXE-633 (Sb, Bi-based amphoteric ion exchanger, neutral exchange capacity 1.8 meq/g, manufactured by Toagosei Co., Ltd.)

(實施例1) (Example 1)

(1)各向異性導電材料之製備：於雙酚A改性環氧樹脂(DIC公司製造之「EPICLON EXA-4850-150」)40重量份、及雙酚F環氧樹脂(DIC公司製造之「EXA-835LV」)30重量份中，添加作為陽離子產生劑之SI-60L(三新化學公司製造之San-Aid)3重量份、作為光硬化性化合物之環氧丙烯酸酯(Daicel-Cytec公司製造之「EBECRYL3702」)20重量份、作為光硬化起始劑之醯基氧化膦系化合物(Ciba Japan公司製造之「DAROCUR TPO」)1重量份、作為填料之平均粒徑0.25 μm之二氧化矽10重量份、平均粒徑10 μm之導電性粒子A 4重量份、作為離子交換體之上述(1)IXE-100(東亞合成公司製造)1重量份、及上述(2)IXE-700F(東亞合成公司製造)1重量份，使用行星式攪拌機以2000 rpm攪拌5分鐘，藉此獲得各向異性導電膏。再者，所使用之導電性粒子A係具有於二乙烯苯樹脂粒子之表面形成有鍍鎳層，且於該鍍鎳層之表面形 成有鍍金層之金屬層的導電性粒子。 (1) Preparation of an anisotropic conductive material: 40 parts by weight of bisphenol A modified epoxy resin ("EPICLON EXA-4850-150" manufactured by DIC Corporation), and bisphenol F epoxy resin (manufactured by DIC Corporation) To 30 parts by weight of the "EXA-835LV", 3 parts by weight of SI-60L (San-Aid, manufactured by Sanshin Chemical Co., Ltd.) as a cation generating agent, and an epoxy acrylate as a photocurable compound (Daicel-Cytec Co., Ltd.) was added. 20 parts by weight of the EB-based phosphine oxide-based compound ("DAROCUR TPO" manufactured by Ciba Japan Co., Ltd.) as a photo-curing initiator, and cerium oxide having an average particle diameter of 0.25 μm as a filler. 10 parts by weight, 4 parts by weight of the conductive particles A having an average particle diameter of 10 μm, 1 part by weight of the above (1) IXE-100 (manufactured by Toagosei Co., Ltd.) as an ion exchanger, and (2) IXE-700F (East Asia) 1 part by weight of a synthetic company, which was stirred at 2000 rpm for 5 minutes using a planetary mixer, thereby obtaining an anisotropic conductive paste. Further, the conductive particles A used have a nickel-plated layer formed on the surface of the divinylbenzene resin particles, and are formed on the surface of the nickel-plated layer. Conductive particles formed into a metal layer of a gold plating layer.

(2)連接結構體(FOG)之製作：準備於上表面形成有L/S為50 μm/50 μm、長度1 mm之鋁電極圖案的玻璃基板(第1連接對象構件)。又，準備於下表面形成有L/S為50 μm/50 μm、長度2 mm之經鍍金之Cu電極圖案的可撓性印刷基板(第2連接對象構件)。 (2) Production of the bonded structure (FOG): A glass substrate (first connection target member) having an aluminum electrode pattern of L/S of 50 μm/50 μm and a length of 1 mm was prepared on the upper surface. Further, a flexible printed circuit board (second connection target member) having a gold-plated Cu electrode pattern having an L/S of 50 μm/50 μm and a length of 2 mm was prepared on the lower surface.

於上述玻璃基板上，使用分注器將剛製作後之各向異性導電膏塗敷成寬度1.5 mm、厚度40 μm，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可撓性印刷基板。以光照射強度為3000 mW/cm2之方式照射365 nm之紫外線3秒，藉由光聚合使各向異性導電膏層半硬化而B階段化。其後，使用大橋製作所公司製造之「BD-02」，一面以各向異性導電膏層之溫度達到170℃(正式壓接溫度)之方式調整加熱壓接頭之溫度，一面於可撓性印刷基板之上表面載置加壓壓接頭，施加1 MPa之壓力於170℃下使各向異性導電膏層硬化5秒，獲得連接結構體。 On the above glass substrate, the anisotropic conductive paste immediately after fabrication was applied to a width of 1.5 mm and a thickness of 40 μm using a dispenser to form an anisotropic conductive paste layer. Then, the flexible printed circuit board is laminated on the anisotropic conductive paste layer so that the electrodes face each other. The ultraviolet light of 365 nm was irradiated for 3 seconds at a light irradiation intensity of 3000 mW/cm 2 , and the anisotropic conductive paste layer was semi-hardened by photopolymerization to be B-staged. Then, using "BD-02" manufactured by Daewoo Seisakusho Co., Ltd., the temperature of the heated crimping joint was adjusted to 170 ° C (the final crimping temperature) while the temperature of the anisotropic conductive paste layer was adjusted to the flexible printed circuit board. A pressure-bonding joint was placed on the upper surface, and the anisotropic conductive paste layer was cured at 170 ° C for 5 seconds under a pressure of 1 MPa to obtain a bonded structure.

