TWI778950B - Conductive material and connecting structure - Google Patents

Conductive material and connecting structure Download PDF

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TWI778950B
TWI778950B TW106102877A TW106102877A TWI778950B TW I778950 B TWI778950 B TW I778950B TW 106102877 A TW106102877 A TW 106102877A TW 106102877 A TW106102877 A TW 106102877A TW I778950 B TWI778950 B TW I778950B
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solder
mentioned
conductive
conductive material
electrode
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TW201732841A (en
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夏井宏
定永周治郎
伊藤将大
保井秀文
石澤英亮
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日商積水化學工業股份有限公司
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
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    • C08K5/17Amines; Quaternary ammonium compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/02Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457Solder materials or compositions; Methods of application thereof
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/36Assembling printed circuits with other printed circuits
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/36Assembling printed circuits with other printed circuits
    • H05K3/361Assembling flexible printed circuits with other printed circuits
    • H05K3/363Assembling flexible printed circuits with other printed circuits by soldering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732Location after the connecting process
    • H01L2224/73201Location after the connecting process on the same surface
    • H01L2224/73203Bump and layer connectors
    • H01L2224/73204Bump and layer connectors the bump connector being embedded into the layer connector

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)
  • Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本發明提供一種導電材料,其保存穩定性較高,於連接對象構件上配置導電材料後即便長時間放置亦顯示出優異之焊料凝集性,因此可表現較高之導通可靠性。 本發明之導電材料包含於導電部之外表面部分具有焊料之複數個導電性粒子、熱硬化性成分及助焊劑,上述助焊劑為酸與鹼之鹽,且於25℃之導電材料中,上述助焊劑係以固體存在。The present invention provides a conductive material, which has high storage stability and exhibits excellent solder agglomeration even after being placed on the member to be connected for a long time, so that it can exhibit high conduction reliability. The conductive material of the present invention includes a plurality of conductive particles with solder on the outer surface of the conductive part, a thermosetting component, and flux. The flux is a salt of acid and alkali, and in the conductive material at 25°C, the above Flux exists as a solid.

Description

導電材料及連接構造體Conductive material and connection structure

本發明係關於一種包含具有焊料之導電性粒子之導電材料。又,本發明係關於一種使用上述導電材料之連接構造體。The present invention relates to a conductive material comprising conductive particles with solder. Also, the present invention relates to a connection structure using the above-mentioned conductive material.

各向異性導電膏及各向異性導電膜等各向異性導電材料廣為人知。上述各向異性導電材料係於黏合劑中分散有導電性粒子。 上述各向異性導電材料例如用於軟性印刷基板與玻璃基板之連接(FOG(Film on Glass,鍍膜玻璃))、半導體晶片與軟性印刷基板之連接(COF(Chip on Film,薄膜覆晶))、半導體晶片與玻璃基板之連接(COG(Chip on Glass,玻璃覆晶))、以及軟性印刷基板與玻璃環氧基板之連接(FOB(Film on Board,鍍膜板))等以獲得各種連接構造體。 例如於藉由上述各向異性導電材料將軟性印刷基板之電極與玻璃環氧基板之電極電性連接時,於玻璃環氧基板上配置包含導電性粒子之各向異性導電材料。繼而,積層軟性印刷基板,進行加熱及加壓。藉此使各向異性導電材料硬化,經由導電性粒子使電極間電性連接而獲得連接構造體。 作為上述各向異性導電材料之一例,下述專利文獻1中記載有包含導電性粒子、與於該導電性粒子之熔點下不會完全硬化之樹脂成分的各向異性導電材料。作為上述導電性粒子,具體而言,可列舉:錫(Sn)、銦(In)、鉍(Bi)、銀(Ag)、銅(Cu)、鋅(Zn)、鉛(Pb)、鎘(Cd)、鎵(Ga)及鉈(Tl)等金屬或該等金屬之合金。 專利文獻1中記載,經過將各向異性導電樹脂加熱至高於上述導電性粒子之熔點且不會使上述樹脂成分完全硬化之溫度之樹脂加熱步驟、與使上述樹脂成分硬化之樹脂成分硬化步驟而實現電極間之電性連接。又,專利文獻1中記載,根據專利文獻1之圖8所示之溫度分佈而進行安裝。於專利文獻1中,於各向異性導電樹脂被加熱之溫度下未完全硬化之樹脂成分內,導電性粒子熔融。 下述專利文獻2中揭示有一種膠帶,其含有包含熱硬化性樹脂之樹脂層、焊料粉及硬化劑,上述焊料粉與上述硬化劑存在於上述樹脂層中。該膠帶為膜狀而非膏狀。 下述專利文獻3中揭示有一種含有焊料粒子、熱硬化性樹脂黏合劑及助焊劑成分之熱硬化性樹脂組合物。於專利文獻3中,作為上述助焊劑成分,可列舉:(1)二羧酸或三羧酸與二乙醇胺類或三乙醇胺類之鹽、以及(2)羧酸酐與二乙醇胺類或三乙醇胺類之加成反應物。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2004-260131號公報 [專利文獻2]WO2008/023452A1 [專利文獻3]日本專利特開2013-256584號公報Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. The above-mentioned anisotropic conductive material has conductive particles dispersed in the binder. The aforementioned anisotropic conductive materials are used, for example, for the connection between flexible printed substrates and glass substrates (FOG (Film on Glass, coated glass)), the connection between semiconductor chips and flexible printed substrates (COF (Chip on Film, chip on film)), The connection between the semiconductor chip and the glass substrate (COG (Chip on Glass, chip on glass)), and the connection between the flexible printed circuit board and the glass epoxy substrate (FOB (Film on Board, coating plate)), etc. to obtain various connection structures. For example, when the electrodes of the flexible printed circuit board and the electrodes of the glass epoxy substrate are electrically connected by the above-mentioned anisotropic conductive material, the anisotropic conductive material including conductive particles is disposed on the glass epoxy substrate. Next, the flexible printed circuit board is laminated and heated and pressed. The anisotropic conductive material is hardened by this, and between electrodes are electrically connected via electroconductive particle, and the connection structure is obtained. As an example of the aforementioned anisotropic conductive material, Patent Document 1 below describes an anisotropic conductive material including conductive particles and a resin component that does not completely harden at the melting point of the conductive particles. As said electroconductive particle, specifically, tin (Sn), indium (In), bismuth (Bi), silver (Ag), copper (Cu), zinc (Zn), lead (Pb), cadmium ( Metals such as Cd), gallium (Ga) and thallium (Tl) or alloys of these metals. Patent Document 1 discloses that the anisotropic conductive resin is heated to a temperature higher than the melting point of the above-mentioned conductive particles and does not completely harden the above-mentioned resin component. Realize the electrical connection between electrodes. In addition, Patent Document 1 describes that mounting is performed based on the temperature distribution shown in FIG. 8 of Patent Document 1. In Patent Document 1, the conductive particles are melted in the resin component that is not completely cured at the temperature at which the anisotropic conductive resin is heated. Patent Document 2 below discloses an adhesive tape comprising a resin layer containing a thermosetting resin, solder powder, and a curing agent, wherein the solder powder and the curing agent are present in the resin layer. The tape comes in film form rather than paste form. Patent Document 3 below discloses a thermosetting resin composition containing solder particles, a thermosetting resin binder, and a flux component. In Patent Document 3, examples of the above flux components include (1) salts of dicarboxylic acids or tricarboxylic acids and diethanolamines or triethanolamines, and (2) carboxylic anhydrides and diethanolamines or triethanolamines. The addition reactant. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2004-260131 [Patent Document 2] WO2008/023452A1 [Patent Document 3] Japanese Patent Laid-Open No. 2013-256584

[發明所欲解決之問題] 先前之包含焊料粉或表面具有焊料層之導電性粒子的各向異性導電膏存在保存穩定性較低之情況。進而,先前之各向異性導電膏存在如下情況:於電極間之連接時,於連接對象構件上配置導電材料後長時間放置之情形時,焊料變得難以於電極上凝集。結果導通可靠性易降低。 本發明之目的在於提供一種導電材料,其保存穩定性較高,於連接對象構件上配置導電材料後即便長時間放置亦顯示出優異之焊料凝集性,因此可表現較高之導通可靠性。又,本發明之目的在於提供一種使用上述導電材料之連接構造體。 [解決問題之技術手段] 根據本發明於廣義上之態樣,提供一種導電材料,其包含於導電部之外表面部分具有焊料之複數個導電性粒子、熱硬化性成分及助焊劑,上述助焊劑為酸與鹼之鹽,且於25℃之導電材料中,上述助焊劑於25℃下係以固體存在。 於本發明之導電材料之某一特定態樣中,於未與上述導電性粒子及上述熱硬化性成分混合之狀態下,上述助焊劑單劑於25℃下為固體。 於本發明之導電材料之某一特定態樣中,上述助焊劑為具有羧基之有機化合物與具有胺基之有機化合物之鹽。 於本發明之導電材料之某一特定態樣中,於25℃之導電材料中,上述助焊劑之平均粒徑為30 μm以下。 於本發明之導電材料之某一特定態樣中,於25℃之導電材料中,上述助焊劑之平均粒徑相對於上述導電性粒子之平均粒徑的比為3以下。 於本發明之導電材料之某一特定態樣中,上述助焊劑之熔點為上述導電性粒子中之焊料之熔點-50℃以上且上述導電性粒子中之焊料之熔點+50℃以下。 於本發明之導電材料之某一特定態樣中,上述導電性粒子為焊料粒子。 於本發明之導電材料之某一特定態樣中,上述熱硬化性成分包含具有三𠯤骨架之熱硬化性化合物。 於本發明之導電材料之某一特定態樣中,上述導電性粒子之表面上附著有上述助焊劑。 於本發明之導電材料之某一特定態樣中,上述導電性粒子之平均粒徑為1 μm以上且40 μm以下。 於本發明之導電材料之某一特定態樣中,於上述導電材料100重量%中,上述導電性粒子之含量為10重量%以上且90重量%以下。 於本發明之導電材料之某一特定態樣中,上述導電材料為導電膏。 根據本發明於廣義上之態樣,提供一種連接構造體,其具備表面具有至少一個第1電極之第1連接對象構件、表面具有至少一個第2電極之第2連接對象構件、及連接上述第1連接對象構件與上述第2連接對象構件之連接部,上述連接部之材料為上述導電材料,且上述第1電極與上述第2電極藉由上述連接部中之焊料部而電性連接。 於本發明之連接構造體之某一特定態樣中,沿上述第1電極與上述連接部及上述第2電極之積層方向觀察上述第1電極與上述第2電極之相對向部分時,上述第1電極與上述第2電極之相對向部分之面積100%中之50%以上配置有上述連接部中之焊料部。 [發明之效果] 本發明之導電材料包含於導電部之外表面部分具有焊料之複數個導電性粒子、熱硬化性成分及助焊劑,上述助焊劑為酸與鹼之鹽,於25℃之導電材料中,上述助焊劑係以固體存在,因此可提高導電材料之保存穩定性,且於連接對象構件上配置導電材料後即便長時間放置亦顯示出優異之焊料凝集性,故可表現較高之導通可靠性。[Problem to be Solved by the Invention] Conventional anisotropic conductive pastes containing solder powder or conductive particles having a solder layer on their surfaces have low storage stability. Furthermore, in conventional anisotropic conductive pastes, when connecting between electrodes, when a conductive material is placed on a member to be connected and then left for a long time, solder becomes difficult to aggregate on the electrodes. As a result, conduction reliability tends to decrease. The object of the present invention is to provide a conductive material which has high storage stability and exhibits excellent solder agglomeration even if it is left for a long time after the conductive material is placed on the member to be connected, so that it can exhibit high conduction reliability. Moreover, the object of this invention is to provide the connection structure using the said electrically-conductive material. [Technical means to solve the problem] According to an aspect of the present invention in a broad sense, a conductive material is provided, which includes a plurality of conductive particles having solder on the outer surface of the conductive part, a thermosetting component, and a flux. Soldering flux is a salt of acid and alkali, and in a conductive material at 25°C, the above-mentioned flux exists as a solid at 25°C. In a specific aspect of the conductive material of the present invention, the single flux flux is solid at 25° C. in a state not mixed with the conductive particles and the thermosetting component. In a specific aspect of the conductive material of the present invention, the flux is a salt of an organic compound having a carboxyl group and an organic compound having an amine group. In a specific aspect of the conductive material of the present invention, in the conductive material at 25° C., the average particle diameter of the above-mentioned flux is 30 μm or less. In a specific aspect of the conductive material of the present invention, in the conductive material at 25° C., the ratio of the average particle diameter of the flux to the average particle diameter of the conductive particles is 3 or less. In a specific aspect of the conductive material of the present invention, the melting point of the flux is -50° C. or higher than the melting point of the solder in the conductive particles and +50° C. or less. In a certain aspect of the conductive material of this invention, the said electroconductive particle is a solder particle. In a specific aspect of the conductive material of the present invention, the thermosetting component includes a thermosetting compound having a three-skeleton skeleton. In a specific aspect of the conductive material of the present invention, the above-mentioned flux is adhered to the surface of the above-mentioned conductive particles. In a specific aspect of the conductive material of the present invention, the average particle diameter of the above-mentioned conductive particles is not less than 1 μm and not more than 40 μm. In a specific aspect of the conductive material of the present invention, the content of the conductive particles is 10% by weight or more and 90% by weight or less in 100% by weight of the conductive material. In a specific aspect of the conductive material of the present invention, the above-mentioned conductive material is a conductive paste. According to an aspect of the present invention in a broad sense, there is provided a connection structure comprising a first connection object member having at least one first electrode on its surface, a second connection object member having at least one second electrode on its surface, and the first connection object member to which the above-mentioned first electrode is connected. 1. A connecting portion between the member to be connected and the second member to be connected, wherein the material of the connecting portion is the above-mentioned conductive material, and the first electrode and the second electrode are electrically connected through the solder portion in the connecting portion. In a specific aspect of the connection structure of the present invention, when the opposing portion of the first electrode and the second electrode is viewed along the lamination direction of the first electrode, the connection portion, and the second electrode, the second electrode 50% or more of the 100% area of the facing portion of the first electrode and the second electrode is provided with the solder portion in the connection portion. [Effects of the Invention] The conductive material of the present invention includes a plurality of conductive particles having solder on the outer surface of the conductive part, a thermosetting component, and flux. The flux is a salt of an acid and an alkali, and conducts electricity at 25°C Among the materials, the above-mentioned flux exists as a solid, so the storage stability of the conductive material can be improved, and after the conductive material is placed on the member to be connected, it shows excellent solder agglomeration even if it is left for a long time, so it can exhibit high performance. conduction reliability.