(實施例2) (Example 2)

將上述(1)IXE-100之調配量變更為0.01重量份，並且將上述(2)IXE-700F之調配量變更為0.01重量份，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 In the same manner as in Example 1, except that the amount of the above (1) IXE-100 was changed to 0.01 part by weight, and the amount of the above (2) IXE-700F was changed to 0.01 part by weight. Heteroconductive paste. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(實施例3) (Example 3)

將上述(1)IXE-100之調配量變更為5重量份，並且將上述(2)IXE-700F之調配量變更為5重量份，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 In the same manner as in Example 1, except that the amount of the above (1) IXE-100 was changed to 5 parts by weight, and the amount of the above (2) IXE-700F was changed to 5 parts by weight. Heteroconductive paste. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(實施例4) (Example 4)

將上述(2)IXE-700F變更為上述(4)IXE-500(東亞合成公司製造)，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the above (2) IXE-700F was changed to the above (4) IXE-500 (manufactured by Toagosei Co., Ltd.). A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(實施例5) (Example 5)

將上述(1)IXE-100變更為上述(3)IXE-300(東亞合成公司製造)，並且將上述(2)IXE-700F變更為上述(4)IXE-500(東亞合成公司製造)，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 The above (1) IXE-100 is changed to the above (3) IXE-300 (manufactured by Toagosei Co., Ltd.), and the above (2) IXE-700F is changed to the above (4) IXE-500 (manufactured by Toagosei Co., Ltd.), except Except that, an anisotropic conductive paste was obtained in the same manner as in Example 1. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(實施例6) (Example 6)

將上述(1)IXE-100變更為上述(3)IXE-300(東亞合成公司製造)，並且將上述(2)IXE-700F變更為上述(5)IXE-530(東亞合成公司製造)，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 The above (1) IXE-100 is changed to the above (3) IXE-300 (manufactured by Toagosei Co., Ltd.), and the above (2) IXE-700F is changed to the above (5) IXE-530 (manufactured by Toagosei Co., Ltd.), except Except that, an anisotropic conductive paste was obtained in the same manner as in Example 1. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(比較例1) (Comparative Example 1)

不添加上述(1)IXE-100及上述(2)IXE-700F兩者，除此 以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 Do not add both (1) IXE-100 and (2) IXE-700F above, except this An anisotropic conductive paste was obtained in the same manner as in Example 1 except for the same. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(比較例2) (Comparative Example 2)

不添加上述(1)IXE-100，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the above (1) IXE-100 was not added. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(比較例3) (Comparative Example 3)

不添加上述(2)IXE-700F，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 1 except that the above (2) IXE-700F was not added. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(比較例4) (Comparative Example 4)

不添加上述(1)IXE-100及上述(2)IXE-700F兩者，而添加IXE-633(東亞合成公司製造)2重量份，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 In the same manner as in Example 1, except that the above (1) IXE-100 and the above (2) IXE-700F were added, and 2 parts by weight of IXE-633 (manufactured by Toagosei Co., Ltd.) was added. Heteroconductive paste. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(參考例1) (Reference example 1)

不添加作為陽離子產生劑之SI-60L，而添加熱硬化劑(咪唑化合物，四國化成工業公司製造之「2P-4MZ」)10重量份，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 The same procedure as in Example 1 was carried out except that 10 parts by weight of a thermosetting agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Co., Ltd.) was added without adding the SI-60L as a cation generating agent. Anisotropic conductive paste. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(參考例2) (Reference example 2)

不添加作為陽離子產生劑之SI-60L，而添加熱硬化劑(咪唑化合物，四國化成工業公司製造之「2P-4MZ」)10重量份，並且不添加上述(1)IXE-100及上述(2)IXE-700F兩者，除此以外，以與實施例1相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例1相同之方式獲得連接結構體。 10 parts by weight of a thermosetting agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Co., Ltd.) was added without adding the SI-60L as a cation generating agent, and the above (1) IXE-100 and the above were not added ( 2) An anisotropic conductive paste was obtained in the same manner as in Example 1 except for the case of both IXE-700F. A bonded structure was obtained in the same manner as in Example 1 using the obtained anisotropic conductive paste.

(實施例1~6、比較例1~4及參考例1、2之評價) (Evaluation of Examples 1 to 6, Comparative Examples 1 to 4, and Reference Examples 1 and 2)

(1)導通可靠性(連接電阻值) (1) Conduction reliability (connection resistance value)

利用四端子法，分別測定所獲得之連接結構體之上下電極間的連接電阻。算出100個部位之連接電阻之平均值。再者，亦可根據電壓=電流×電阻之關係，藉由測定流通固定電流時之電壓，而求出連接電阻。以下述之基準對所獲得之連接結構體之導通可靠性進行判定。 The connection resistance between the lower electrodes on the obtained connection structure was measured by a four-terminal method. The average value of the connection resistance of 100 parts was calculated. Further, the connection resistance can be obtained by measuring the voltage at which a fixed current flows in accordance with the relationship of voltage=current×resistance. The conduction reliability of the obtained connection structure was determined on the basis of the following criteria.