以下詳細說明本發明。 (導電材料) 本發明之導電材料包含複數個導電性粒子與黏合劑。上述導電性粒子具有導電部。上述導電性粒子於導電部之外表面部分具有焊料。焊料包含於導電部中,為導電部之一部分或全部。上述黏合劑係除上述導電材料所含之導電性粒子以外之成分。 本發明之導電材料包含熱硬化性成分與助焊劑作為上述黏合劑。上述熱硬化性成分較佳為包含熱硬化性化合物與熱硬化劑。 於本發明之導電材料中,上述助焊劑為酸與鹼之鹽。進而,於本發明之導電材料中,於25℃之導電材料中上述助焊劑係以固體存在。更具體而言,於本發明之導電材料中,於25℃之導電材料中上述助焊劑於25℃下係以固體存在。 再者,關於上述助焊劑於25℃之導電材料中是否為固體,可藉由如下方式判斷。於本說明書中,關於25℃下並非液體之助焊劑,將包含助焊劑之導電材料於25℃下靜置5分鐘時保持形狀之助焊劑定義為25℃下固體之助焊劑,將包含助焊劑之導電材料於25℃下靜置5分鐘時未保持形狀之助焊劑定義為25℃下半固體之助焊劑。又,25℃下半固體之助焊劑不包含於25℃下固體之助焊劑中。 於本發明中,由於具備上述構成,故而可提高導電材料之保存穩定性。進而,於本發明中,由於具備上述構成,故而於連接對象構件上配置導電材料後即便長時間放置亦顯示出優異之焊料凝集性,因此可表現較高之導通可靠性。 於本發明中,較佳為於未與上述導電性粒子及上述熱硬化性成分混合之狀態下,上述助焊劑單劑於25℃下為固體。較佳為與上述導電性粒子及上述熱硬化性成分混合前之上述助焊劑單劑於25℃下為固體。於該等情形時,容易使上述助焊劑以固體存在於25℃之導電材料中。 再者,關於上述助焊劑單劑於25℃下是否為固體,可藉由如下方式判斷。於本說明書中,關於25℃下並非液體之助焊劑,將助焊劑單劑於25℃下靜置5分鐘時保持形狀之助焊劑定義為25℃下固體之助焊劑,將助焊劑單劑於25℃下靜置5分鐘時未保持形狀之助焊劑定義為25℃下半固體之助焊劑。又,25℃下半固體之助焊劑不包含於25℃下固體之助焊劑中。 於獲得連接構造體時存在如下情況:於第1連接對象構件上配置導電材料後,於導電材料上配置第2連接對象構件前將第1連接對象構件與導電材料之積層體暫時加以保管。本發明中,即便上述積層體經過保管而亦可獲得導通可靠性優異之連接構造體。 又,於本發明中,由於具備上述構成,故而即便電極寬度較窄而亦可有效率地於電極上配置導電性粒子中之焊料。於電極寬度較窄之情形時存在難以使導電性粒子之焊料聚集至電極上之傾向,但本發明中,即便電極寬度較窄而亦可使焊料充分地聚集至電極上。於本發明中,由於具備上述構成,故而於將電極間進行電性連接之情形時,導電性粒子中之焊料容易位於上下對向之電極間,而可有效率地將導電性粒子中之焊料配置於電極(線)上。又,於本發明中,若電極寬度較寬,則更有效率地於電極上配置導電性粒子中之焊料。 又,導電性粒子中之焊料之一部分不易被配置至未形成電極之區域(間隔),可明顯減少配置於未形成電極之區域之焊料之量。於本發明中,可使並非位於對向之電極間之焊料有效率地移動至對向之電極間。因此,可提高電極間之導通可靠性。並且,可防止於禁止連接之橫向上鄰接之電極間之電性連接,可提高絕緣可靠性。 進而,於本發明中,可提高導電材料之硬化物之耐熱性。尤其於光半導體裝置中使用有導電材料之情形時,受到光照射時發熱而令導電材料之硬化物置於高溫下。本發明之導電材料由於硬化物之耐熱性優異,故而可較佳地用於光半導體裝置。尤其於熱硬化性化合物包含具有三𠯤骨架之熱硬化性化合物之情形時,硬化物之耐熱性變高。 進而,於本發明中,可防止電極間之位置偏離。於本發明中,於使上表面配置有導電材料之第1連接對象構件與第2連接對象構件重合時,即便於第1連接對象構件與第2連接對象構件在第1連接對象構件之電極與第2連接對象構件之電極未對準之狀態下經重合之情形時,亦可修正該偏離而使第1連接對象構件之電極與第2連接對象構件之電極連接(自定位(self alignment)效應)。 為了更有效率地於電極上配置導電性粒子中之焊料,上述導電材料較佳為於25℃下為液狀,較佳為導電膏。為了更有效率地於電極上配置導電性粒子中之焊料,上述導電材料於25℃下之黏度(η25)較佳為10 Pa•s以上,更佳為50 Pa•s以上,進而較佳為100 Pa•s以上,又,較佳為800 Pa•s以下,更佳為600 Pa•s以下,進而較佳為500 Pa•s以下。上述黏度(η25)可藉由調配成分之種類及調配量而進行調整。 上述黏度(η25)可使用例如E型黏度計(東機產業公司製造,「TVE22L」)等於25℃及5 rpm之條件下進行測定。 上述導電材料可以導電膏及導電膜等形式使用。上述導電膜較佳為各向異性導電膜。就更有效率地於電極上配置導電性粒子中之焊料之觀點而言,上述導電材料較佳為導電膏。上述導電材料適用於電極之電性連接。上述導電材料較佳為電路連接材料。 以下說明上述導電材料所含之各成分。再者,本說明書中,「(甲基)丙烯酸酯」意指「丙烯酸酯」與「甲基丙烯酸酯」中之一者或雙方,「(甲基)丙烯酸」意指「丙烯酸」與「甲基丙烯酸」中之一者或雙方,「(甲基)丙烯醯基」意指「丙烯醯基」與「甲基丙烯醯基」中之一者或雙方。 (導電性粒子) 上述導電性粒子使連接對象構件之電極間進行電性連接。上述導電性粒子於導電部之外表面部分具有焊料。上述導電性粒子亦可為由焊料形成之焊料粒子。上述焊料粒子於導電部之外表面部分具有焊料。上述焊料粒子其中心部分及導電部之外表面部分均由焊料形成。上述焊料粒子係中心部分及導電性外表面均為焊料之粒子。上述焊料粒子不具有作為芯粒子之基材粒子。上述焊料粒子不同於具備基材粒子與配置於上述基材粒子之表面上之導電部的導電性粒子。上述焊料粒子例如較佳為包含焊料80重量%以上,更佳為90重量%以上,進而較佳為95重量%以上。上述導電性粒子可具有基材粒子與配置於該基材粒子之表面上之導電部。於該情形時,上述導電性粒子於導電部之外表面部分具有焊料。 再者,與使用上述焊料粒子之情形相比,於使用具備並非由焊料形成之基材粒子與配置於基材粒子之表面上之焊料部的導電性粒子之情形時,導電性粒子難以聚集於電極上,導電性粒子彼此之焊料接合性較低,因此存在已移動至電極上之導電性粒子易向電極外移動之傾向,存在電極間之位置偏離之抑制效果亦變低之傾向。因此,上述導電性粒子較佳為由焊料形成之焊料粒子。 就有效地降低連接構造體中之連接電阻、有效地抑制空隙產生之觀點而言,較佳為於上述導電性粒子之外表面(焊料之外表面)存在羧基或胺基,較佳為存在羧基,較佳為存在胺基。較佳為於上述導電性粒子之外表面(焊料之外表面)經由Si-O鍵、醚鍵、酯鍵或下述式(X)所表示之基而共價鍵結有包含羧基或胺基之基。包含羧基或胺基之基亦可包含羧基與胺基雙方。再者,於下述式(X)中,右端部及左端部表示鍵結部位。 [化1]

Figure 02_image001
焊料之表面存在羥基。藉由使該羥基與包含羧基之基進行共價鍵結,可形成強於以其他配位鍵結(螯合配位)等形態鍵結之情形時之鍵,而獲得能夠降低電極間之連接電阻且抑制空隙產生之導電性粒子。 關於上述導電性粒子,焊料之表面與包含羧基之基的鍵結形態可不包括配位鍵結,可不包括螯合配位形態之鍵結。 就有效地降低連接構造體中之連接電阻、有效地抑制空隙產生之觀點而言,上述導電性粒子較佳為藉由使用具有可與羥基反應之官能基及羧基或胺基之化合物(以下有時記為化合物X),使焊料之表面之羥基和上述可與羥基反應之官能基進行反應而獲得。於上述反應中形成共價鍵。藉由使焊料之表面之羥基和上述化合物X中之可與上述羥基反應之官能基進行反應,可容易地獲得於焊料之表面共價鍵結有包含羧基或胺基之基的焊料粒子,亦可獲得於焊料之表面經由醚鍵或酯鍵而共價鍵結有包含羧基或胺基之基的焊料粒子。藉由使上述焊料之表面之羥基和上述可與羥基反應之官能基進行反應,可使上述化合物X以共價鍵結之形態化學鍵結於焊料之表面。 作為上述可與羥基反應之官能基,可列舉:羥基、羧基、酯基及羰基等。較佳為羥基或羧基。上述可與羥基反應之官能基可為羥基,亦可為羧基。 作為具有可與羥基反應之官能基之化合物,可列舉:乙醯丙酸、戊二酸、乙醇酸、琥珀酸、蘋果酸、草酸、丙二酸、己二酸、5-酮基己酸、3-羥基丙酸、4-胺基丁酸、3-巰基丙酸、3-巰基異丁酸、3-甲基硫代丙酸、3-苯基丙酸、3-苯基異丁酸、4-苯基丁酸、癸酸、十二酸、十四酸、十五酸、十六酸、9-十六碳烯酸、十七酸、硬脂酸、油酸、異油酸、亞麻油酸、(9,12,15)-次亞麻油酸、十九酸、花生酸、癸烷二酸及十二烷二酸等。較佳為戊二酸或乙醇酸。上述具有可與羥基反應之官能基之化合物可僅使用1種,亦可將2種以上併用。上述具有可與羥基反應之官能基之化合物較佳為具有至少1個羧基之化合物。 上述化合物X較佳為具有助焊劑作用,上述化合物X較佳為於鍵結於焊料表面之狀態下具有助焊劑作用。具有助焊劑作用之化合物能夠去除焊料表面之氧化膜及電極表面之氧化膜。羧基具有助焊劑作用。 作為具有助焊劑作用之化合物,可列舉:乙醯丙酸、戊二酸、乙醇酸、己二酸、琥珀酸、5-酮基己酸、3-羥基丙酸、4-胺基丁酸、3-巰基丙酸、3-巰基異丁酸、3-甲基硫代丙酸、3-苯基丙酸、3-苯基異丁酸及4-苯基丁酸等。較佳為戊二酸、己二酸或乙醇酸。上述具有助焊劑作用之化合物可僅使用1種,亦可將2種以上併用。 就有效地降低連接構造體中之連接電阻、有效地抑制空隙產生之觀點而言,上述化合物X中之上述可與羥基反應之官能基較佳為羥基或羧基。上述化合物X中之上述可與羥基反應之官能基可為羥基,亦可為羧基。於上述可與羥基反應之官能基為羧基之情形時,上述化合物X較佳為具有至少2個羧基。藉由使具有至少2個羧基之化合物中之一部分羧基與焊料之表面之羥基反應,可獲得於焊料之表面共價鍵結有包含羧基之基的導電性粒子。 上述導電性粒子之製造方法具備如下步驟:例如使用導電性粒子,將該導電性粒子、具有可與羥基反應之官能基及羧基之化合物、觸媒以及溶劑加以混合。上述導電性粒子之製造方法中,藉由上述混合步驟而可容易地獲得於焊料之表面共價鍵結有包含羧基之基的導電性粒子。 又,上述導電性粒子之製造方法中,較佳為使用導電性粒子,將該導電性粒子、上述具有可與羥基反應之官能基及羧基之化合物、上述觸媒以及上述溶劑加以混合,並進行加熱。藉由混合及加熱步驟而可更容易地獲得於焊料之表面共價鍵結有包含羧基之基的導電性粒子。 作為上述溶劑,可列舉:甲醇、乙醇、丙醇、丁醇等醇溶劑、或丙酮、甲基乙基酮、乙酸乙酯、甲苯及二甲苯等。上述溶劑較佳為有機溶劑,更佳為甲苯。上述溶劑可僅使用1種,亦可將2種以上併用。 作為上述觸媒,可列舉:對甲苯磺酸、苯磺酸及10-樟腦磺酸等。上述觸媒較佳為對甲苯磺酸。上述觸媒可僅使用1種,亦可將2種以上併用。 較佳為於上述混合時進行加熱。加熱溫度較佳為90℃以上,更佳為100℃以上,又,較佳為130℃以下,更佳為110℃以下。 就有效地降低連接構造體中之連接電阻、有效地抑制空隙產生之觀點而言,上述導電性粒子較佳為經過如下步驟,即,使用異氰酸酯化合物,使焊料之表面之羥基與上述異氰酸酯化合物進行反應而獲得。於上述反應中形成共價鍵。藉由使焊料之表面之羥基與上述異氰酸酯化合物進行反應,可容易地獲得於焊料之表面共價鍵結有源自異氰酸酯基之基之氮原子的導電性粒子。藉由使上述焊料之表面之羥基與上述異氰酸酯化合物進行反應,可使源自異氰酸酯基之基以共價鍵結之形態化學鍵結於焊料之表面。 又,源自異氰酸酯基之基可容易地與矽烷偶合劑進行反應。由於可容易地獲得上述導電性粒子,故而上述包含羧基之基較佳為藉由使用具有羧基之矽烷偶合劑之反應而導入、或者藉由於使用矽烷偶合劑之反應後使源自矽烷偶合劑之基與具有至少1個羧基之化合物反應而導入。上述導電性粒子較佳為藉由使用上述異氰酸酯化合物,使焊料之表面之羥基與上述異氰酸酯化合物反應後,與具有至少1個羧基之化合物反應而獲得。 就有效地降低連接構造體中之連接電阻、有效地抑制空隙產生之觀點而言,上述具有至少1個羧基之化合物較佳為具有複數個羧基。 作為上述異氰酸酯化合物,可列舉:二苯基甲烷-4,4'-二異氰酸酯(MDI)、六亞甲基二異氰酸酯(HDI)、甲苯二異氰酸酯(TDI)及異佛爾酮二異氰酸酯(IPDI)等。亦可使用該等以外之異氰酸酯化合物。於使該化合物與焊料之表面反應後,使剩餘之異氰酸酯基和與該剩餘之異氰酸酯基具有反應性且具有羧基之化合物進行反應,藉此可於焊料之表面經由式(X)所表示之基而導入羧基。 作為上述異氰酸酯化合物,亦可使用具有不飽和雙鍵且具有異氰酸酯基之化合物。例如可列舉異氰酸2-丙烯醯氧基乙酯及甲基丙烯酸2-異氰酸酯基乙酯。於使該化合物之異氰酸酯基與焊料之表面反應後,與具有對殘存之不飽和雙鍵具有反應性之官能基且具有羧基的化合物進行反應,藉此可於焊料之表面經由式(X)所表示之基而導入羧基。 作為上述矽烷偶合劑,可列舉3-異氰酸酯基丙基三乙氧基矽烷(Shin-Etsu Silicones公司製造,「KBE-9007」)及3-異氰酸酯基丙基三甲氧基矽烷(MOMENTIVE公司製造,「Y-5187」)等。上述矽烷偶合劑可僅使用1種,亦可將2種以上併用。 作為上述具有至少1個羧基之化合物,可列舉:乙醯丙酸、戊二酸、乙醇酸、琥珀酸、蘋果酸、草酸、丙二酸、己二酸、5-酮基己酸、3-羥基丙酸、4-胺基丁酸、3-巰基丙酸、3-巰基異丁酸、3-甲基硫代丙酸、3-苯基丙酸、3-苯基異丁酸、4-苯基丁酸、癸酸、十二酸、十四酸、十五酸、十六酸、9-十六碳烯酸、十七酸、硬脂酸、油酸、異油酸、亞麻油酸、(9,12,15)-次亞麻油酸、十九酸、花生酸、癸烷二酸及十二烷二酸等。較佳為戊二酸、己二酸或乙醇酸。上述具有至少1個羧基之化合物可僅使用1種,亦可將2種以上併用。 使用上述異氰酸酯化合物,使焊料之表面之羥基與上述異氰酸酯化合物反應後,使具有複數個羧基之化合物之一部分羧基與焊料之表面之羥基反應,藉此可使包含羧基之基殘存。 上述導電性粒子之製造方法中,使用導電性粒子且使用異氰酸酯化合物,使焊料之表面之羥基與上述異氰酸酯化合物反應後,與具有至少1個羧基之化合物反應,而獲得於焊料之表面經由上述式(X)所表示之基而鍵結有包含羧基之基的導電性粒子。上述導電性粒子之製造方法中,藉由上述步驟,可容易地獲得於焊料之表面導入有包含羧基之基的導電性粒子。 作為上述導電性粒子之具體之製造方法,可列舉以下方法。使導電性粒子分散於有機溶劑,添加具有異氰酸酯基之矽烷偶合劑。其後,使用導電性粒子之焊料之表面之羥基與異氰酸酯基的反應觸媒,使矽烷偶合劑共價鍵結於焊料之表面。繼而,使矽烷偶合劑之矽原子上所鍵結之烷氧基水解,藉此生成羥基。使所生成之羥基與具有至少1個羧基之化合物之羧基進行反應。 又,作為上述導電性粒子之具體之製造方法,可列舉以下方法。使導電性粒子分散於有機溶劑,添加具有異氰酸酯基與不飽和雙鍵之化合物。其後,使用導電性粒子之焊料之表面之羥基與異氰酸酯基的反應觸媒而形成共價鍵。其後,對於所導入之不飽和雙鍵,使不飽和雙鍵與具有羧基之化合物反應。 作為導電性粒子之焊料之表面之羥基與異氰酸酯基的反應觸媒,可列舉:錫系觸媒(二月桂酸二丁基錫等)、胺系觸媒(三伸乙基二胺等)、羧酸酯觸媒(環烷酸鉛、乙酸鉀等)、及三烷基膦觸媒(三乙基膦等)等。 就有效地降低連接構造體中之連接電阻、有效地抑制空隙產生之觀點而言,上述具有至少1個羧基之化合物較佳為下述式(1)所表示之化合物。下述式(1)所表示之化合物具有助焊劑作用。又,下述式(1)所表示之化合物於被導入至焊料表面之狀態下具有助焊劑作用。 [化2]
Figure 02_image003
上述式(1)中,X表示可與羥基反應之官能基,R表示碳數1~5之2價有機基。該有機基可包含碳原子、氫原子及氧原子。該有機基可為碳數1~5之2價烴基。上述有機基之主鏈較佳為2價烴基。該有機基可於2價烴基上鍵結有羧基或羥基。上述式(1)所表示之化合物例如包含檸檬酸。 上述具有至少1個羧基之化合物較佳為下述式(1A)或下述式(1B)所表示之化合物。上述具有至少1個羧基之化合物較佳為下述式(1A)所表示之化合物,更佳為下述式(1B)所表示之化合物。 [化3]
Figure 02_image005
上述式(1A)中,R表示碳數1~5之2價有機基。上述式(1A)中之R與上述式(1)中之R相同。 [化4]
Figure 02_image007
上述式(1B)中,R表示碳數1~5之2價有機基。上述式(1B)中之R與上述式(1)中之R相同。 焊料之表面較佳為鍵結有下述式(2A)或下述式(2B)所表示之基。焊料之表面較佳為鍵結有下述式(2A)所表示之基,更佳為鍵結有下述式(2B)所表示之基。再者,下述式(2A)及下述式(2B)中,左端部表示鍵結部位。 [化5]
Figure 02_image009
上述式(2A)中,R表示碳數1~5之2價有機基。上述式(2A)中之R與上述式(1)中之R相同。 [化6]
Figure 02_image011
上述式(2B)中,R表示碳數1~5之2價有機基。上述式(2B)中之R與上述式(1)中之R相同。 就提高焊料之表面之潤濕性之觀點而言,上述具有至少1個羧基之化合物之分子量較佳為10000以下,更佳為1000以下,進而較佳為500以下。就更有效地抑制遷移之觀點、及更有效地降低連接構造體中之連接電阻之觀點而言,上述具有至少1個羧基之化合物之分子量較佳為80以上,更佳為100以上,進而較佳為120以上。 上述分子量於上述具有至少1個羧基之化合物並非聚合物之情形、及上述具有至少1個羧基之化合物之結構式能夠特定之情形時,意指可根據該結構式而算出之分子量。又,於上述具有至少1個羧基之化合物為聚合物之情形時,意指重量平均分子量。 就可有效地提高導電連接時導電性粒子之凝集性之方面而言,上述導電性粒子較佳為具有導電性粒子本身、與配置於上述導電性粒子本身之表面上之陰離子聚合物。上述導電性粒子較佳為藉由利用陰離子聚合物或會成為陰離子聚合物之化合物對導電性粒子本身進行表面處理而獲得。上述導電性粒子較佳為利用陰離子聚合物或會成為陰離子聚合物之化合物進行處理而得之表面處理物。上述陰離子聚合物及上述會成為陰離子聚合物之化合物分別可僅使用1種,亦可將2種以上併用。上述陰離子聚合物為具有酸性基之聚合物。 作為利用陰離子聚合物對導電性粒子本身進行表面處理之方法,可列舉使陰離子聚合物之羧基與導電性粒子本身之表面之羥基反應之方法,作為陰離子聚合物,使用例如使(甲基)丙烯酸共聚合而成之(甲基)丙烯酸聚合物、由二羧酸與二醇所合成且兩末端具有羧基之聚酯聚合物、由二羧酸之分子間脫水縮合反應所獲得且兩末端具有羧基之聚合物、由二羧酸與二胺所合成且兩末端具有羧基之聚酯聚合物、以及具有羧基之改性聚乙烯醇(日本合成化學公司製造,「GOHSENX T」)等。 作為上述陰離子聚合物之陰離子部分,可列舉上述羧基,除此以外,可列舉:對甲苯磺醯基(p-H3 CC6 H4 S(=O)2 -)、磺酸根離子基(-SO3 - )及磷酸根離子基(-PO4 - )等。 又,作為表面處理之其他方法,可列舉使用如下化合物而使該化合物於導電性粒子本身之表面上進行聚合物化之方法,上述化合物具有可與導電性粒子本身之表面之羥基反應之官能基,進而具有藉由加成、縮合反應而能夠聚合之官能基。作為與導電性粒子本身之表面之羥基反應之官能基,可列舉羧基及異氰酸酯基等,作為藉由加成、縮合反應而聚合之官能基,可列舉:羥基、羧基、胺基及(甲基)丙烯醯基。 上述陰離子聚合物之重量平均分子量較佳為2000以上,更佳為3000以上,又,較佳為10000以下,更佳為8000以下。若上述重量平均分子量為上述下限以上及上述上限以下,則可對導電性粒子之表面導入充足量之電荷、及賦予助焊劑性。藉此,於導電連接時可有效地提高導電性粒子之凝集性,且於連接對象構件之連接時可有效地去除電極之表面之氧化膜。 若上述重量平均分子量為上述下限以上及上述上限以下,則易於導電性粒子本身之表面上配置陰離子聚合物,可有效地提高導電連接時導電性粒子之凝集性,可更有效率地於電極上配置導電性粒子。 上述重量平均分子量表示藉由凝膠滲透層析法(GPC)所測得之經聚苯乙烯換算之重量平均分子量。 藉由利用會成為陰離子聚合物之化合物對導電性粒子本身進行表面處理所獲得之聚合物之重量平均分子量可以如下方式求出,即,使導電性粒子中之焊料熔解,利用不會引起聚合物分解之稀鹽酸等而去除導電性粒子後,測定殘存之聚合物之重量平均分子量。 關於陰離子聚合物於導電性粒子之表面之導入量,每1 g導電性粒子之酸值較佳為1 mgKOH以上,更佳為2 mgKOH以上,又,較佳為10 mgKOH以下,更佳為6 mgKOH以下。 上述酸值可藉由如下方式測定。將1 g導電性粒子添加至36 g丙酮中,利用超音波使之分散1分鐘。其後,使用酚酞作為指示劑,利用0.1 mol/L之氫氧化鉀乙醇溶液進行滴定。 其次,一面參照圖式一面說明導電性粒子之具體例。 圖4係表示可用於導電材料之導電性粒子之第1例的剖視圖。 圖4所示之導電性粒子21為焊料粒子。導電性粒子21整體由焊料形成。導電性粒子21於芯部不具有基材粒子,其並非芯-殼粒子。導電性粒子21其中心部分及導電部之外表面部分均由焊料形成。 圖5係表示可用於導電材料之導電性粒子之第2例的剖視圖。 圖5所示之導電性粒子31具備基材粒子32、與配置於基材粒子32之表面上之導電部33。導電部33被覆基材粒子32之表面。導電性粒子31為基材粒子32之表面經導電部33被覆之被覆粒子。 導電部33具有第2導電部33A與焊料部33B(第1導電部)。導電性粒子31於基材粒子32與焊料部33B之間具備第2導電部33A。因此,導電性粒子31具備基材粒子32、配置於基材粒子32之表面上之第2導電部33A、及配置於第2導電部33A之外表面上之焊料部33B。 圖6係表示可用於導電材料之導電性粒子之第3例的剖視圖。 如上所述,導電性粒子31中之導電部33具有雙層構造。圖6所示之導電性粒子41具有焊料部42作為單層之導電部。導電性粒子41具備基材粒子32、與配置於基材粒子32之表面上之焊料部42。 作為上述基材粒子,可列舉:樹脂粒子、除金屬粒子以外之無機粒子、有機無機混合粒子及金屬粒子等。上述基材粒子較佳為除金屬以外之基材粒子,較佳為樹脂粒子、除金屬粒子以外之無機粒子或有機無機混合粒子。上述基材粒子亦可為銅粒子。 作為用以形成上述樹脂粒子之樹脂,適宜使用各種有機物。作為用以形成上述樹脂粒子之樹脂,例如可列舉:聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚偏二氯乙烯、聚異丁烯、聚丁二烯等聚烯烴樹脂;聚甲基丙烯酸甲酯及聚丙烯酸甲酯等丙烯酸系樹脂;聚碳酸酯、聚醯胺、苯酚甲醛樹脂、三聚氰胺甲醛樹脂、苯胍胺甲醛樹脂、脲甲醛樹脂、酚系樹脂、三聚氰胺樹脂、苯胍胺樹脂、脲樹脂、環氧樹脂、不飽和聚酯樹脂、飽和聚酯樹脂、聚對苯二甲酸乙二酯、聚碸、聚苯醚、聚縮醛、聚醯亞胺、聚醯胺醯亞胺、聚醚醚酮、聚醚碸、二乙烯苯聚合物、以及二乙烯苯系共聚物等。作為上述二乙烯苯系共聚物等,可列舉二乙烯苯-苯乙烯共聚物及二乙烯苯-(甲基)丙烯酸酯共聚物等。用以形成上述樹脂粒子之樹脂較佳為使1種或2種以上之具有乙烯性不飽和基之聚合性單體進行聚合而成之聚合物,其原因在於可容易地將上述樹脂粒子之硬度控制於適宜範圍。 於使具有乙烯性不飽和基之聚合性單體進行聚合而獲得上述樹脂粒子之情形時,作為該具有乙烯性不飽和基之聚合性單體,可列舉非交聯性單體與交聯性單體。 作為上述非交聯性單體,例如可列舉:苯乙烯、α-甲基苯乙烯等苯乙烯系單體;(甲基)丙烯酸、順丁烯二酸、順丁烯二酸酐等含羧基之單體;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異𦯉酯等(甲基)丙烯酸烷基酯化合物;(甲基)丙烯酸2-羥基乙酯、甘油(甲基)丙烯酸酯、聚氧乙烯(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯等含氧原子之(甲基)丙烯酸酯化合物;(甲基)丙烯腈等含腈基之單體;甲基乙烯醚、乙基乙烯醚、丙基乙烯醚等乙烯醚化合物;乙酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等酸乙烯酯化合物;乙烯、丙烯、異戊二烯、丁二烯等不飽和烴;(甲基)丙烯酸三氟甲酯、(甲基)丙烯酸五氟乙酯、氯乙烯、氟乙烯、氯苯乙烯等含鹵素之單體等。 作為上述交聯性單體,例如可列舉:四羥甲基甲烷四(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、甘油二(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、(聚)四亞甲基二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯化合物;異氰尿酸三烯丙酯、偏苯三酸三烯丙酯、二乙烯苯、苯二甲酸二烯丙酯、二烯丙基丙烯醯胺、二烯丙醚、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、三甲氧基矽烷基苯乙烯、乙烯基三甲氧基矽烷等含矽烷之單體等。 藉由利用公知方法使上述具有乙烯性不飽和基之聚合性單體進行聚合而可獲得上述樹脂粒子。作為該方法,例如可列舉如下方法等:於自由基聚合起始劑之存在下進行懸浮聚合;以及使用非交聯之種粒子,與自由基聚合起始劑一併使單體膨潤而聚合。 於上述基材粒子為除金屬以外之無機粒子或有機無機混合粒子之情形時,作為用以形成基材粒子之無機物,可列舉:二氧化矽、氧化鋁、鈦酸鋇、氧化鋯及碳黑等。由上述二氧化矽所形成之粒子並無特別限定,例如可列舉藉由使具有2個以上之水解性烷氧基矽烷基之矽化合物水解而形成交聯聚合物粒子後視需要進行焙燒所獲得的粒子。作為上述有機無機混合粒子,例如可列舉由經交聯而成之烷氧基矽烷基聚合物與丙烯酸系樹脂所形成的有機無機混合粒子等。 於上述基材粒子為金屬粒子之情形時,作為用以形成該金屬粒子之金屬,可列舉:銀、銅、鎳、矽、金及鈦等。於上述基材粒子為金屬粒子之情形時,該金屬粒子較佳為銅粒子。但上述基材粒子較佳為並非金屬粒子。 於上述基材粒子之表面上形成導電部之方法、以及於上述基材粒子之表面上或上述第2導電部之表面上形成焊料部之方法並無特別限定。作為形成上述導電部及上述焊料部之方法,例如可列舉:無電鍍方法、電鍍方法、物理碰撞方法、藉由機械化學反應之方法、物理蒸鍍方法或物理吸附方法、以及於基材粒子之表面塗佈金屬粉末或包含金屬粉末與黏合劑之漿料之方法等。適宜為無電鍍方法、電鍍方法或物理碰撞方法。作為上述物理蒸鍍方法,可列舉:真空蒸鍍、離子鍍覆及離子濺鍍等方法。又,關於上述物理碰撞方法,例如使用Theta-composer(德壽工作所公司製造)等。 上述基材粒子之熔點較佳為高於上述焊料部之熔點。上述基材粒子之熔點較佳為超過160℃,更佳為超過300℃,進而較佳為超過400℃,尤佳為超過450℃。再者,上述基材粒子之熔點亦可未達400℃。上述基材粒子之熔點亦可為160℃以下。上述基材粒子之軟化點較佳為260℃以上。上述基材粒子之軟化點亦可未達260℃。 上述導電性粒子可具有單層之焊料部。