[導通可靠性之判定基準] [Determination of Conductivity Reliability]

○○：未達3 Ω ○○: less than 3 Ω

○：3 Ω以上且未達5 Ω ○: 3 Ω or more and less than 5 Ω

×：5 Ω以上 ×: 5 Ω or more

(2)耐濕絕緣可靠性 (2) Resistance to humidity insulation

於在所獲得之連接結構體的相互絕緣之測定用端子間施加有20 V電壓之狀態下，於85℃及85% RH之環境下暴露500小時，測定在此期間測定用端子間之電阻值變化。將電阻值變為105 Ω以下之情形判斷為絕緣故障。以下述基準判定耐濕絕緣可靠性。 The battery was exposed to an environment of 85 ° C and 85% RH for 500 hours while applying a voltage of 20 V between the terminals for measurement of mutual insulation of the obtained connection structure, and the resistance value between the terminals for measurement was measured during this period. Variety. The case where the resistance value becomes 10 5 Ω or less is judged to be an insulation failure. The moisture-resistant insulation reliability was determined on the basis of the following criteria.

[耐濕絕緣可靠性之判定基準] [Determination of moisture-resistant insulation reliability]

○○：10個連接結構體中，無產生絕緣故障之連接結構體，且耐濕絕緣可靠性試驗後之平均電阻值為107 Ω以上 ○○: Among the 10 connected structures, there is no connection structure that causes insulation failure, and the average resistance value after the humidity insulation reliability test is 10 7 Ω or more.

○：10個連接結構體中，無產生絕緣故障之連接結構體，且耐濕絕緣可靠性試驗後之平均電阻值為106 Ω以上、未達107 Ω ○: Among the 10 connected structures, there is no connection structure that causes insulation failure, and the average resistance value after the humidity insulation reliability test is 10 6 Ω or more and less than 10 7 Ω.

△：10個連接結構體中，無產生絕緣故障之連接結構體，且耐濕絕緣可靠性試驗後之平均電阻值為105 Ω以上、未達106 Ω △: Among the 10 connected structures, there is no connection structure in which insulation failure occurs, and the average resistance value after the humidity insulation reliability test is 10 5 Ω or more and less than 10 6 Ω.

×：10個連接結構體中，有1個以上產生絕緣故障之連接結構體 ×: Among the 10 connected structures, there are one or more connected structures that cause insulation failure.

將結果示於下述之表1。 The results are shown in Table 1 below.

(實施例7) (Example 7)

(1)導電性粒子之製作：對平均粒徑10 μm之二乙烯苯樹脂粒子(積水化學工業公司製造，Micropearl SP-210)進行非電解鍍鎳，於樹脂粒子 之表面上形成厚度0.1 μm之基底鍍鎳層。繼而，對形成有基底鍍鎳層之樹脂粒子進行電解鍍銅，形成厚度1 μm之銅層。進而，使用含有錫及鉍之電解鍍敷液進行電解鍍敷，形成厚度1 μm之焊料層。如此，製作於樹脂粒子之表面上形成有厚度1 μm之銅層，且於該銅層之表面形成有厚度1 μm之焊料層(錫：鉍=43重量%：57重量%)的導電性粒子B。 (1) Preparation of conductive particles: Electroless nickel plating on resin particles was carried out on divinylbenzene resin particles (Micropearl SP-210, manufactured by Sekisui Chemical Co., Ltd.) having an average particle diameter of 10 μm. A nickel plating layer of a substrate having a thickness of 0.1 μm was formed on the surface. Then, the resin particles on which the underlying nickel plating layer was formed were subjected to electrolytic copper plating to form a copper layer having a thickness of 1 μm. Further, electrolytic plating was carried out using an electrolytic plating solution containing tin and antimony to form a solder layer having a thickness of 1 μm. Thus, a copper layer having a thickness of 1 μm was formed on the surface of the resin particle, and a conductive layer having a thickness of 1 μm (tin: 铋 = 43% by weight: 57% by weight) was formed on the surface of the copper layer. B.