上述導電性粒子可具有複數層之導電部(焊料部、第2導電部)。即,上述導電性粒子中可積層2層以上之導電部。 上述焊料較佳為熔點450℃以下之金屬(低熔點金屬)。上述焊料部較佳為熔點450℃以下之金屬層(低熔點金屬層)。上述低熔點金屬層為包含低熔點金屬之層。上述導電性粒子中之焊料較佳為熔點450℃以下之金屬粒子(低熔點金屬粒子)。上述低熔點金屬粒子為包含低熔點金屬之粒子。該低熔點金屬係指熔點為450℃以下之金屬。低熔點金屬之熔點較佳為300℃以下,更佳為160℃以下。又,上述導電性粒子中之焊料較佳為包含錫。於上述焊料部所含之金屬100重量%中及上述導電性粒子中之焊料所含之金屬100重量%中,錫之含量較佳為30重量%以上,更佳為40重量%以上,進而較佳為70重量%以上,尤佳為90重量%以上。若上述導電性粒子中之焊料中之錫之含量為上述下限以上,則導電性粒子與電極之導通可靠性進一步變高。 再者,上述錫之含量可使用高頻感應耦合電漿發射光譜分析裝置(堀場製作所公司製造,「ICP-AES」)或螢光X射線分析裝置(島津製作所公司製造,「EDX-800HS」)等進行測定。 藉由使用於導電部之外表面部分具有上述焊料之導電性粒子,焊料熔融而與電極接合,焊料使電極間導通。例如焊料與電極易成為面接觸而非點接觸,因此連接電阻變低。又,藉由使用於導電部之外表面部分具有焊料之導電性粒子,焊料與電極之接合強度變高,結果焊料與電極更不易發生剝離,導通可靠性顯著變高。 構成上述焊料部及上述焊料粒子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。作為該合金,可列舉:錫-銀合金、錫-銅合金、錫-銀-銅合金、錫-鉍合金、錫-鋅合金、錫-銦合金等。就對電極之潤濕性優異之方面而言,上述低熔點金屬較佳為錫、錫-銀合金、錫-銀-銅合金、錫-鉍合金、錫-銦合金。更佳為錫-鉍合金、錫-銦合金。 構成上述焊料(焊料部)之材料較佳為基於JIS Z3001:焊接用語而液相線為450℃以下之溶加材料。作為上述焊料之組成,例如可列舉包含鋅、金、銀、鉛、銅、錫、鉍、銦等之金屬組成。較佳為低熔點且無鉛之錫-銦系(117℃共晶)或錫-鉍系(139℃共晶)。即,上述焊料較佳為不含鉛,較佳為包含錫與銦之焊料或包含錫與鉍之焊料。 為了進一步提高上述焊料與電極之接合強度,上述導電性粒子中之焊料可包含鎳、銅、銻、鋁、鋅、鐵、金、鈦、磷、鍺、碲、鈷、鉍、錳、鉻、鉬、鈀等金屬。又,就更進一步提高焊料與電極之接合強度之觀點而言,上述導電性粒子中之焊料較佳為包含鎳、銅、銻、鋁或鋅。就更進一步提高焊料部或導電性粒子中之焊料與電極之接合強度之觀點而言,於上述導電性粒子中之焊料100重量%中,用以提高接合強度之該等金屬之含量較佳為0.0001重量%以上,且較佳為1重量%以下。 上述第2導電部之熔點較佳為高於上述焊料部之熔點。上述第2導電部之熔點較佳為超過160℃,更佳為超過300℃,進而較佳為超過400℃,進而更佳為超過450℃,尤佳為超過500℃,最佳為超過600℃。上述焊料部由於熔點較低,故而於導電連接時熔融。上述第2導電部較佳為於導電連接時不熔融。上述導電性粒子較佳為於焊料熔融之狀態下使用,較佳為於上述焊料部熔融之狀態下使用,較佳為於上述焊料部熔融且上述第2導電部未熔融之狀態下使用。藉由上述第2導電部之熔點高於上述焊料部之熔點,而於導電連接時,可僅使上述焊料部熔融而不會使上述第2導電部熔融。 上述焊料部之熔點與上述第2導電部之熔點的差之絕對值超過0℃,較佳為5℃以上,更佳為10℃以上,進而較佳為30℃以上,尤佳為50℃以上,最佳為100℃以上。 上述第2導電部較佳為包含金屬。構成上述第2導電部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,作為上述金屬,亦可使用摻錫氧化銦(ITO)。上述金屬可僅使用1種,亦可將2種以上併用。 上述第2導電部較佳為鎳層、鈀層、銅層或金層,更佳為鎳層或金層,進而較佳為銅層。導電性粒子較佳為具有鎳層、鈀層、銅層或金層,更佳為具有鎳層或金層,進而較佳為具有銅層。藉由使用具有該等較佳導電部之導電性粒子進行電極間之連接,電極間之連接電阻進一步變低。又,該等較佳導電部之表面上可更容易地形成焊料部。 上述焊料部之厚度較佳為0.005 μm以上,更佳為0.01 μm以上,又,較佳為10 μm以下,更佳為1 μm以下,進而較佳為0.3 μm以下。若焊料部之厚度為上述下限以上及上述上限以下,則可獲得充分之導電性,且導電性粒子不會變得過硬,於電極間之連接時導電性粒子可充分變形。 上述導電部之厚度(導電部整體之厚度)較佳為0.005 μm以上,更佳為0.01 μm以上,又,較佳為10 μm以下,更佳為1 μm以下,進而較佳為0.5 μm以下,尤佳為0.3 μm以下。上述導電部之厚度於導電部為多層之情形時乃全部之導電層之厚度。若導電部之厚度為上述下限以上及上述上限以下,則可獲得充分之導電性,且導電性粒子不會變得過硬,於電極間之連接時導電性粒子可充分變形。 於上述導電部係由複數層形成之情形時,最外層之導電層之厚度較佳為0.001 μm以上,更佳為0.01 μm以上,又,較佳為0.5 μm以下,更佳為0.1 μm以下。若上述最外層之導電層之厚度為上述下限以上及上述上限以下,則藉由最外層之導電層所進行之被覆變得均勻,耐腐蝕性充分變高,且電極間之連接電阻進一步變低。又,於上述最外層為金層之情形時,金層之厚度越薄則成本越低。 上述導電部之厚度可使用例如場發射型掃描式電子顯微鏡(FE-SEM)觀察導電性粒子之剖面而進行測定。 將所獲得之導電性粒子以其含量成為30重量%之方式添加至Kulzer公司製造之「Technovit 4000」中,使之分散,而製作導電性粒子檢查用嵌入樹脂。使用離子研磨裝置(Hitachi High-Technologies公司製造,「IM4000」),以通過該檢查用嵌入樹脂中所分散之導電性粒子之中心附近之方式切出導電性粒子之剖面。 進而,較佳為使用場發射型掃描式電子顯微鏡(FE-SEM),將圖像倍率設定為5萬倍,隨機選擇50個導電性粒子,觀察各導電性粒子之導電部。較佳為計測所獲得之導電性粒子中之導電部之厚度,將其進行算術平均而作為導電部之厚度。 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,進而較佳為3 μm以上,又,較佳為100 μm以下,更佳為50 μm以下,進而較佳為40 μm以下,尤佳為30 μm以下。若上述導電性粒子之平均粒徑為上述下限以上及上述上限以下,則可更有效率地於電極上配置導電性粒子中之焊料,易於電極間較多地配置導電性粒子中之焊料,導通可靠性進一步變高。 上述導電性粒子之「平均粒徑」表示數量平均粒徑。導電性粒子之平均粒徑係藉由如下方式求出,例如利用電子顯微鏡或光學顯微鏡觀察任意之50個導電性粒子,算出平均值。 再者,於與熱硬化性成分及助焊劑混合前之導電性粒子單獨成分的狀態下和於與熱硬化性成分及助焊劑混合後之導電材料中之導電性粒子的狀態下,導電性粒子之平均粒徑一般而言相同。 上述導電性粒子之形狀並無特別限定。上述導電性粒子之形狀可為球狀,亦可為扁平狀等球形狀以外之形狀。 於上述導電材料100重量%中,上述導電性粒子之含量較佳為1重量%以上,更佳為2重量%以上,進而較佳為10重量%以上,尤佳為20重量%以上,最佳為30重量%以上,又,較佳為90重量%以下,更佳為80重量%以下,進而較佳為60重量%以下,尤佳為50重量%以下。若上述導電性粒子之含量為上述下限以上及上述上限以下,則可更有效率地於電極上配置導電性粒子中之焊料,易於電極間較多地配置導電性粒子中之焊料,導通可靠性進一步變高。就進一步提高導通可靠性之觀點而言,上述導電性粒子之含量宜為較多。 (熱硬化性化合物) 上述熱硬化性化合物為藉由加熱而能夠硬化之化合物。作為上述熱硬化性化合物,可列舉:氧雜環丁烷化合物、環氧化合物、環硫化合物、(甲基)丙烯酸系化合物、酚化合物、胺基化合物、不飽和聚酯化合物、聚胺基甲酸酯化合物、聚矽氧化合物及聚醯亞胺化合物等。就進一步優化導電材料之硬化性及黏度、進一步提高導通可靠性及連接可靠性之觀點而言,較佳為環氧化合物或環硫化合物,更佳為環氧化合物。上述導電材料較佳為包含環氧化合物。上述熱硬化性化合物可僅使用1種,亦可將2種以上併用。 就有效地提高硬化物之耐熱性之觀點、以及有效地降低硬化物之介電常數之觀點而言,上述熱硬化性化合物較佳為包含具有氮原子之熱硬化性化合物,更佳為包含具有三𠯤骨架之熱硬化性化合物。 作為上述具有三𠯤骨架之熱硬化性化合物,可列舉三𠯤三縮水甘油醚等,可列舉日產化學工業公司製造之TEPIC系列(TEPIC-G、TEPIC-S、TEPIC-SS、TEPIC-HP、TEPIC-L、TEPIC-PAS、TEPIC-VL、TEPIC-UC)等。 作為上述環氧化合物,可列舉芳香族環氧化合物。較佳為間苯二酚型環氧化合物、萘型環氧化合物、聯苯型環氧化合物、二苯甲酮型環氧化合物等結晶性環氧化合物。較佳為於常溫(23℃)下為固體且熔融溫度為焊料之熔點以下之環氧化合物。熔融溫度較佳為100℃以下,更佳為80℃以下,較佳為40℃以上。藉由使用上述較佳之環氧化合物,而於將連接對象構件進行貼合之階段中因黏度較高、搬送等衝擊而產生加速度時,可抑制第1連接對象構件與第2連接對象構件之位置偏離,再者,可藉由硬化時之熱而大幅降低導電材料之黏度,可使焊料效率良好地進行凝集。 於上述導電材料100重量%中,上述熱硬化性化合物之含量較佳為20重量%以上,更佳為40重量%以上,進而較佳為50重量%以上,又,較佳為99重量%以下,更佳為98重量%以下,進而較佳為90重量%以下,尤佳為80重量%以下。就進一步提高耐衝擊性之觀點而言,上述熱硬化性化合物之含量宜為較多。 (熱硬化劑) 上述熱硬化劑可使上述熱硬化性化合物熱硬化。作為上述熱硬化劑,存在咪唑硬化劑、酚系硬化劑、硫醇硬化劑、胺硬化劑、酸酐硬化劑、熱陽離子起始劑及熱自由基產生劑等。上述熱硬化劑可僅使用1種,亦可將2種以上併用。 作為上述咪唑硬化劑,並無特別限定,可列舉:2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基第二-三𠯤及2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基第二-三𠯤異三聚氰酸加成物等。 作為上述硫醇硬化劑,並無特別限定,可列舉:三羥甲基丙烷三-3-巰基丙酸酯、季戊四醇四-3-巰基丙酸酯及二季戊四醇六-3-巰基丙酸酯等。 上述硫醇硬化劑之溶解度參數較佳為9.5以上,且較佳為12以下。上述溶解度參數係藉由Fedors法而計算。例如三羥甲基丙烷三-3-巰基丙酸酯之溶解度參數為9.6,二季戊四醇六-3-巰基丙酸酯之溶解度參數為11.4。 作為上述胺硬化劑,並無特別限定,可列舉:六亞甲基二胺、八亞甲基二胺、十亞甲基二胺、3,9-雙(3-胺基丙基)-2,4,8,10-四螺[5.5]十一烷、雙(4-胺基環己基)甲烷、間苯二胺及二胺基二苯基碸等。 作為上述熱陽離子起始劑,可列舉:錪系陽離子硬化劑、氧鎓系陽離子硬化劑及鋶系陽離子硬化劑等。作為上述錪系陽離子硬化劑,可列舉六氟磷酸雙(4-第三丁基苯基)錪等。作為上述氧鎓系陽離子硬化劑,可列舉四氟硼酸三甲基氧鎓等。作為上述鋶系陽離子硬化劑,可列舉六氟磷酸三對甲苯基鋶等。 作為上述熱自由基產生劑,並無特別限定,可列舉偶氮化合物及有機過氧化物等。作為上述偶氮化合物,可列舉偶氮二異丁腈(AIBN)等。作為上述有機過氧化物,可列舉二-第三丁基過氧化物及甲基乙基酮過氧化物等。 上述熱硬化劑之反應起始溫度較佳為50℃以上,更佳為70℃以上,進而較佳為80℃以上,又,較佳為250℃以下,更佳為200℃以下,進而較佳為150℃以下,尤佳為140℃以下。若上述熱硬化劑之反應起始溫度為上述下限以上及上述上限以下,則更有效率地於電極上配置導電性粒子中之焊料。上述熱硬化劑之反應起始溫度尤佳為80℃以上且140℃以下。 就更有效率地於電極上配置導電性粒子中之焊料之觀點而言,上述熱硬化劑之反應起始溫度較佳為高於上述導電性粒子中之焊料之熔點,更佳為高5℃以上,進而較佳為高10℃以上。 上述熱硬化劑之反應起始溫度意指利用DSC(differential scanning calorimeter,示差掃描熱量計)所測得之發熱波峰之上升起始之溫度。 上述熱硬化劑之含量並無特別限定。相對於上述熱硬化性化合物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1重量份以上,又,較佳為200重量份以下,更佳為100重量份以下,進而較佳為75重量份以下。若熱硬化劑之含量為上述下限以上,則容易使導電材料充分硬化。若熱硬化劑之含量為上述上限以下,則硬化後不易殘存未參與硬化之剩餘之熱硬化劑,且硬化物之耐熱性進一步變高。 (助焊劑) 上述導電材料包含助焊劑。藉由使用助焊劑而可更有效地於電極上配置導電性粒子中之焊料。又,於本發明中,上述助焊劑為具有清洗金屬表面之效果之酸與具有中和該酸之作用之鹼的組合,為該等酸與鹼之鹽。 若該作為特定之酸與鹼之鹽的上述助焊劑於25℃下為固體,則導電材料之保存穩定性變高,於連接對象構件上配置導電材料後即便長時間放置亦顯示出優異之焊料凝集性,因此可提供能夠表現較高之導通可靠性之導電材料。上述助焊劑較佳為酸與鹼之鹽且於25℃下為固體。 上述助焊劑例如為具有羧基之有機化合物與具有胺基之化合物的鹽,較佳為具有羧基之有機化合物與具有胺基之有機化合物的鹽。 又,就有效地提高導電材料之保存穩定性、於連接對象構件上配置導電材料後即便長時間放置亦顯示出優異之焊料凝集性、表現較高之導通可靠性的觀點而言,作為特定之酸與鹼之鹽的上述助焊劑較佳為於25℃下為固體。上述助焊劑可僅使用1種,亦可將2種以上併用。 上述助焊劑例如可藉由使羧酸或羧酸酐與含胺基之化合物進行中和反應而獲得。上述助焊劑較佳為羧酸或羧酸酐與含胺基之化合物之中和反應物。 作為上述羧酸或羧酸酐,可列舉:作為脂肪族系羧酸之琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、蘋果酸,作為環狀脂肪族羧酸之環己基羧酸、1,4-環己基二羧酸,作為芳香族羧酸之間苯二甲酸、對苯二甲酸、偏苯三甲酸,及乙二胺四乙酸、以及該等之酸酐等。 為了進一步提高助焊劑效果,上述酸及上述具有羧基之有機化合物較佳為具有複數個羧基。作為具有複數個羧基之有機化合物,可列舉二羧酸及三羧酸等。又,為了易於形成鹽,上述酸及上述具有羧基之有機化合物較佳為具有烷基,該烷基與羧基之碳數之合計較佳為4以上且較佳為8以下。 為了獲得上述反應物,亦可使用羧酸之酯。作為羧酸之酯,可列舉上述羧酸之烷基酯等。作為上述羧酸之烷基酯之烷基,可列舉碳數1~4之烷基,該烷基之碳數較佳為3以下,更佳為2以下。 作為上述含胺基之化合物中之不具有芳香族骨架之含胺基之化合物,可列舉:二乙醇胺、三乙醇胺、甲基二乙醇胺、乙基二乙醇胺、環己基胺及二環己基胺等。 作為上述含胺基之化合物中之具有芳香族骨架之含胺基之化合物,可列舉:苄基胺、二苯甲基胺、2-甲基苄基胺、3-甲基苄基胺及4-第三丁基苄基胺等。作為二級胺,可列舉:N-甲基苄基胺、N-乙基苄基胺、N-苯基苄基胺、N-第三丁基苄基胺及N-異丙基苄基胺等。作為三級胺,可列舉:N,N-二甲基苄基胺、咪唑化合物及三唑化合物。就有效地提高導電材料之保存穩定性、使除導電性粒子以外之成分於電極間之連接時更難移動的觀點而言,上述含胺基之化合物較佳為芳香族胺化合物或脂肪族脂環式胺化合物。 上述助焊劑之活性溫度(熔點)較佳為40℃以上,更佳為50℃以上。若上述助焊劑之活性溫度為上述下限以上,則保存穩定性進一步變高。 就更有效率地於電極上配置導電性粒子中之焊料之觀點而言,上述助焊劑之熔點較佳為上述導電性粒子中之焊料之熔點-50℃以上,更佳為上述導電性粒子中之焊料之熔點-30℃以上,又,較佳為上述導電性粒子中之焊料之熔點+50℃以下,更佳為上述導電性粒子中之焊料之熔點+30℃以下,進而較佳為未達上述導電性粒子中之焊料之熔點。若上述助焊劑之熔點為上述下限以上及上述上限以下,則更有效地發揮助焊劑效果,更有效率地於電極上配置焊料。 就更有效率地於電極上配置導電性粒子中之焊料之觀點而言,上述助焊劑之熔點較佳為低於上述熱硬化劑之反應起始溫度,更佳為低5℃以上,進而較佳為低10℃以上。 上述助焊劑可分散於導電材料中,亦可附著於導電性粒子之表面上。 於25℃之導電材料中,上述助焊劑係以固體存在。於導電材料中以均勻熔解之狀態添加有助焊劑之情形時,存在因熱硬化性成分與助焊劑其等一部分發生反應而導致導電材料之黏度上升的情況。又,存在如下情況:若於連接對象構件上配置導電材料而令導電材料長時間處於與空氣接觸之狀態,則空氣中之水分會促進助焊劑與熱硬化性化合物之反應、或會因助焊劑與焊料表面之反應而生成金屬離子等,從而對焊料之凝集性或鄰接電極間之絕緣性造成不良影響。相對於此,若上述助焊劑以固體存在於25℃之導電材料中,則僅助焊劑之表面會受到上述影響,因此可表現較高之保存穩定性、或長時間放置後亦較高之導通性、絕緣性。 又,於上述助焊劑以固體存在於25℃之導電材料中、且上述助焊劑會於低於焊料熔點之溫度下熔解的情形時,於導電材料為漿料之情況下,則可對導電材料賦予室溫(23℃)下之觸變性。藉此,可防止導電性粒子發生沈澱、或可實現於塗佈後之形狀保持性,可進一步防止導電材料向不必要部位流出。於導電材料為膜之情況下,藉由上述助焊劑為固體而可減少導電材料中之液狀成分,因此可提高膜之切割性,可抑制自切割面之滲出。 又,於上述助焊劑會於低於焊料熔點之溫度下熔解之情形時,若於焊料之熔點下則助焊劑呈熔解狀態,因此導電材料之熔融黏度充分降低,可表現出更良好之焊料凝集性。 進而,於上述助焊劑會於低於焊料熔點之溫度下熔解之情形時,若於焊料之熔點以上之溫度下,則助焊劑熔解至熱硬化性化合物或熱硬化劑中,進而,熱硬化性化合物或熱硬化劑與助焊劑之羧基、胺基發生反應,藉此助焊劑成分被取入至硬化系中。藉此,可使鄰接電極間表現出較高之絕緣性,進而可防止電極腐蝕。 於25℃之導電材料中,助焊劑之平均粒徑較佳為30 μm以下。藉由助焊劑之平均粒徑處於上述範圍,可使助焊劑以不會與樹脂反應之狀態存在於導電材料中,可進一步提高導電材料之保存穩定性。基於相同原因,助焊劑之平均粒徑較佳為0.1 μm以上。 上述助焊劑之「平均粒徑」表示數量平均粒徑。助焊劑之平均粒徑係藉由如下方式求出,例如利用電子顯微鏡或光學顯微鏡觀察任意之50個導電性粒子,算出平均值。 再者,若於與導電性粒子及熱硬化性成分混合前之助焊劑單劑的狀態下和於與導電性粒子及熱硬化性成分混合後之導電材料中之助焊劑的狀態下,助焊劑之平均粒徑無差異,則可利用與導電性粒子及熱硬化性成分混合前之助焊劑單劑而評價平均粒徑。 又,於25℃之導電材料中,助焊劑之平均粒徑相對於導電性粒子之平均粒徑的比(助焊劑之平均粒徑/導電性粒子之平均粒徑)較佳為3以下,更佳為1以下,進而較佳為0.2以下。若上述比為上述上限以下,則可使助焊劑有效地接觸導電性粒子,可進一步提高加熱時之助焊劑性能。基於相同原因,上述比(助焊劑之平均粒徑/導電性粒子之平均粒徑)較佳為0.005以上,更佳為0.01以上,進而較佳為0.02以上。 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,又,較佳為30重量%以下,更佳為25重量%以下。 (絕緣性粒子) 就高精度地控制藉由導電材料之硬化物而連接之連接對象構件間之間隔、以及藉由導電性粒子中之焊料而連接之連接對象構件間之間隔的觀點而言,上述導電材料較佳為包含絕緣性粒子。上述導電材料中,上述絕緣性粒子可並非附著於導電性粒子之表面。上述導電材料中,上述絕緣性粒子較佳為與導電性粒子分開存在。 上述絕緣性粒子之平均粒徑較佳為10 μm以上,更佳為20 μm以上,進而較佳為25 μm以上,又,較佳為100 μm以下,更佳為75 μm以下,進而較佳為50 μm以下。若上述絕緣性粒子之平均粒徑為上述下限以上及上述上限以下,則藉由導電材料之硬化物而連接之連接對象構件間之間隔、以及藉由導電性粒子中之焊料而連接之連接對象構件間之間隔變得更適度。 上述絕緣性粒子之「平均粒徑」表示數量平均粒徑。絕緣性粒子之平均粒徑係藉由如下方式求出,例如利用電子顯微鏡或光學顯微鏡觀察任意之50個導電性粒子,算出平均值。 再者,於與導電性粒子、熱硬化性成分及助焊劑混合前之絕緣性粒子單獨成分的狀態下和於與導電性粒子、熱硬化性成分及助焊劑混合後之導電材料中之絕緣性粒子的狀態下,絕緣性粒子之平均粒徑一般而言相同。 作為上述絕緣性粒子之材料,可列舉絕緣性樹脂及絕緣性無機物等。作為上述絕緣性樹脂,可列舉作為用以形成能夠用作基材粒子之樹脂粒子的樹脂所列舉之上述樹脂。作為上述絕緣性無機物,可列舉作為用以形成能夠用作基材粒子之無機粒子的無機物所列舉之上述無機物。 關於作為上述絕緣性粒子之材料的絕緣性樹脂之具體例,可列舉:聚烯烴類、(甲基)丙烯酸酯聚合物、(甲基)丙烯酸酯共聚物、嵌段聚合物、熱塑性樹脂、熱塑性樹脂之交聯物、熱硬化性樹脂及水溶性樹脂等。 作為上述聚烯烴類,可列舉:聚乙烯、乙烯-乙酸乙烯酯共聚物及乙烯-丙烯酸酯共聚物等。作為上述(甲基)丙烯酸酯聚合物,可列舉:聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸乙酯及聚(甲基)丙烯酸丁酯等。作為上述嵌段聚合物,可列舉:聚苯乙烯、苯乙烯-丙烯酸酯共聚物、SB型苯乙烯-丁二烯嵌段共聚物、及SBS型苯乙烯-丁二烯嵌段共聚物、以及該等之氫化物等。作為上述熱塑性樹脂,可列舉乙烯基聚合物及乙烯基共聚物等。作為上述熱硬化性樹脂,可列舉:環氧樹脂、酚系樹脂及三聚氰胺樹脂等。作為上述水溶性樹脂,可列舉:聚乙烯醇、聚丙烯酸、聚丙烯醯胺、聚乙烯基吡咯啶酮、聚環氧乙烷及甲基纖維素等。其中,較佳為水溶性樹脂,更佳為聚乙烯醇。 於上述導電材料100重量%中,上述絕緣性粒子之含量較佳為0.1重量%以上,更佳為0.5重量%以上,又,較佳為10重量%以下,更佳為5重量%以下。上述導電材料亦可不含絕緣性粒子。若絕緣性粒子之含量為上述下限以上及上述上限以下,則藉由導電材料之硬化物而連接之連接對象構件間之間隔、以及藉由導電性粒子中之焊料而連接之連接對象構件間之間隔變得更適度。 (其他成分) 上述導電材料視需要亦可包含例如填充劑、增量劑、軟化劑、塑化劑、聚合觸媒、硬化觸媒、著色劑、抗氧化劑、熱穩定劑、光穩定劑、紫外線吸收劑、潤滑劑、抗靜電劑及阻燃劑等各種添加劑。 (連接構造體及連接構造體之製造方法) 本發明之連接構造體具備表面具有至少一個第1電極之第1連接對象構件、表面具有至少一個第2電極之第2連接對象構件、及連接上述第1連接對象構件與上述第2連接對象構件之連接部。本發明之連接構造體中,上述連接部之材料為上述導電材料,上述連接部係由上述導電材料形成。本發明之連接構造體中,上述第1電極與上述第2電極藉由上述連接部中之焊料部而電性連接。 上述連接構造體之製造方法具備如下步驟:使用上述導電材料,於表面具有至少一個第1電極之第1連接對象構件之表面上配置上述導電材料;於上述導電材料之與上述第1連接對象構件側相反之表面上,以上述第1電極與上述第2電極對向之方式配置表面具有至少一個第2電極之第2連接對象構件;將上述導電材料加熱至上述導電性粒子中之焊料之熔點以上,藉此由上述導電材料之硬化物形成連接上述第1連接對象構件與上述第2連接對象構件之連接部,且藉由上述連接部中之焊料部使上述第1電極與上述第2電極電性連接。較佳為將上述導電材料加熱至上述熱硬化性成分、熱硬化性化合物之硬化溫度以上。 於本發明之連接構造體及上述連接構造體之製造方法中,由於使用特定之導電材料,故而複數個導電性粒子中之焊料容易聚集至第1電極與第2電極之間,可有效率地於電極(線)上配置焊料。又,焊料之一部分不易被配置至未形成電極之區域(間隔),可明顯減少配置於未形成電極之區域之焊料之量。因此,可提高第1電極與第2電極之間之導通可靠性。並且,可防止於禁止連接之橫向上鄰接之電極間之電性連接,可提高絕緣可靠性。 又,為了有效率地於電極上配置複數個導電性粒子中之焊料、且明顯減少未形成電極之區域所配置之焊料之量,較佳為使用導電膏而非導電膜。 電極間之焊料部之厚度較佳為10 μm以上,更佳為20 μm以上,又,較佳為100 μm以下,更佳為80 μm以下。電極之表面上之焊料潤濕面積(電極所露出之面積100%中之焊料所接觸之面積,相對於形成上述連接部前之上述第1電極及待與上述第1電極電性連接之上述第2電極所露出之面積100%的形成上述連接部後之上述焊料部所接觸之面積)較佳為50%以上,更佳為70%以上,又,較佳為100%以下。 於本發明之連接構造體之製造方法中,較佳為於配置上述第2連接對象構件之步驟及形成上述連接部之步驟中不進行加壓,而使上述第2連接對象構件之重量施加於上述導電材料;或較佳為於配置上述第2連接對象構件之步驟及形成上述連接部之步驟中之至少一步驟中進行加壓,且於配置上述第2連接對象構件之步驟及形成上述連接部之步驟該兩步驟中,加壓之壓力未達1 MPa。藉由未施加1 MPa以上之加壓之壓力而顯著促進導電性粒子中之焊料之凝集。就抑制連接對象構件翹曲之觀點而言,於本發明之連接構造體之製造方法中,可於配置上述第2連接對象構件之步驟及形成上述連接部之步驟中之至少一步驟中進行加壓,且於配置上述第2連接對象構件之步驟及形成上述連接部之步驟該兩步驟中,加壓之壓力未達1 MPa。於進行加壓之情形時,可僅於配置上述第2連接對象構件之步驟中進行加壓,亦可僅於形成上述連接部之步驟中進行加壓,亦可於配置上述第2連接對象構件之步驟與形成上述連接部之步驟該兩步驟中進行加壓。加壓之壓力未達1 MPa包括未進行加壓之情況。於進行加壓之情形時,加壓之壓力較佳為0.9 MPa以下,更佳為0.8 MPa以下。與加壓之壓力超過0.8 MPa之情形相比,於加壓之壓力為0.8 MPa以下之情形時,更顯著地促進導電性粒子中之焊料之凝集。 於本發明之連接構造體之製造方法中,較佳為於配置上述第2連接對象構件之步驟及形成上述連接部之步驟中不進行加壓,而使上述第2連接對象構件之重量施加於上述導電材料;較佳為於配置上述第2連接對象構件之步驟及形成上述連接部之步驟中,未對上述導電材料施加超過上述第2連接對象構件之重量之力的加壓壓力。於該等情形時,可進一步提高複數個焊料部中之焊料量之均勻性。進而,可更有效地使焊料部之厚度變厚,複數個導電性粒子中之焊料容易較多地聚集至電極間,更有效率地於電極(線)上配置複數個導電性粒子中之焊料。又,複數個導電性粒子中之焊料之一部分不易被配置至未形成電極之區域(間隔),可進一步減少配置於未形成電極之區域之導電性粒子中之焊料之量。因此,可進一步提高電極間之導通可靠性。並且,可進一步防止於禁止連接之橫向上鄰接之電極間之電性連接,可進一步提高絕緣可靠性。 進而,本發明者等人亦發現,若於配置上述第2連接對象構件之步驟及形成上述連接部之步驟中不進行加壓,而使上述第2連接對象構件之重量施加於上述導電材料,則於形成連接部前被配置至未形成電極之區域(間隔)之焊料更容易聚集至第1電極與第2電極之間,可更有效率地於電極(線)上配置複數個導電性粒子中之焊料。於本發明中,將使用導電膏而非導電膜之構成、與不進行加壓而使上述第2連接對象構件之重量施加於上述導電膏之構成組合採用對於以更高等級獲得本發明之效果具有重大意義。 再者,WO2008/023452A1中記載有就推動焊料粉使之效率良好地移動至電極表面之觀點而言,宜於接著時以特定壓力進行加壓;並記載有就更確實地形成焊料區域之觀點而言,加壓壓力例如設為0 MPa以上、較佳為設為1 MPa以上;進而記載有對膠帶有意施加之壓力可為0 MPa,亦可藉由配置於膠帶上之構件之自重而對膠帶施加特定壓力。雖然WO2008/023452A1中記載有對膠帶有意施加之壓力可為0 MPa,但關於施加超過0 MPa之壓力之情形時與設為0 MPa之情形時效果之差異未作任何記載。又,WO2008/023452A1中對於使用膏狀之導電膏而非膜狀之重要性亦未有任何認識。 又,若使用導電膏而非導電膜,則容易藉由導電膏之塗佈量而調整連接部及焊料部之厚度。另一方面,若為導電膜則存在如下問題:為了變更或調整連接部之厚度而必須準備不同厚度之導電膜或必須準備特定厚度之導電膜。又,與導電膏相比,導電膜存在如下傾向:於焊料之熔融溫度下無法充分降低導電膜之熔融黏度,容易阻礙焊料之凝集。 以下,一面參照圖式一面說明本發明之具體之實施形態。 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所獲得之連接構造體的剖視圖。 圖1所示之連接構造體1具備第1連接對象構件2、第2連接對象構件3、及連接第1連接對象構件2與第2連接對象構件3之連接部4。連接部4係由上述導電材料形成。本實施形態中,導電材料包含焊料粒子作為導電性粒子。 連接部4具有複數個焊料粒子聚集並相互接合而成之焊料部4A、及使熱硬化性成分熱硬化而成之硬化物部4B。於本實施形態中,為了形成焊料部4A,使用焊料粒子作為導電性粒子。焊料粒子其中心部分及導電部之外表面均由焊料形成。 第1連接對象構件2於表面(上表面)具有複數個第1電極2a。第2連接對象構件3於表面(下表面)具有複數個第2電極3a。第1電極2a與第2電極3a藉由焊料部4A而電性連接。因此,第1連接對象構件2與第2連接對象構件3藉由焊料部4A而電性連接。再者,於連接部4中,與聚集至第1電極2a與第2電極3a之間之焊料部4A不同之區域(硬化物部4B部分)不存在焊料。與焊料部4A不同之區域(硬化物部4B部分)不存在與焊料部4A分離之焊料。再者,若為少量,則與聚集至第1電極2a與第2電極3a之間之焊料部4A不同之區域(硬化物部4B部分)亦可存在焊料。 如圖1所示,於連接構造體1中,複數個焊料粒子聚集於第1電極2a與第2電極3a之間,複數個焊料粒子熔融後,焊料粒子之熔融物於電極之表面潤濕擴散後固化,形成焊料部4A。因此,焊料部4A與第1電極2a、以及焊料部4A與第2電極3a之連接面積變大。即,與使用導電部之外表面部分為鎳、金或銅等金屬之導電性粒子之情形相比,藉由使用焊料粒子,焊料部4A與第1電極2a、以及焊料部4A與第2電極3a之接觸面積變大。因此,連接構造體1之導通可靠性及連接可靠性變高。 再者,於圖1所示之連接構造體1中,整個焊料部4A均位於第1、第2電極2a、3a間之對向區域。圖3所示之變化例之連接構造體1X僅其連接部4X不同於圖1所示之連接構造體1。連接部4X具有焊料部4XA與硬化物部4XB。可如連接構造體1X般,焊料部4XA之大部分位於第1、第2電極2a、3a對向之區域,焊料部4XA之一部分自第1、第2電極2a、3a對向之區域向側方伸出。自第1、第2電極2a、3a對向之區域向側方伸出之焊料部4XA為焊料部4XA之一部分,而非與焊料部4XA分離之焊料。再者,本實施形態中,可減少與焊料部分離之焊料之量,但硬化物部中亦可存在與焊料部分離之焊料。 若減少焊料粒子之使用量,則容易獲得連接構造體1。若增多焊料粒子之使用量,則容易獲得連接構造體1X。 就進一步提高導通可靠性之觀點而言,較佳為於連接構造體1、1X中,沿第1電極2a與連接部4、4X及第2電極3a之積層方向觀察第1電極2a與第2電極3a之相對向部分時,第1電極2a與第2電極3a之相對向部分之面積100%中之50%以上(更佳為60%以上,進而較佳為70%以上,尤佳為80%以上,最佳為90%以上)配置有連接部4、4X中之焊料部4A、4XA。 就進一步提高導通可靠性之觀點而言,較佳為於沿上述第1電極與上述連接部及上述第2電極之積層方向觀察上述第1電極與上述第2電極之相對向部分時,上述第1電極與上述第2電極之相對向部分之面積100%中之50%以上(更佳為60%以上,進而較佳為70%以上,尤佳為80%以上,最佳為90%以上)配置有上述連接部中之焊料部。 就進一步提高導通可靠性之觀點而言,較佳為於沿和上述第1電極與上述連接部及上述第2電極之積層方向正交的方向觀察上述第1電極與上述第2電極之相對向部分時,上述連接部中之焊料部之60%以上(更佳為70%以上,進而較佳為80%以上,進而更佳為90%以上,尤佳為95%以上,最佳為99%以上)配置於上述第1電極與上述第2電極之相對向部分。 繼而,對使用本發明之一實施形態之導電材料而製造連接構造體1之方法之一例進行說明。 首先,準備表面(上表面)具有第1電極2a之第1連接對象構件2。繼而,如圖2(a)所示,於第1連接對象構件2之表面上配置包含熱硬化性成分11B、複數個焊料粒子11A、及特定助焊劑之導電材料11(第1步驟)。所使用之導電材料包含熱硬化性化合物與熱硬化劑作為熱硬化性成分11B。 於第1連接對象構件2之設置有第1電極2a之表面上配置導電材料11。配置導電材料11後,焊料粒子11A被配置於第1電極2a(線)上與未形成第1電極2a之區域(間隔)上該兩者上。 作為導電材料11之配置方法,並無特別限定,可列舉:利用分注器之塗佈、網版印刷、及利用噴墨裝置之噴塗等。 又,準備表面(下表面)具有第2電極3a之第2連接對象構件3。繼而,如圖2(b)所示,於第1連接對象構件2之表面上之導電材料11中之與導電材料11之第1連接對象構件2側為相反側之表面上配置第2連接對象構件3(第2步驟)。於導電材料11之表面上自第2電極3a側配置第2連接對象構件3。此時,使第1電極2a與第2電極3a對向。 繼而,將導電材料11加熱至焊料粒子11A之熔點以上(第3步驟)。較佳為將導電材料11加熱至熱硬化性成分11B(黏合劑)之硬化溫度以上。於該加熱時,未形成電極之區域所存在之焊料粒子11A會向第1電極2a與第2電極3a之間聚集(自凝集效應)。於使用導電膏而非導電膜之情形時,焊料粒子11A有效地向第1電極2a與第2電極3a之間聚集。又,焊料粒子11A熔融而相互接合。又,熱硬化性成分11B熱硬化。其結果如圖2(c)所示,由導電材料11形成連接第1連接對象構件2與第2連接對象構件3之連接部4。由導電材料11形成連接部4,藉由複數個焊料粒子11A接合而形成焊料部4A,藉由熱硬化性成分11B熱硬化而形成硬化物部4B。若焊料粒子11A充分移動,則自並非位於第1電極2a與第2電極3a之間之焊料粒子11A開始移動起至焊料粒子11A完成向第1電極2a與第2電極3a之間之移動為止,此期間之溫度未保持恆定亦無妨。 於本實施形態中,較佳為於上述第2步驟及上述第3步驟中不進行加壓。於該情形時,第2連接對象構件3之重量施加於導電材料11。因此,於形成連接部4時,焊料粒子11A有效地聚集至第1電極2a與第2電極3a之間。再者,若於上述第2步驟及上述第3步驟中之至少一步驟中進行加壓,則焊料粒子欲向第1電極與第2電極之間聚集之作用受到抑制之傾向變高。 又,於本實施形態中,由於未進行加壓,故而於使塗佈有導電材料之第1連接對象構件與第2連接對象構件重合時,即便於第1連接對象構件與第2連接對象構件在第1連接對象構件之電極與第2連接對象構件之電極未對準之狀態下經重合之情形時,亦可修正該偏離而使第1連接對象構件之電極與第2連接對象構件之電極連接(自定位效應)。其原因在於:關於自行聚集至第1連接對象構件之電極與第2連接對象構件之電極之間且已熔融之焊料,若第1連接對象構件之電極與第2連接對象構件之電極之間之焊料和導電材料之其他成分的接觸面積成為最小則於能量上保持穩定,因此欲實現成為該最小面積之連接構造即存在對準之連接構造的力發揮作用。此時,較理想的是導電材料未硬化,且於該溫度下在該時間內導電材料之導電性粒子以外之成分之黏度足夠低。 如此獲得圖1所示之連接構造體1。再者,上述第2步驟與上述第3步驟可連續進行。又,可於進行上述第2步驟後,使所獲得之第1連接對象構件2與導電材料11與第2連接對象構件3之積層體移動至加熱部而進行上述第3步驟。為了進行上述加熱,可於加熱構件上配置上述積層體,亦可於經加熱之空間內配置上述積層體。 上述第3步驟中之上述加熱溫度較佳為140℃以上,更佳為160℃以上,又,較佳為450℃以下,更佳為250℃以下,進而較佳為200℃以下。 作為上述第3步驟中之加熱方法,可列舉:使用回焊爐或使用烘箱對連接構造體整體進行加熱而達到焊料之熔點以上及熱硬化性化合物之硬化溫度以上之方法、或者僅對連接構造體之連接部進行局部加熱之方法。 作為局部加熱方法所使用之器具,可列舉:加熱板、吹送熱風之熱風槍、烙鐵、及紅外線加熱器等。 又,於利用加熱板進行局部加熱時,較佳為於連接部正下方,由導熱性較高之金屬形成加熱板上表面,於其他不易加熱之部位,由氟樹脂等導熱性較低之材質形成加熱板上表面。 上述第1、第2連接對象構件並無特別限定。作為上述第1、第2連接對象構件,具體而言,可列舉:半導體晶片、半導體組件、LED晶片、LED組件、電容器及二極體等電子零件,以及樹脂膜、印刷基板、軟性印刷基板、撓性扁平電纜、剛柔性基板、玻璃環氧基板及玻璃基板等電路基板等電子零件等。上述第1、第2連接對象構件較佳為電子零件。 較佳為上述第1連接對象構件及上述第2連接對象構件中之至少一者為半導體晶片、樹脂膜、軟性印刷基板、剛柔性基板或撓性扁平電纜,更佳為樹脂膜、軟性印刷基板、撓性扁平電纜或剛柔性基板。較佳為上述第2連接對象構件為半導體晶片、樹脂膜、軟性印刷基板、剛柔性基板或撓性扁平電纜,更佳為樹脂膜、軟性印刷基板、撓性扁平電纜或剛柔性基板。樹脂膜、軟性印刷基板、撓性扁平電纜及剛柔性基板具有柔軟性較高且相對較輕量之性質。於使用導電膜進行此種連接對象構件之連接之情形時,存在導電性粒子中之焊料不易聚集至電極上之傾向。相對於此,藉由使用導電膏,即便使用樹脂膜、軟性印刷基板、撓性扁平電纜或剛柔性基板,亦可有效率地使導電性粒子中之焊料聚集至電極上,藉此可充分提高電極間之導通可靠性。與使用半導體晶片等其他連接對象構件之情形相比,於使用樹脂膜、軟性印刷基板、撓性扁平電纜或剛柔性基板之情形時,可更有效地獲得由不進行加壓所實現之電極間之導通可靠性之提高效果。 上述連接對象構件之形態存在周邊或面陣列等。作為各構件之特徵,若為周邊基板,則僅於基板之外周部存在電極。若為面陣列基板,則於面內存在電極。 作為上述連接對象構件上所設置之電極,可列舉:金電極、鎳電極、錫電極、鋁電極、銅電極、鉬電極、銀電極、SUS電極及鎢電極等金屬電極。於上述連接對象構件為軟性印刷基板之情形時,上述電極較佳為金電極、鎳電極、錫電極、銀電極或銅電極。於上述連接對象構件為玻璃基板之情形時,上述電極較佳為鋁電極、銅電極、鉬電極、銀電極或鎢電極。再者,於上述電極為鋁電極之情形時,可為僅由鋁所形成之電極,亦可為於金屬氧化物層之表面積層鋁層而成之電極。作為上述金屬氧化物層之材料,可列舉摻雜有3價金屬元素之氧化銦及摻雜有3價金屬元素之氧化鋅等。作為上述3價金屬元素,可列舉Sn、Al及Ga等。 以下,列舉實施例及比較例而具體地說明本發明。本發明並非僅限定於以下之實施例。 熱硬化性化合物1:間苯二酚型環氧化合物,共榮社化學製造,「Epolight TDC-LC」,環氧當量120 g/eq 熱硬化性化合物2:高反應型環氧化合物,ADEKA股份有限公司製造,「EP-3300S」,環氧當量165 g/eq 熱硬化劑1:三羥甲基丙烷三(3-巰基丙酸酯),SC有機化學公司製造,「TMMP」 熱硬化劑2:二季戊四醇六(3-巰基丙酸酯),SC有機化學公司製造,「DPMP」 潛伏性環氧熱硬化劑1:T&K TOKA公司製造,「FUJICURE 7000」 助焊劑1之製作方法: 向三口燒瓶內添加丙酮160 g與戊二酸(和光純藥工業公司製造)32 g,於室溫下溶解至均勻狀態。其後,歷時30分鐘滴加苄基胺(和光純藥工業公司製造)26 g,滴加結束後於室溫下攪拌2小時。藉由過濾而分取所析出之白色結晶,利用丙酮洗淨,進行真空乾燥而獲得助焊劑1。平均粒徑係使用掃描式電子顯微鏡(日立製作所公司製造,「S-4300SEN」),對任意之50個粒子進行測定,算出平均值。又,熔點係使用DSC(Seiko Instruments公司製造,「DSC6200」)測定吸熱波峰。 助焊劑2之製作方法: 對於藉由與助焊劑1相同之方法所獲得之白色結晶,利用乳缽將其粉碎至平均粒徑成為10 μm,而獲得助焊劑2。 助焊劑3之製作方法: 對於藉由與助焊劑1相同之方法所獲得之白色結晶,利用乳缽將其粉碎至平均粒徑成為1 μm,而獲得助焊劑3。 助焊劑4之製作方法: 對於藉由與助焊劑1相同之方法所獲得之白色結晶,利用乳缽將其粉碎至平均粒徑成為0.05 μm,而獲得助焊劑4。 助焊劑5之製作方法: 向三口燒瓶內添加丙酮160 g與環己烷羧酸(和光純藥工業公司製造)31 g,於室溫下溶解至均勻狀態。其後,歷時30分鐘滴加環己基胺(東京化成工業製造)24 g,滴加結束後於室溫下攪拌2小時。藉由過濾而分取所析出之白色結晶,利用丙酮洗淨,進行真空乾燥。其後,利用乳缽粉碎至平均粒徑成為10 μm,而獲得助焊劑5。 助焊劑6之製作方法: 向三口燒瓶內添加丙酮160 g與己二酸(和光純藥工業公司製造)35 g,於室溫下溶解至均勻狀態。其後,歷時30分鐘滴加苄基胺(和光純藥工業公司製造)26 g,滴加結束後於室溫下攪拌2小時。藉由過濾而分取所析出之白色結晶,利用丙酮洗淨,進行真空乾燥。其後,利用乳缽粉碎至平均粒徑成為10 μm,而獲得助焊劑6。 助焊劑7之製作方法: 於三口燒瓶內,對檸檬酸一水合物12.6 g添加三乙醇胺26.8 g,於120℃之油浴中一面攪拌一面使檸檬酸溶解。所獲得之檸檬酸三乙醇胺鹽(助焊劑7)於25℃下為液體。 助焊劑8之製作方法: 於三口燒瓶內,對戊二酸35.0 g添加三乙醇胺37.25 g,於120℃之油浴中一面攪拌一面使戊二酸溶解。所獲得之戊二酸三乙醇胺鹽(助焊劑8)於25℃下為半固體。 再者,關於25℃下為固體之助焊劑,於與導電性粒子及熱硬化性成分混合前之助焊劑單劑的狀態下和於與導電性粒子及熱硬化性成分混合後之導電材料中之助焊劑的狀態下,助焊劑之平均粒徑相同。 焊料粒子1(SnBi焊料粒子,熔點139℃,三井金屬公司製造,「DS-10」,平均粒徑(中值徑12 μm)) 焊料粒子2(SAC焊料粒子,熔點217℃,三井金屬公司製造,「DS-10」,平均粒徑(中值徑12 μm)) 焊料粒子3之製作方法: 向三口燒瓶內添加丙酮160 g與戊二酸(和光純藥工業公司製造)32 g,於室溫下溶解至均勻狀態。其後,添加100 g焊料粒子1並攪拌15分鐘後,歷時30分鐘滴加苄基胺(和光純藥工業公司製造)26 g,滴加結束後於室溫下攪拌2小時,藉此使助焊劑析出至焊料粒子之表面。其後,利用丙酮清洗焊料粒子1次,進行真空乾燥而獲得焊料粒子3。 (實施例1~17及比較例1~2) (1)各向異性導電膏之製作 以下述表1、2所示之調配量調配下述表1、2所示之成分,而獲得各向異性導電膏。助焊劑以表1、2所示之狀態存在於所獲得之各向異性導電膏中。 (2)連接構造體(面陣列)之製作 作為第1連接對象構件,準備如下半導體晶片,其於半導體晶片本體(尺寸5×5 mm,厚度0.4 mm)之表面以400 μm間距、以面陣列方式配置有直徑250 μm、厚度10 μm之銅電極。關於銅電極之個數,每一半導體晶片上為10個×10個之合計100個。 作為第2連接對象構件,準備如下玻璃環氧基板,其於玻璃環氧基板本體(尺寸20×20 mm,厚度1.2 mm,材質FR-4)之表面,以對照第1連接對象構件之電極而成為與之相同之圖案之方式配置有金電極,且於未配置金電極之區域形成有阻焊膜。銅電極之表面與阻焊膜之表面的階差為15 μm,阻焊膜相較於銅電極而突出。 於上述玻璃環氧基板之上表面以厚度成為50 μm之方式塗佈剛製作後不久之各向異性導電膏,而形成各向異性導電膏層。於23℃、50%RH下放置2小時後,於各向異性導電膏層之上表面以電極彼此對向之方式積層半導體晶片。上述半導體晶片之重量施加於各向異性導電膏層。自該狀態起,以各向異性導電膏層之溫度於升溫開始後之5秒後達到焊料之熔點(實施例1~9、12~17及比較例1、2中為139℃,實施例10、11中為217℃)之方式進行加熱。進而,以各向異性導電膏層之溫度於升溫開始後之15秒後達到焊料之熔點+21℃(實施例1~9、12~17及比較例1、2中為160℃,實施例10、11中為238℃)之方式進行加熱,保持5分鐘,藉此使各向異性導電膏層硬化,而獲得連接構造體。加熱時未進行加壓。 (評價) (1)黏度 使用E型黏度計(東機產業公司製造,「TVE22L」),於25℃及5 rpm之條件下測定各向異性導電膏於25℃下之黏度(η25)。 (2)保存穩定性 將各向異性導電膏裝入至注射器內,於23℃下保管24小時。於保管後,使用E型黏度計(東機產業公司製造,「TVE22L」),於25℃及5 rpm之條件下測定各向異性導電膏於25℃下之黏度(η25)。依據下述基準判定保存穩定性。 [保存穩定性之判定基準] ○○:保管後之黏度為保管前之黏度之±25%以內 ○:不及○○之基準,保管後之黏度為保管前之黏度之±50%以內 △:不及○○及○之基準,保管後之黏度為保管前之黏度之±75%以內 ×:不及○○、○及△之基準 (3)焊料部之厚度 藉由對所獲得之連接構造體進行剖面觀察,而評價位於上下電極間之焊料部之厚度。 (4)電極上之焊料之配置精度1 評價如下比率X,該比率X係於所獲得之連接構造體中,沿第1電極與連接部及第2電極之積層方向觀察第1電極與第2電極之相對向部分時,第1電極與第2電極之相對向部分之面積100%中的配置有連接部中之焊料部之面積之比率。依據下述基準判定電極上之焊料之配置精度1。 [電極上之焊料之配置精度1之判定基準] ○○:比率X為70%以上 ○:比率X為60%以上且未達70% △:比率X為50%以上且未達60% ×:比率X未達50% (5)電極上之焊料之配置精度2 評價如下比率Y,該比率Y係於所獲得之連接構造體中,沿和第1電極與連接部及第2電極之積層方向正交的方向觀察第1電極與第2電極之相對向部分時,連接部中之焊料部100%中的配置於第1電極與第2電極之相對向部分之連接部中之焊料部之比率。依據下述基準判定電極上之焊料之配置精度2。 [電極上之焊料之配置精度2之判定基準] ○○:比率Y為99%以上 ○:比率Y為90%以上且未達99% △:比率Y為70%以上且未達90% ×:比率Y未達70% (6)上下之電極間之導通可靠性 針對所獲得之連接構造體(n=15個),分別藉由4端子法測定上下之電極間之每一連接部位之連接電阻。算出連接電阻之平均值。再者,可基於電壓=電流×電阻之關係,藉由測定使規定電流流通時之電壓而求出連接電阻。依據下述基準判定導通可靠性。其中,n=15個中出現一例上下之電極間未導通之情況即判定為「×」。 [導通可靠性之判定基準] ○○:連接電阻之平均值為50 mΩ以下 ○:連接電阻之平均值超過50 mΩ且為70 mΩ以下 △:連接電阻之平均值超過70 mΩ且為100 mΩ以下 ×:連接電阻之平均值超過100 mΩ或發生連接不良 (7)於橫向上鄰接之電極間之絕緣可靠性 針對所獲得之連接構造體(n=15個),於85℃、濕度85%之環境中放置100小時後,對橫向上鄰接之電極間施加15 V,於25處測定電阻值。依據下述基準判定絕緣可靠性。其中,n=15個中出現一例於橫向上鄰接之電極間導通之情況即判定為「×」。 [絕緣可靠性之判定基準] ○○○:連接電阻之平均值為1014 Ω以上 ○○:連接電阻之平均值為108 Ω以上且未達1014 Ω ○:連接電阻之平均值為106 Ω以上且未達108 Ω △:連接電阻之平均值為105 Ω以上且未達106 Ω ×:連接電阻之平均值未達105 Ω 將詳細內容及結果示於下述表1、2。   [表1]
Figure 106102877-A0304-0001
[表2]
Figure 106102877-A0304-0002
The present invention will be described in detail below. (Conductive Material) The conductive material of the present invention includes a plurality of conductive particles and a binder. The said electroconductive particle has an electroconductive part. The said electroconductive particle has solder in the outer surface part of a conductive part. Solder is included in the conductive part and is part or all of the conductive part. The above-mentioned binder is a component other than the conductive particles contained in the above-mentioned conductive material. The conductive material of the present invention includes thermosetting components and flux as the above-mentioned binder. The above-mentioned thermosetting component preferably contains a thermosetting compound and a thermosetting agent. In the conductive material of the present invention, the above-mentioned flux is a salt of acid and alkali. Furthermore, in the conductive material of the present invention, the above-mentioned flux exists as a solid in the conductive material at 25°C. More specifically, in the conductive material of the present invention, the above-mentioned flux exists as a solid at 25°C in the conductive material at 25°C. Furthermore, whether the above-mentioned flux is solid in a conductive material at 25° C. can be judged by the following method. In this specification, regarding fluxes that are not liquid at 25°C, fluxes that retain their shape when conductive materials containing fluxes are left standing at 25°C for 5 minutes are defined as fluxes that are solid at 25°C, including fluxes The flux that does not retain its shape when the conductive material is left standing at 25°C for 5 minutes is defined as semi-solid flux at 25°C. Also, fluxes that are semi-solid at 25°C are not included in fluxes that are solid at 25°C. In this invention, since it has the said structure, the storage stability of a conductive material can be improved. Furthermore, in the present invention, due to the above configuration, even if the conductive material is placed on the member to be connected and left for a long time, it exhibits excellent solder agglomeration property, so that high conduction reliability can be exhibited. In this invention, it is preferable that the said flux single agent is solid at 25 degreeC in the state which is not mixed with the said electroconductive particle and the said thermosetting component. It is preferable that the said flux single agent is solid at 25 degreeC before mixing with the said electroconductive particle and the said thermosetting