(2)各向異性導電材料之製備：於雙酚A改性環氧樹脂(DIC公司製造之「EPICLON EXA-4850-150」)40重量份、及雙酚F環氧樹脂(DIC公司製造之「EXA-835LV」)30重量份中，添加作為陽離子產生劑之SI-60L(三新化學公司製造之San-Aid)3重量份、作為光硬化性化合物之環氧丙烯酸酯(Daicel-Cytec公司製造之「EBECRYL3702」)20重量份、作為光硬化起始劑之醯基氧化膦系化合物(Ciba Japan公司製造之「DAROCUR TPO」)1重量份、作為填料之平均粒徑0.25 μm之二氧化矽10重量份、作為助焊劑之松香3重量份、所獲得之導電性粒子B4重量份、作為離子交換體之上述(1)IXE-100(東亞合成公司製造)1重量份、及上述(2)IXE-700F(東亞合成公司製造)1重量份，使用行星式攪拌機以2000 rpm攪拌5分鐘，藉此獲得各向異性導電膏。 (2) Preparation of an anisotropic conductive material: 40 parts by weight of bisphenol A modified epoxy resin ("EPICLON EXA-4850-150" manufactured by DIC Corporation), and bisphenol F epoxy resin (manufactured by DIC Corporation) To 30 parts by weight of the "EXA-835LV", 3 parts by weight of SI-60L (San-Aid, manufactured by Sanshin Chemical Co., Ltd.) as a cation generating agent, and an epoxy acrylate as a photocurable compound (Daicel-Cytec Co., Ltd.) was added. 20 parts by weight of the EB-based phosphine oxide-based compound ("DAROCUR TPO" manufactured by Ciba Japan Co., Ltd.) as a photo-curing initiator, and cerium oxide having an average particle diameter of 0.25 μm as a filler. 10 parts by weight, 3 parts by weight of the rosin as a flux, 4 parts by weight of the conductive particles obtained, 1 part by weight of the above (1) IXE-100 (manufactured by Toagosei Co., Ltd.) as an ion exchanger, and the above (2) 1 part by weight of IXE-700F (manufactured by Toagosei Co., Ltd.) was stirred at 2000 rpm for 5 minutes using a planetary mixer, whereby an anisotropic conductive paste was obtained.

(2)連接結構體(FOB)之製作 (2) Production of connection structure (FOB)

準備於上表面形成有L/S為100 μm/100 μm、長度4 mm之經鍍金之Cu電極圖案的環氧玻璃基板(第1連接對象構 件)。又，準備於下表面形成有L/S為100 μm/100 μm、長度4 mm之經鍍金之Cu電極圖案的可撓性印刷基板(第2連接對象構件)。 An epoxy glass substrate having a gold-plated Cu electrode pattern having an L/S of 100 μm/100 μm and a length of 4 mm is formed on the upper surface (first connection structure) Pieces). Further, a flexible printed circuit board (second connection target member) having a gold-plated Cu electrode pattern having an L/S of 100 μm/100 μm and a length of 4 mm was prepared on the lower surface.

於上述玻璃基板上，使用分注器將剛製作後之各向異性導電膏塗敷成寬度1.5 mm、厚度40 μm，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可撓性印刷基板。以光照射強度為3000 mW/cm2之方式照射365 nm之紫外線3秒，藉由光聚合使各向異性導電膏層半硬化而B階段化。其後，使用大橋製作所公司製造之「BD-02」，一面以各向異性導電膏層之溫度達到170℃(正式壓接溫度)之方式調整加熱壓接頭之溫度，一面於可撓性印刷基板之上表面載置加壓壓接頭，施加1 MPa之壓力於170℃下使各向異性導電膏層硬化5秒，獲得連接結構體。 On the above glass substrate, the anisotropic conductive paste immediately after fabrication was applied to a width of 1.5 mm and a thickness of 40 μm using a dispenser to form an anisotropic conductive paste layer. Then, the flexible printed circuit board is laminated on the anisotropic conductive paste layer so that the electrodes face each other. The ultraviolet light of 365 nm was irradiated for 3 seconds at a light irradiation intensity of 3000 mW/cm 2 , and the anisotropic conductive paste layer was semi-hardened by photopolymerization to be B-staged. Then, using "BD-02" manufactured by Daewoo Seisakusho Co., Ltd., the temperature of the heated crimping joint was adjusted to 170 ° C (the final crimping temperature) while the temperature of the anisotropic conductive paste layer was adjusted to the flexible printed circuit board. A pressure-bonding joint was placed on the upper surface, and the anisotropic conductive paste layer was cured at 170 ° C for 5 seconds under a pressure of 1 MPa to obtain a bonded structure.

(實施例8) (Example 8)

將上述(1)IXE-100之調配量變更為0.01重量份，並且將上述(2)IXE-700F之調配量變更為0.01重量份，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 In the same manner as in Example 7, except that the amount of the above (1) IXE-100 was changed to 0.01 part by weight, and the amount of the above (2) IXE-700F was changed to 0.01 part by weight. Heteroconductive paste. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例9) (Example 9)

將上述(1)IXE-100之調配量變更為5重量份，並且將上述(2)IXE-700F之調配量變更為5重量份，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之 各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 In the same manner as in Example 7, except that the amount of the above (1) IXE-100 was changed to 5 parts by weight, and the amount of the above (2) IXE-700F was changed to 5 parts by weight. Heteroconductive paste. Use obtained An anisotropic conductive paste was obtained in the same manner as in Example 7 to obtain a bonded structure.