component. In these cases, it is easy to make the above-mentioned flux exist as a solid in the conductive material at 25°C. Furthermore, whether the above-mentioned flux single agent is solid at 25° C. can be judged by the following method. In this specification, regarding the flux that is not liquid at 25°C, the flux that maintains its shape when the single flux is left at 25°C for 5 minutes is defined as the flux that is solid at 25°C. Flux that does not retain its shape when left standing at 25°C for 5 minutes is defined as semi-solid flux at 25°C. Also, fluxes that are semi-solid at 25°C are not included in fluxes that are solid at 25°C. When the connection structure is obtained, the laminate of the first connection object member and the conductive material may be temporarily stored after disposing the conductive material on the first connection object member and before arranging the second connection object member on the conductive material. In the present invention, even if the above-mentioned laminate is stored, a connection structure excellent in conduction reliability can be obtained. Moreover, in this invention, since it has the said structure, even if an electrode width is narrow, the solder in electroconductive particle can be arrange|positioned efficiently on an electrode. When the electrode width is narrow, it tends to be difficult to gather the solder of the conductive particles on the electrode, but in the present invention, even if the electrode width is narrow, the solder can be sufficiently gathered on the electrode. In the present invention, due to the above-mentioned structure, when the electrodes are electrically connected, the solder in the conductive particles is easily located between the electrodes facing up and down, and the solder in the conductive particles can be efficiently connected. Arranged on the electrode (line). Moreover, in this invention, if the electrode width is wide, the solder in electroconductive particle will be arrange|positioned more efficiently on an electrode. In addition, part of the solder in the conductive particles is less likely to be placed in the region (space) where no electrodes are formed, and the amount of solder placed in the region where no electrodes are formed can be significantly reduced. In the present invention, the solder that is not located between the opposing electrodes can be efficiently moved to between the opposing electrodes. Therefore, the conduction reliability between electrodes can be improved. Furthermore, electrical connection between electrodes adjacent in the lateral direction where connection is prohibited can be prevented, and insulation reliability can be improved. Furthermore, in the present invention, the heat resistance of the cured product of the conductive material can be improved. In particular, when a conductive material is used in an optical semiconductor device, the cured product of the conductive material is exposed to high temperature due to heat generated when irradiated with light. Since the conductive material of the present invention is excellent in heat resistance of a cured product, it can be suitably used for an optical semiconductor device. In particular, when the thermosetting compound contains a thermosetting compound having a three-skeleton skeleton, the heat resistance of the cured product becomes high. Furthermore, in the present invention, positional deviation between electrodes can be prevented. In the present invention, when the first connection object member and the second connection object member on which the conductive material is arranged on the upper surface are overlapped, even if the first connection object member and the second connection object member are connected between the electrodes of the first connection object member and the second connection object member. When the electrodes of the second object to be connected are overlapped in a state where they are misaligned, the deviation can also be corrected so that the electrodes of the first object to be connected are connected to the electrodes of the second object to be connected (self alignment effect) ). In order to more efficiently arrange the solder in the conductive particles on the electrodes, the above-mentioned conductive material is preferably liquid at 25° C., preferably a conductive paste. In order to more efficiently arrange the solder in the conductive particles on the electrodes, the viscosity (η25) of the above-mentioned conductive material at 25°C is preferably 10 Pa·s or more, more preferably 50 Pa·s or more, and even more preferably 100 Pa•s or more, and preferably 800 Pa•s or less, more preferably 600 Pa•s or less, further preferably 500 Pa•s or less. The above-mentioned viscosity (η25) can be adjusted by the type and amount of compounded ingredients. The aforementioned viscosity (η25) can be measured using, for example, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "TVE22L") at 25°C and 5 rpm. The above-mentioned conductive material can be used in the form of conductive paste, conductive film and the like. The above-mentioned conductive film is preferably an anisotropic conductive film. It is preferable that the said electrically-conductive material is an electrically-conductive paste from a viewpoint of arrange|positioning the solder in electroconductive particle more efficiently on an electrode. The above-mentioned conductive materials are suitable for electrical connection of electrodes. The above-mentioned conductive material is preferably a circuit connection material. Each component contained in the above-mentioned conductive material will be described below. Furthermore, in this specification, "(meth)acrylate" means one or both of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylate". "(meth)acryl" means one or both of "acryl" and "methacryl". (Electroconductive particle) The said electroconductive particle electrically connects between the electrodes of a connection object member. The said electroconductive particle has solder in the outer surface part of a conductive part. The said electroconductive particle may be the solder particle which consists of solder. The above-mentioned solder particles have solder on the outer surface of the conductive part. Both the central portion and the outer surface portion of the conductive portion of the above-mentioned solder particle are formed of solder. The above-mentioned solder particles are particles in which both the central part and the conductive outer surface are solder. The said solder particle does not have the base particle which is a core particle. The said solder particle is different from the electroconductive particle provided with the electroconductive part arrange|positioned on the surface of the base material particle and the said base material particle. The above-mentioned solder particles contain, for example, preferably 80% by weight or more of solder, more preferably 90% by weight or more, and still more preferably 95% by weight or more. The said electroconductive particle may have the electroconductive part arrange|positioned on the surface of a base material particle and this base material particle. In this case, the said electroconductive particle has a solder in the electroconductive part outer surface part. Furthermore, compared with the case of using the above-mentioned solder particles, in the case of using conductive particles having base particles not formed of solder and a solder portion arranged on the surface of the base particles, the conductive particles are less likely to gather on the surface of the base particle. On the electrodes, the solder bondability between the conductive particles is low, so the conductive particles that have moved on the electrodes tend to move out of the electrodes easily, and the effect of suppressing positional deviation between electrodes also tends to be low. Therefore, it is preferable that the said electroconductive particle is a solder particle which consists of solder. From the standpoint of effectively reducing the connection resistance in the connection structure and effectively suppressing the generation of voids, it is preferable to have a carboxyl group or an amine group on the outer surface (outer surface of the solder) of the above-mentioned conductive particles, and it is more preferable to have a carboxyl group. , preferably an amine group is present. Preferably, a carboxyl group or an amine group is covalently bonded to the outer surface of the conductive particle (the outer surface of the solder) via a Si-O bond, an ether bond, an ester bond, or a group represented by the following formula (X). foundation. The group containing a carboxyl group or an amino group may contain both a carboxyl group and an amino group. In addition, in the following formula (X), the right end part and the left end part represent a bonding site. [chemical 1]
Figure 02_image001
Hydroxyl groups exist on the surface of the solder. By covalently bonding the hydroxyl group to a group including a carboxyl group, a bond stronger than that in the case of bonding in other forms of coordination bonding (chelate coordination) can be formed, and the connection between electrodes can be reduced. Conductive particles that resist and suppress the generation of voids. Regarding the above-mentioned electroconductive particle, the bonding form of the surface of the solder and the group containing a carboxyl group may not include a coordination bond, and may not include a bond of a chelate coordination form. From the viewpoint of effectively reducing the connection resistance in the connection structure and effectively suppressing the generation of voids, the above-mentioned conductive particles are preferably obtained by using a compound having a functional group that can react with a hydroxyl group and a carboxyl or amine group (hereinafter referred to as When it is recorded as compound X), it is obtained by reacting the hydroxyl group on the surface of the solder with the above-mentioned functional group that can react with the hydroxyl group. A covalent bond is formed in the above reaction. By reacting the hydroxyl group on the surface of the solder with the functional group in the above-mentioned compound X that can react with the above-mentioned hydroxyl group, it is possible to easily obtain a solder particle in which a group containing a carboxyl group or an amino group is covalently bonded to the surface of the solder. Solder particles in which a group containing a carboxyl group or an amine group is covalently bonded to the surface of the solder via an ether bond or an ester bond can be obtained. By reacting the hydroxyl group on the surface of the solder with the functional group reactive with the hydroxyl group, the compound X can be chemically bonded to the surface of the solder in the form of covalent bonding. Examples of the functional group capable of reacting with a hydroxyl group include a hydroxyl group, a carboxyl group, an ester group, and a carbonyl group. Preferably it is a hydroxyl group or a carboxyl group. The above-mentioned functional group that can react with a hydroxyl group can be a hydroxyl group or a carboxyl group. Examples of the compound having a functional group capable of reacting with a hydroxyl group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketocaproic acid, 