(實施例10) (Embodiment 10)

將上述(2)IXE-700F變更為上述(4)IXE-500(東亞合成公司製造)，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the above (2) IXE-700F was changed to the above (4) IXE-500 (manufactured by Toagosei Co., Ltd.). A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例11) (Example 11)

將上述(1)IXE-100變更成上述(3)IXE-300(東亞合成公司製造)，並且將上述(2)IXE-700F變更成上述(4)IXE-500(東亞合成公司製造)，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 The above (1) IXE-100 was changed to the above (3) IXE-300 (manufactured by Toagosei Co., Ltd.), and the above (2) IXE-700F was changed to the above (4) IXE-500 (manufactured by Toagosei Co., Ltd.), except Except that, an anisotropic conductive paste was obtained in the same manner as in Example 7. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例12) (Embodiment 12)

將上述(1)IXE-100變更成上述(3)IXE-300(東亞合成公司製造)，並且將上述(2)IXE-700F變更成上述(5)IXE-530(東亞合成公司製造)，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 The above (1) IXE-100 was changed to the above (3) IXE-300 (manufactured by Toagosei Co., Ltd.), and the above (2) IXE-700F was changed to the above (5) IXE-530 (manufactured by Toagosei Co., Ltd.), except Except that, an anisotropic conductive paste was obtained in the same manner as in Example 7. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例13) (Example 13)

不調配作為助焊劑之松香，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that rosin as a flux was not blended. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例14) (Example 14)

將上述導電性粒子B變更成上述導電性粒子A，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the above-mentioned conductive particles B were changed to the above-mentioned conductive particles A. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例15) (Example 15)

將上述導電性粒子B變更成上述導電性粒子A，除此以外，以與實施例8相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 8 except that the above-mentioned conductive particles B were changed to the above-mentioned conductive particles A. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例16) (Embodiment 16)

將上述導電性粒子B變更成上述導電性粒子A，除此之外，以與實施例9相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 9 except that the above-mentioned conductive particles B were changed to the above-mentioned conductive particles A. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例17) (Example 17)

將上述導電性粒子B變更成上述導電性粒子A，除此以外，以與實施例10相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 10 except that the above-mentioned conductive particles B were changed to the above-mentioned conductive particles A. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例18) (Embodiment 18)

將上述導電性粒子B變更成上述導電性粒子A，除此以外，以與實施例11相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 11 except that the above-mentioned conductive particles B were changed to the above-mentioned conductive particles A. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例19) (Embodiment 19)

將上述導電性粒子B變更成上述導電性粒子A，除此以外，以與實施例12相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 12 except that the conductive particles B were changed to the conductive particles A. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例20) (Embodiment 20)

將熱硬化性化合物之種類及調配量由雙酚A改性環氧樹脂(DIC公司製造之「EPICLON EXA-4850-150」)40重量份、及雙酚F環氧樹脂(DIC公司製造之「EXA-835LV」)30重量份變更為雙酚E環氧樹脂(Printec公司製造之「R1710」)70重量份，並且將上述導電性粒子B變更為上述導電性粒子A，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 The type and amount of the thermosetting compound were 40 parts by weight of bisphenol A-modified epoxy resin ("EPICLON EXA-4850-150" manufactured by DIC Corporation), and bisphenol F epoxy resin (manufactured by DIC Corporation). 30 parts by weight of the EXA-835LV" was changed to 70 parts by weight of bisphenol E epoxy resin ("R1710" manufactured by Printec Co., Ltd.), and the conductive particles B were changed to the conductive particles A, and An anisotropic conductive paste was obtained in the same manner as in Example 7. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例21) (Example 21)

將陽離子產生劑之種類由SI-60L(三新化學公司製造之San-Aid)變更為CXC-1612(楠本化成公司製造之K-PURE)，並且將上述導電性粒子B變更為上述導電性粒子A，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 The type of the cation generating agent was changed from SI-60L (San-Aid manufactured by Sanshin Chemical Co., Ltd.) to CXC-1612 (K-PURE manufactured by Kumoto Chemical Co., Ltd.), and the conductive particles B were changed to the above-mentioned conductive particles. A, an anisotropic conductive paste was obtained in the same manner as in Example 7 except for the above. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(比較例5) (Comparative Example 5)

不添加上述(1)IXE-100及上述(2)IXE-700F兩者，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使 用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the above (1) IXE-100 and the above (2) IXE-700F were not added. Make A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(比較例6) (Comparative Example 6)

不添加上述(1)IXE-100，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the above (1) IXE-100 was not added. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(比較例7) (Comparative Example 7)

不添加上述(2)IXE-700F，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Example 7 except that the above (2) IXE-700F was not added. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(比較例8) (Comparative Example 8)

將上述導電性粒子B變更為上述導電性粒子A，除此以外，以與比較例5相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Comparative Example 5 except that the conductive particles B were changed to the conductive particles A described above. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(比較例9) (Comparative Example 9)

將上述導電性粒子B變更為上述導電性粒子A，除此以外，以與比較例6相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Comparative Example 6, except that the conductive particles B were changed to the conductive particles A described above. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(比較例10) (Comparative Example 10)

將上述導電性粒子B變更為上述導電性粒子A，除此以外，以與比較例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得 連接結構體。 An anisotropic conductive paste was obtained in the same manner as in Comparative Example 7, except that the conductive particles B were changed to the conductive particles A described above. Using the obtained anisotropic conductive paste, it was obtained in the same manner as in Example 7. Connect the structure.

(比較例11) (Comparative Example 11)

不添加上述(1)IXE-100及上述(2)IXE-700F兩者，而添加IXE-633(東亞合成公司製造)2重量份，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 In the same manner as in Example 7, except that the above (1) IXE-100 and the above (2) IXE-700F were added, and 2 parts by weight of IXE-633 (manufactured by Toagosei Co., Ltd.) was added. Heteroconductive paste. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(參考例3) (Reference Example 3)

不添加作為陽離子產生劑之SI-60L，而添加熱硬化劑(咪唑化合物，四國化成工業公司製造之「2P-4MZ」)10重量份，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 The same procedure as in Example 7 was carried out except that 10 parts by weight of a thermosetting agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Co., Ltd.) was added without adding the SI-60L as a cation generating agent. Anisotropic conductive paste. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(參考例4) (Reference example 4)

不添加作為陽離子產生劑之SI-60L，而添加熱硬化劑(咪唑化合物，四國化成工業公司製造「2P-4MZ」)10重量份，並且不添加上述(1)IXE-100及上述(2)IXE-700F兩者，除此以外，以與實施例7相同之方式獲得各向異性導電膏。使用所獲得之各向異性導電膏，以與實施例7相同之方式獲得連接結構體。 10 parts by weight of a thermosetting agent (imidazole compound, "2P-4MZ" manufactured by Shikoku Chemicals Co., Ltd.) was added without adding the SI-60L as a cation generating agent, and the above (1) IXE-100 and the above (2) were not added. An anisotropic conductive paste was obtained in the same manner as in Example 7 except for the case of both IXE-700F. A bonded structure was obtained in the same manner as in Example 7 using the obtained anisotropic conductive paste.

(實施例7~21、比較例5~11及參考例3、4之評價) (Evaluation of Examples 7 to 21, Comparative Examples 5 to 11, and Reference Examples 3 and 4)

(1)導通可靠性(連接電阻值) (1) Conduction reliability (connection resistance value)

利用四端子法，分別測定所獲得之連接結構體之上下電極間的連接電阻。算出10個連接結構體之連接電阻之平均 值。再者，亦可根據電壓=電流×電阻之關係，藉由測定流通固定電流時之電壓而求出連接電阻。以下述之基準，對所獲得之連接結構體之導通可靠性進行判定。 The connection resistance between the lower electrodes on the obtained connection structure was measured by a four-terminal method. Calculate the average of the connection resistance of 10 connected structures value. Further, the connection resistance can be obtained by measuring the voltage at which the fixed current flows in accordance with the relationship of voltage=current×resistance. The conduction reliability of the obtained connection structure was determined on the basis of the following criteria.

[導通可靠性之判定基準] [Determination of Conductivity Reliability]

○○：未達8 Ω ○○: less than 8 Ω

○：8 Ω以上且未達10 Ω ○: 8 Ω or more and less than 10 Ω

×：10 Ω以上 ×: 10 Ω or more

(2)耐濕絕緣可靠性 (2) Resistance to humidity insulation

於在所獲得之連接結構體的相互絕緣之測定用端子間施加有15 V電壓之狀態下，於85℃及85% RH之環境下暴露500小時，測定在此期間測定用端子間之電阻值變化。將電阻值變為105 Ω以下之情形判斷為絕緣故障。以下述基準判定耐濕絕緣可靠性。 The battery was exposed to an environment of 85 ° C and 85% RH for 500 hours while applying a voltage of 15 V between the terminals for measurement of mutual insulation of the obtained connection structure, and the resistance value between the terminals for measurement during this period was measured. Variety. The case where the resistance value becomes 10 5 Ω or less is judged to be an insulation failure. The moisture-resistant insulation reliability was determined on the basis of the following criteria.

[耐濕絕緣可靠性之判定基準] [Determination of moisture-resistant insulation reliability]

○○：10個連接結構體中，無產生絕緣故障之連接結構體，且耐濕絕緣可靠性試驗後之平均電阻值為107 Ω以上 ○○: Among the 10 connected structures, there is no connection structure that causes insulation failure, and the average resistance value after the humidity insulation reliability test is 10 7 Ω or more.

○：10個連接結構體中，無產生絕緣故障之連接結構體，且耐濕絕緣可靠性試驗後之平均電阻值為106 Ω以上、未達107 Ω ○: Among the 10 connected structures, there is no connection structure that causes insulation failure, and the average resistance value after the humidity insulation reliability test is 10 6 Ω or more and less than 10 7 Ω.

△：10個連接結構體中，無產生絕緣故障之連接結構體，且耐濕絕緣可靠性試驗後之平均電阻值為105 Ω以上、未達106 Ω △: Among the 10 connected structures, there is no connection structure in which insulation failure occurs, and the average resistance value after the humidity insulation reliability test is 10 5 Ω or more and less than 10 6 Ω.

×：10個連接結構體中，有1個以上產生絕緣故障之連接結構體 ×: Among the 10 connected structures, there are one or more connected structures that cause insulation failure.