3-hydroxypropionic acid, 4-aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-Phenylbutyric acid, capric acid, dodecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vacuolic acid, linoleic acid Sesameoleic acid, (9,12,15)-linolenic acid, nonadecanoic acid, arachidic acid, decaneddioic acid and dodecanedioic acid, etc. Glutaric acid or glycolic acid is preferred. As for the compound which has the said functional group reactive with a hydroxyl group, only 1 type may be used, and 2 or more types may be used together. The compound having a functional group capable of reacting with a hydroxyl group is preferably a compound having at least one carboxyl group. It is preferable that the above-mentioned compound X has a flux action, and it is preferable that the above-mentioned compound X has a flux action in a state bonded to a solder surface. The compound with flux function can remove the oxide film on the surface of the solder and the oxide film on the electrode surface. The carboxyl group has a flux effect. Examples of compounds having a flux function include: acetylpropionic acid, glutaric acid, glycolic acid, adipic acid, succinic acid, 5-ketocaproic acid, 3-hydroxypropionic acid, 4-aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid and 4-phenylbutyric acid, etc. Preferred is glutaric acid, adipic acid or glycolic acid. The above-mentioned compounds having a flux action may be used alone or in combination of two or more. From the viewpoint of effectively reducing the connection resistance in the connection structure and effectively suppressing the generation of voids, the above-mentioned functional group reactive with a hydroxyl group in the above-mentioned compound X is preferably a hydroxyl group or a carboxyl group. The above-mentioned functional group that can react with a hydroxyl group in the above-mentioned compound X may be a hydroxyl group or a carboxyl group. When the above-mentioned functional group that can react with a hydroxyl group is a carboxyl group, the above-mentioned compound X preferably has at least two carboxyl groups. Conductive particles in which groups including carboxyl groups are covalently bonded to the surface of solder can be obtained by reacting some carboxyl groups in compounds having at least two carboxyl groups with hydroxyl groups on the surface of the solder. The manufacturing method of the said electroconductive particle has a process of using a conductive particle, for example, and mixing this electroconductive particle, the compound which has a functional group and a carboxyl group which can react with a hydroxyl group, a catalyst, and a solvent. In the manufacturing method of the said electroconductive particle, the electroconductive particle in which the group containing a carboxyl group was covalently bonded to the surface of a solder can be obtained easily by the said mixing process. In addition, in the above-mentioned method for producing conductive particles, it is preferable to use conductive particles, mix the conductive particles, the above-mentioned compound having a functional group and a carboxyl group capable of reacting with a hydroxyl group, the above-mentioned catalyst, and the above-mentioned solvent, and perform heating. Conductive particles in which groups including carboxyl groups are covalently bonded to the surface of the solder can be more easily obtained through the mixing and heating steps. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, methyl ethyl ketone, ethyl acetate, toluene, and xylene. The above-mentioned solvent is preferably an organic solvent, more preferably toluene. The said solvent may use only 1 type, and may use 2 or more types together. As said catalyst, p-toluenesulfonic acid, benzenesulfonic acid, 10-camphorsulfonic acid, etc. are mentioned. The above-mentioned catalyst is preferably p-toluenesulfonic acid. The said catalyst may use only 1 type, and may use 2 or more types together. It is preferable to heat during said mixing. The heating temperature is preferably at least 90°C, more preferably at least 100°C, and is preferably at most 130°C, more preferably at most 110°C. From the standpoint of effectively reducing the connection resistance in the connection structure and effectively suppressing the generation of voids, it is preferable that the above-mentioned conductive particles pass through the following steps, that is, the hydroxyl groups on the surface of the solder and the above-mentioned isocyanate compound are reacted using an isocyanate compound. obtained by the reaction. A covalent bond is formed in the above reaction. By reacting the hydroxyl group on the surface of the solder with the above-mentioned isocyanate compound, the conductive particle in which the nitrogen atom derived from the isocyanate group is covalently bonded to the surface of the solder can be easily obtained. By reacting the hydroxyl group on the surface of the above-mentioned solder with the above-mentioned isocyanate compound, the group derived from the isocyanate group can be chemically bonded to the surface of the solder in the form of covalent bonding. Also, a group derived from an isocyanate group can easily react with a silane coupling agent. Since the above-mentioned conductive particles can be easily obtained, the above-mentioned group containing a carboxyl group is preferably introduced by a reaction using a silane coupling agent having a carboxyl group, or by introducing a group derived from a silane coupling agent after the reaction using a silane coupling agent. The group is introduced by reacting with a compound having at least one carboxyl group. It is preferable that the said electroconductive particle is obtained by reacting the hydroxyl group on the surface of a solder with the said isocyanate compound using the said isocyanate compound, and the compound which has at least 1 carboxyl group. The compound having at least one carboxyl group preferably has a plurality of carboxyl groups from the viewpoint of effectively reducing the connection resistance in the connection structure and effectively suppressing the generation of voids. Examples of the isocyanate compound include diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI). Wait. Isocyanate compounds other than these can also be used. After the compound is reacted with the surface of the solder, the remaining isocyanate group is reacted with a compound having a carboxyl group which is reactive with the remaining isocyanate group, whereby the group represented by the formula (X) can pass through the surface of the solder And the carboxyl group is introduced. As said isocyanate compound, the compound which has an unsaturated double bond and isocyanate group can also be used. For example, 2-acryloxyethyl isocyanate and 2-isocyanatoethyl methacrylate are mentioned. After reacting the isocyanate group of the compound with the surface of the solder, it reacts with a compound having a carboxyl group having a functional group reactive to the remaining unsaturated double bond, so that the formula (X) can pass through the surface of the solder. Introduce the carboxyl group by expressing the group. Examples of the silane coupling agent include 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicones, "KBE-9007") and 3-isocyanatopropyltrimethoxysilane (manufactured by MOMENTIVE, "Y-5187"), etc. The said silane coupling agent may use only 1 type, and may use 2 or more types together. Examples of the compound having at least one carboxyl group include: acetylpropionic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketocaproic acid, 3- Hydroxypropionic acid, 4-aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4- Phenylbutyric acid, capric acid, dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vacantoleic acid, linolenic acid , (9,12,15)-linolenic acid, nonadecanic acid, arachidic acid, decaneddioic acid and dodecanedioic acid, etc. Preferred is glutaric acid, adipic acid or glycolic acid. The above-mentioned compounds having at least one carboxyl group may be used alone or in combination of two or more. Using the above-mentioned isocyanate compound, after the hydroxyl group on the surface of the solder is reacted with the above-mentioned isocyanate compound, a part of the carboxyl group of the compound having a plurality of carboxyl groups is reacted with the hydroxyl group on the surface of the solder, thereby allowing the group including the carboxyl group to remain. In the above method of producing conductive particles, using conductive particles and isocyanate compounds, reacting the hydroxyl group on the surface of the solder with the above isocyanate compound, and then reacting with a compound having at least one carboxyl group, to obtain on the surface of the solder via the above formula The group represented by (X) is the electroconductive particle in which the group containing a carboxyl group was bonded. In the manufacturing method of the said electroconductive particle, the electroconductive particle in which the group containing a carboxyl group was introduced into the surface of a solder can be obtained easily by the said process. As a specific manufacturing method of the said electroconductive particle, the following method is mentioned. The conductive particles are dispersed in an organic solvent, and a silane coupling agent having an isocyanate group is added. Thereafter, the silane coupling agent is covalently bonded to the surface of the solder by using the reaction catalyst of the hydroxyl group and the isocyanate group on the surface of the solder of the conductive particles. Then, the alkoxy group bonded to the silicon atom of the silane coupling agent is hydrolyzed to generate a hydroxyl group. The generated hydroxyl group is reacted with a carboxyl group of a compound having at least one carboxyl group. Moreover, the following methods are mentioned as a specific manufacturing method of the said electroconductive particle. The conductive particles are dispersed in an organic solvent, and a compound having an isocyanate group and an unsaturated double bond is added. Then, a covalent bond is formed using the reaction catalyst of the hydroxyl group and the isocyanate group on the surface of the solder of electroconductive particle. Thereafter, for the introduced unsaturated double bond, the unsaturated double bond is reacted with a compound having a carboxyl group. Examples of catalysts for the reaction between hydroxyl groups and isocyanate groups on the surface of the solder on conductive particles include: tin-based catalysts (dibutyltin dilaurate, etc.), amine-based catalysts (triethylenediamine, etc.), carboxylic acid catalysts, etc. Ester catalysts (lead naphthenate, potassium acetate, etc.), and trialkylphosphine catalysts (triethylphosphine, etc.), etc. The compound having at least one carboxyl group is preferably a compound represented by the following formula (1) from the viewpoint of effectively reducing the connection resistance in the connection structure and effectively suppressing the generation of voids. The compound represented by the following formula (1) has a flux action. Moreover, the compound represented by following formula (1) has a flux action in the state introduced into the solder surface. [Chem 2]
Figure 02_image003