將結果示於下述之表2。再者，於使用導電性粒子B之實施例、比較例及參考例之連接結構體在製作連接結構體時，導電性粒子B之焊料層熔融之後固化，導電性粒子B之銅層接觸連接結構體之電極。 The results are shown in Table 2 below. In the case of using the conductive structure B, the bonded structure of the comparative example and the reference example, when the bonded structure is produced, the solder layer of the conductive particles B is solidified and then solidified, and the copper layer contact connection structure of the conductive particles B is formed. The electrode of the body.

再者，實施例3、16與參考例1~4之導通可靠性之評價結果均為「○」。其中，實施例3、16之導通可靠性之評價中的連接電阻之值低於參考例1~4之連接電阻之值。 In addition, the evaluation results of the conduction reliability of Examples 3 and 16 and Reference Examples 1 to 4 were both "○". Among them, the values of the connection resistances in the evaluation of the conduction reliability of Examples 3 and 16 were lower than the values of the connection resistances of Reference Examples 1 to 4.

再者，實施例7與實施例14之導通可靠性之評價結果均 為「○○」，實施例8與實施例15之導通可靠性之評價結果均為「○○」，實施例10與實施例17之導通可靠性之評價結果均為「○○」，實施例11與實施例18之導通可靠性之評價結果均為「○○」，實施例12與實施例19之導通可靠性之評價結果均為「○○」。 Furthermore, the evaluation results of the conduction reliability of Example 7 and Example 14 are both In the case of "○○", the evaluation results of the conduction reliability of Example 8 and Example 15 were both "○○", and the evaluation results of the conduction reliability of Example 10 and Example 17 were both "○○", and Examples The evaluation results of the conduction reliability of Example 11 and Example 18 were both "○○", and the evaluation results of the conduction reliability of Example 12 and Example 19 were both "○○".

其中，實施例7之導通可靠性之評價中的連接電阻較實施例14之導通可靠性之評價中的連接電阻低0.7 Ω，實施例8之導通可靠性之評價中的連接電阻較實施例15之導通可靠性之評價中的連接電阻低0.9 Ω，實施例10之導通可靠性之評價中的連接電阻較實施例17之導通可靠性之評價中的連接電阻低0.8 Ω，實施例11之導通可靠性之評價中的連接電阻較實施例18之導通可靠性之評價中的連接電阻低0.8 Ω，實施例12之導通可靠性之評價中的連接電阻較實施例19之導通可靠性之評價中的連接電阻低0.7 Ω。 The connection resistance in the evaluation of the conduction reliability of Example 7 was 0.7 Ω lower than the connection resistance in the evaluation of the conduction reliability of Example 14, and the connection resistance in the evaluation of the conduction reliability of Example 8 was compared with that in Example 15. The connection resistance in the evaluation of the conduction reliability was 0.9 Ω lower, and the connection resistance in the evaluation of the conduction reliability of Example 10 was 0.8 Ω lower than the connection resistance in the evaluation of the conduction reliability of Example 17, and the conduction of Example 11 was achieved. The connection resistance in the evaluation of reliability was 0.8 Ω lower than the connection resistance in the evaluation of the conduction reliability of Example 18, and the connection resistance in the evaluation of the conduction reliability of Example 12 was evaluated in comparison with the conduction reliability of Example 19. The connection resistance is 0.7 Ω low.

再者，以上僅示出將實施例、比較例及參考例之各向異性導電材料用於連接結構體(FOG或FOB)之評價結果。本發明者等人確認，將實施例、比較例及參考例之各向異性導電材料用於未評價之其他連接結構體(FOB、FOG、COF及COG等)之情形時，以及將實施例、比較例及參考例之各向異性導電材料用作導電材料，而將有機電致發光顯示元件中之電極電性連接之情形時，(1)導通可靠性及(2)耐濕絕緣可靠性之評價結果均顯示出與上述之實施例、比較例及參考例之評價結果相同的傾向。 Further, the above only shows the evaluation results of using the anisotropic conductive materials of the examples, the comparative examples, and the reference examples for the bonded structure (FOG or FOB). The inventors of the present invention confirmed that when the anisotropic conductive materials of the examples, the comparative examples, and the reference examples are used for other connected structures (FOB, FOG, COF, COG, etc.) which are not evaluated, and the examples, When the anisotropic conductive material of the comparative example and the reference example is used as a conductive material and the electrodes in the organic electroluminescence display element are electrically connected, (1) conduction reliability and (2) reliability of wet insulation resistance The evaluation results showed the same tendency as the evaluation results of the above-described examples, comparative examples, and reference examples.