In the above formula (1), X represents a functional group capable of reacting with a hydroxyl group, and R represents a divalent organic group having 1 to 5 carbon atoms. The organic group may contain carbon atoms, hydrogen atoms and oxygen atoms. The organic group may be a divalent hydrocarbon group having 1 to 5 carbon atoms. The main chain of the above-mentioned organic group is preferably a divalent hydrocarbon group. The organic group may have a carboxyl group or a hydroxyl group bonded to the divalent hydrocarbon group. The compound represented by said formula (1) contains citric acid, for example. The compound having at least one carboxyl group is preferably a compound represented by the following formula (1A) or the following formula (1B). The compound having at least one carboxyl group is preferably a compound represented by the following formula (1A), more preferably a compound represented by the following formula (1B). [Chem 3]
Figure 02_image005
In the above formula (1A), R represents a divalent organic group having 1 to 5 carbon atoms. R in the above formula (1A) is the same as R in the above formula (1). [chemical 4]
Figure 02_image007
In the above formula (1B), R represents a divalent organic group having 1 to 5 carbon atoms. R in the above formula (1B) is the same as R in the above formula (1). The surface of the solder is preferably bonded with a group represented by the following formula (2A) or the following formula (2B). The surface of the solder is preferably bonded with a group represented by the following formula (2A), more preferably bonded with a group represented by the following formula (2B). In addition, in the following formula (2A) and the following formula (2B), the left end represents a bonding site. [chemical 5]
Figure 02_image009
In the above formula (2A), R represents a divalent organic group having 1 to 5 carbon atoms. R in the above formula (2A) is the same as R in the above formula (1). [chemical 6]
Figure 02_image011
In the above formula (2B), R represents a divalent organic group having 1 to 5 carbon atoms. R in the above formula (2B) is the same as R in the above formula (1). The molecular weight of the compound having at least one carboxyl group is preferably 10,000 or less, more preferably 1,000 or less, and still more preferably 500 or less, from the viewpoint of improving the wettability of the surface of the solder. From the viewpoint of more effectively inhibiting migration and more effectively reducing the connection resistance in the connection structure, the molecular weight of the compound having at least one carboxyl group is preferably 80 or more, more preferably 100 or more, and even more preferably Preferably it is above 120. When the above-mentioned molecular weight is not a polymer, and when the structural formula of the above-mentioned compound having at least one carboxyl group can be specified, it means a molecular weight that can be calculated from the structural formula. Moreover, when the compound which has the said at least 1 carboxyl group is a polymer, it means weight average molecular weight. It is preferable that the said electroconductive particle is an anionic polymer which has electroconductive particle itself and arrange|positioned on the surface of the said electroconductive particle itself from the point which can effectively improve the aggregation property of electroconductive particle at the time of electroconductive connection. The above-mentioned conductive particles are preferably obtained by surface-treating the conductive particles themselves with an anionic polymer or a compound that becomes an anionic polymer. It is preferable that the said electroconductive particle is the surface-treated thing obtained by treating with an anionic polymer or the compound which becomes an anionic polymer. The said anionic polymer and the said compound which will become an anionic polymer may use only 1 type, respectively, and may use 2 or more types together. The aforementioned anionic polymer is a polymer having an acidic group. As a method of surface-treating the conductive particle itself with an anionic polymer, a method of reacting the carboxyl group of the anionic polymer with the hydroxyl group on the surface of the conductive particle itself is mentioned. As the anionic polymer, for example, (meth)acrylic acid is used. Copolymerized (meth)acrylic polymers, polyester polymers synthesized from dicarboxylic acids and diols with carboxyl groups at both ends, obtained from intermolecular dehydration condensation reactions of dicarboxylic acids with carboxyl groups at both ends polymers, polyester polymers synthesized from dicarboxylic acids and diamines with carboxyl groups at both ends, and modified polyvinyl alcohols with carboxyl groups (manufactured by Nippon Synthetic Chemicals Corporation, "GOHSENX T"), etc. Examples of the anionic moiety of the above-mentioned anionic polymer include the above-mentioned carboxyl group, and other examples include: p-toluenesulfonyl group (pH 3 CC 6 H 4 S(=O) 2 -), sulfonate ion group (-SO 3 - ) and phosphate ion group (-PO 4 - ), etc. In addition, as another method of surface treatment, a method of polymerizing the compound on the surface of the conductive particle itself by using a compound having a functional group capable of reacting with a hydroxyl group on the surface of the conductive particle itself, Furthermore, it has a functional group capable of polymerizing through addition and condensation reactions. As the functional group reacting with the hydroxyl group on the surface of the conductive particle itself, carboxyl group and isocyanate group, etc. can be mentioned, and as the functional group polymerized by addition or condensation reaction, hydroxyl group, carboxyl group, amino group and (methyl group) can be mentioned. ) acryl group. The weight average molecular weight of the above-mentioned anionic polymer is preferably at least 2,000, more preferably at least 3,000, and is preferably at most 10,000, more preferably at most 8,000. When the said weight average molecular weight is more than the said minimum and below the said upper limit, sufficient electric charge can be introduced to the surface of electroconductive particle, and a flux property can be provided. Thereby, the agglomeration of the conductive particles can be effectively improved during the conductive connection, and the oxide film on the surface of the electrode can be effectively removed when the member to be connected is connected. If the above-mentioned weight average molecular weight is more than the above-mentioned lower limit and below the above-mentioned upper limit, the anionic polymer can be easily arranged on the surface of the conductive particles themselves, and the aggregation of the conductive particles can be effectively improved during the conductive connection, and can be more efficiently deposited on the electrode. Arrange conductive particles. The above-mentioned weight average molecular weight represents the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). The weight average molecular weight of the polymer obtained by surface-treating the conductive particle itself with a compound that becomes an anionic polymer can be obtained by melting the solder in the conductive particle and using a compound that does not cause the polymer to dissolve. After decomposing dilute hydrochloric acid etc. to remove conductive particles, measure the weight average molecular weight of the remaining polymer. Regarding the introduction amount of the anionic polymer on the surface of the conductive particles, the acid value per 1 g of the conductive particles is preferably 1 mgKOH or more, more preferably 2 mgKOH or more, and preferably 10 mgKOH or less, more preferably 6 mgKOH or less. The said acid value can be measured as follows. 1 g of conductive particles was added to 36 g of acetone, and it was dispersed for 1 minute by ultrasonic waves. Thereafter, titration was performed with 0.1 mol/L potassium hydroxide ethanol solution using phenolphthalein as an indicator. Next, specific examples of electroconductive particles will be described with reference to the drawings. Fig. 4 is a cross-sectional view showing a first example of conductive particles that can be used as a conductive material. The electroconductive particle 21 shown in FIG. 4 is a solder particle. The whole electroconductive particle 21 is formed with solder. The electroconductive particle 21 does not have a base material particle in a core part, and it is not a core-shell particle. The central part of the electroconductive particle 21 and the outer surface part of a conductive part are both formed of solder. Fig. 5 is a cross-sectional view showing a second example of conductive particles that can be used as a conductive material. The electroconductive particle 31 shown in FIG. 5 is equipped with the electroconductive part 33 arrange|positioned on the surface of the base material particle 32 and the base material particle 32. As shown in FIG. The conductive part 33 covers the surface of the substrate particle 32 . The electroconductive particle 31 is the coated particle which the surface of the base material particle 32 was coated with the electroconductive part 33. The conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion). The electroconductive particle 31 is equipped with the 2nd electroconductive part 33A between the base material particle 32 and the solder part 33B. Therefore, the electroconductive particle 31 has the base material particle 32, the 2nd conductive part 33A arrange|positioned on the surface of the base material particle 32, and the solder part 33B arrange|positioned on the outer surface of the 2nd conductive part 33A. Fig. 6 is a cross-sectional view showing a third example of conductive particles that can be used as a conductive material. As mentioned above, the electroconductive part 33 in the electroconductive particle 31 has a two-layer structure. The electroconductive particle 41 shown in FIG. 6 has the solder part 42 as a single-layer electroconductive part. The electroconductive particle 41 is provided with the base material particle 32 and the solder part 42 arrange|positioned on the surface of the base material particle 32. As shown in FIG. Examples of the substrate particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, metal particles, and the like. The aforementioned substrate particles are preferably substrate particles other than metal particles, preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles. The above-mentioned substrate particles may be copper particles. Various organic substances are used suitably as resin for forming the said resin particle. Examples of the resin used to form the above-mentioned resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; polymethacrylic acid Acrylic resins such as methyl ester and polymethyl acrylate; polycarbonate, polyamide, phenol-formaldehyde resin, melamine-formaldehyde resin, benzoguanamine-formaldehyde resin, urea-formaldehyde resin, phenolic resin, melamine resin, benzoguanamine resin, Urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polyethylene, polyphenylene ether, polyacetal, polyimide, polyamideimide, Polyetheretherketone, polyethersulfone, divinylbenzene polymer, and divinylbenzene-based copolymer, etc. As said divinylbenzene type copolymer etc., a divinylbenzene-styrene copolymer, a