1‧‧‧連接結構體 1‧‧‧Connected structure

2‧‧‧第1連接對象構件 2‧‧‧1st connection object component

2a‧‧‧表面 2a‧‧‧ surface

2b‧‧‧第1電極 2b‧‧‧1st electrode

3‧‧‧連接部 3‧‧‧Connecting Department

3a‧‧‧上表面 3a‧‧‧Upper surface

3A‧‧‧導電材料層 3A‧‧‧ Conductive material layer

3B‧‧‧經B階段化之導電材料層 3B‧‧‧B-staged conductive material layer

4‧‧‧第2連接對象構件 4‧‧‧2nd connection object component

4a‧‧‧表面 4a‧‧‧ surface

4b‧‧‧第2電極 4b‧‧‧2nd electrode

5‧‧‧導電性粒子 5‧‧‧Electrical particles

圖1係模式性地表示使用本發明之一實施形態之導電材料之連接結構體的正面剖面圖。 Fig. 1 is a front cross-sectional view schematically showing a bonded structure using a conductive material according to an embodiment of the present invention.

圖2(a)~(c)係用以說明使用本發明之一實施形態之導電材料獲得連接結構體之各步驟的正面剖面圖。 2(a) to 2(c) are front cross-sectional views for explaining respective steps of obtaining a bonded structure using a conductive material according to an embodiment of the present invention.

1‧‧‧連接結構體 1‧‧‧Connected structure

2‧‧‧第1連接對象構件 2‧‧‧1st connection object component

2a‧‧‧表面 2a‧‧‧ surface

2b‧‧‧第1電極 2b‧‧‧1st electrode

3‧‧‧連接部 3‧‧‧Connecting Department

4‧‧‧第2連接對象構件 4‧‧‧2nd connection object component

4a‧‧‧表面 4a‧‧‧ surface

4b‧‧‧第2電極 4b‧‧‧2nd electrode

5‧‧‧導電性粒子 5‧‧‧Electrical particles

Claims (11)

一種導電材料，其包含硬化性成分、陽離子交換體、陰離子交換體及導電性粒子，且上述硬化性成分含有硬化性化合物及陽離子產生劑。 A conductive material comprising a curable component, a cation exchanger, an anion exchanger, and conductive particles, wherein the curable component contains a curable compound and a cation generator. 如請求項1之導電材料，其中上述陽離子交換體之中***換容量為2 meq/g以上，且上述陰離子交換體之中***換容量為1 meq/g以上。 The conductive material according to claim 1, wherein the cation exchanger has a neutral exchange capacity of 2 meq/g or more, and the anion exchanger has a neutral exchange capacity of 1 meq/g or more. 如請求項1或2之導電材料，其中上述陽離子交換體包含鋯原子。 The conductive material of claim 1 or 2, wherein the cation exchanger comprises a zirconium atom. 如請求項1或2之導電材料，其中上述陰離子交換體包含鎂原子及鋁原子。 The conductive material of claim 1 or 2, wherein the anion exchanger comprises a magnesium atom and an aluminum atom. 如請求項1或2之導電材料，其中相對於上述硬化性化合物100重量份，上述陽離子交換體之含量為0.01重量份以上、5重量份以下，且上述陰離子交換體之含量為0.01重量份以上、5重量份以下。 The conductive material according to claim 1 or 2, wherein the content of the cation exchanger is 0.01 parts by weight or more and 5 parts by weight or less, and the content of the anion exchanger is 0.01 parts by weight or more based on 100 parts by weight of the curable compound. 5 parts by weight or less. 如請求項1之導電材料，其中上述導電性粒子包含樹脂粒子、及配置於上述樹脂粒子之表面上之導電層，且上述導電層之至少外側之表面為熔點450℃以下之低熔點金屬層。 The conductive material according to claim 1, wherein the conductive particles comprise resin particles and a conductive layer disposed on a surface of the resin particles, and at least an outer surface of the conductive layer has a low melting point metal layer having a melting point of 450 ° C or lower. 如請求項1、2或6之導電材料，其進而包含助焊劑。 A conductive material as claimed in claim 1, 2 or 6, which in turn comprises a flux. 如請求項1、2或6之導電材料，其係用於連接具有銅電極之連接對象構件的各向異性導電材料。 A conductive material according to claim 1, 2 or 6, which is used for connecting an anisotropic conductive material having a connection member of a copper electrode. 如請求項1、2或6之導電材料，其為各向異性導電材料。 A conductive material according to claim 1, 2 or 6, which is an anisotropic conductive material. 一種連接結構體，其包含第1連接對象構件、第2連接對象構件、及將上述第1、第2連接對象構件電性連接之連接部，且上述連接部係藉由如請求項1至9中任一項之導電材料而形成。 A connection structure including a first connection target member, a second connection target member, and a connection portion electrically connecting the first and second connection target members, wherein the connection portion is by the claims 1 to 9 Formed from any of the conductive materials. 如請求項10之連接結構體，其中上述第1連接對象構件於表面具有第1電極，上述第2連接對象構件於表面具有第2電極，上述第1電極與上述第2電極藉由上述導電性粒子而電性連接，且上述第1電極及上述第2電極中之至少一者為銅電極。 The connection structure according to claim 10, wherein the first connection target member has a first electrode on a surface thereof, the second connection target member has a second electrode on a surface thereof, and the first electrode and the second electrode have the conductivity The particles are electrically connected, and at least one of the first electrode and the second electrode is a copper electrode.
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