divinylbenzene-(meth)acrylate copolymer, etc. are mentioned. The resin used to form the above-mentioned resin particles is preferably a polymer obtained by polymerizing one or more polymerizable monomers having ethylenically unsaturated groups, because the hardness of the above-mentioned resin particles can be easily reduced. controlled within an appropriate range. When polymerizing a polymerizable monomer having an ethylenically unsaturated group to obtain the aforementioned resin particles, examples of the polymerizable monomer having an ethylenically unsaturated group include non-crosslinkable monomers and crosslinkable monomers. monomer. Examples of the non-crosslinkable monomer include: styrene-based monomers such as styrene and α-methylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; Monomer; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) Alkyl (meth)acrylate compounds such as lauryl acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, iso(meth)acrylate, etc. 2-Hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl (meth)acrylate and other oxygen-containing (meth)acrylate compounds ;(meth)acrylonitrile and other nitrile-containing monomers; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acetate, vinyl butyrate, vinyl laurate, stearin Acid vinyl ester compounds such as vinyl acid esters; unsaturated hydrocarbons such as ethylene, propylene, isoprene, butadiene; trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, vinyl chloride, fluorine Halogen-containing monomers such as ethylene and chlorostyrene, etc. Examples of the crosslinkable monomer include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and tetramethylolmethane di(meth)acrylate. , trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate ester, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, 1,4-butyl Polyfunctional (meth)acrylate compounds such as diol di(meth)acrylate; triallyl isocyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, di Silane-containing monomers such as allyl acrylamide, diallyl ether, γ-(meth)acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane, etc. . The said resin particle can be obtained by polymerizing the said polymerizable monomer which has an ethylenically unsaturated group by a well-known method. As this method, for example, a method of performing suspension polymerization in the presence of a radical polymerization initiator, and using non-crosslinked seed particles to swell a monomer together with a radical polymerization initiator to polymerize. When the above-mentioned substrate particles are inorganic particles other than metals or organic-inorganic hybrid particles, the inorganic substances used to form the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black. Wait. The particles made of the above-mentioned silica are not particularly limited, and examples thereof include those obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form cross-linked polymer particles, followed by firing as necessary particle of. Examples of the above-mentioned organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin. When the said base material particle is a metal particle, silver, copper, nickel, silicon, gold, titanium, etc. are mentioned as a metal for forming this metal particle. When the above-mentioned substrate particles are metal particles, the metal particles are preferably copper particles. However, the above-mentioned substrate particles are preferably not metal particles. The method of forming the conductive portion on the surface of the substrate particle and the method of forming the solder portion on the surface of the substrate particle or the surface of the second conductive portion are not particularly limited. As the method of forming the above-mentioned conductive part and the above-mentioned solder part, for example, an electroless plating method, an electroplating method, a physical collision method, a method by mechanochemical reaction, a physical vapor deposition method or a physical adsorption method, and the method of forming the substrate particles A method of coating metal powder or a slurry containing metal powder and a binder on the surface, etc. Suitable is an electroless plating method, an electroplating method or a physical collision method. As said physical vapor deposition method, methods, such as vacuum vapor deposition, ion plating, and ion sputtering, are mentioned. In addition, for the above-mentioned physical collision method, for example, Theta-composer (manufactured by Tokusu Works Co., Ltd.) or the like is used. It is preferable that the melting point of the said base material particle|grains is higher than the melting point of the said solder part. The melting point of the substrate particles is preferably higher than 160°C, more preferably higher than 300°C, further preferably higher than 400°C, especially preferably higher than 450°C. In addition, the melting point of the said base material particle does not need to be 400 degreeC or less. The melting point of the above-mentioned substrate particles may be 160° C. or lower. The softening point of the above-mentioned substrate particles is preferably 260° C. or higher. The softening point of the above-mentioned substrate particles may not be 260°C. The said electroconductive particle may have the solder part of a single layer. The said electroconductive particle may have the electroconductive part (solder part, 2nd electroconductive part) of several layers. That is, the electroconductive part of 2 or more layers may be laminated|stacked in the said electroconductive particle. The aforementioned solder is preferably a metal having a melting point of 450° C. or lower (low melting point metal). The above-mentioned solder portion is preferably a metal layer (low melting point metal layer) having a melting point of 450° C. or lower. The above-mentioned low-melting-point metal layer is a layer containing a low-melting-point metal. The solder in the above-mentioned conductive particles is preferably metal particles (low melting point metal particles) having a melting point of 450° C. or lower. The above-mentioned low-melting-point metal particles are particles containing a low-melting-point metal. The low-melting-point metal refers to a metal whose melting point is below 450°C. The melting point of the low melting point metal is preferably not higher than 300°C, more preferably not higher than 160°C. Moreover, it is preferable that the solder in the said electroconductive particle contains tin. In 100% by weight of the metal contained in the above-mentioned solder portion and in 100% by weight of the metal contained in the solder in the above-mentioned conductive particles, the content of tin is preferably at least 30% by weight, more preferably at least 40% by weight, and even more preferably It is preferably at least 70% by weight, particularly preferably at least 90% by weight. The conduction|electrical_connection reliability of electroconductive particle and an electrode becomes it still higher that content of tin in the solder in the said electroconductive particle is more than the said minimum. In addition, the content of the above-mentioned tin can be determined using a high-frequency inductively coupled plasma emission spectroscopic analyzer (manufactured by Horiba Corporation, "ICP-AES") or a fluorescent X-ray analyzer (manufactured by Shimadzu Corporation, "EDX-800HS") Wait for the measurement. By using the electroconductive particle which has the said solder on the outer surface part of a conductive part, a solder melt|dissolves and joins with an electrode, and a solder makes conduction between electrodes. For example, solder and electrodes tend to be in surface contact rather than point contact, so the connection resistance becomes lower. In addition, by using conductive particles with solder on the outer surface of the conductive part, the bonding strength between the solder and the electrode becomes higher, and as a result, the solder and the electrode are less likely to be peeled off, and the conduction reliability is significantly improved. The low melting point metal which comprises the said solder part and the said solder particle is not specifically limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of such alloys include tin-silver alloys, tin-copper alloys, tin-silver-copper alloys, tin-bismuth alloys, tin-zinc alloys, and tin-indium alloys. The above-mentioned low-melting-point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, and tin-indium alloy in terms of excellent wettability to the electrode. More preferred are tin-bismuth alloys and tin-indium alloys. It is preferable that the material which comprises the said solder (solder part) is the molten material whose liquidus line is 450 degreeC or less based on JIS Z3001: Soldering term. As a composition of the said solder, the metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium, etc. is mentioned, for example. It is preferably low melting point and lead-free tin-indium system (117°C eutectic) or tin-bismuth system (139°C eutectic). That is, the above-mentioned solder is preferably lead-free, and is preferably a solder containing tin and indium or a solder containing tin and bismuth. In order to further improve the bonding strength between the above-mentioned solder and the electrode, the solder in the above-mentioned conductive particles may include nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, Molybdenum, palladium and other metals. Moreover, it is preferable that the solder in the said electroconductive particle contains nickel, copper, antimony, aluminum, or zinc from a viewpoint of improving the joint strength of solder and an electrode further. From the viewpoint of further improving the joint strength between the solder and the electrode in the solder portion or conductive particles, the content of these metals for improving the joint strength in 100% by weight of the solder in the above-mentioned conductive particles is preferably 0.0001% by weight or more, and preferably 1% by weight or less. The melting point of the second conductive portion is preferably higher than the melting point of the solder portion. The melting point of the second conductive portion is preferably over 160°C, more preferably over 300°C, more preferably over 400°C, still more preferably over 450°C, especially preferably over 500°C, most preferably over 600°C . Since the above-mentioned solder portion has a low melting point, it melts during conductive connection. It is preferable that the said 2nd electroconductive part does not fuse|melt at the time of electroconductive connection. The conductive particles are preferably used in a molten state of solder, preferably in a state in which the solder portion is molten, and are preferably used in a state in which the solder portion is molten and the second conductive portion is not molten. Since the melting point of the second conductive portion is higher than that of the solder portion, only the solder portion can be melted without melting the second conductive portion during conductive connection. The absolute value of the difference between the melting point of the solder portion and the melting point of the second conductive portion exceeds 0°C, preferably 5°C or higher, more preferably 10°C or higher, still more preferably 30°C or higher, most preferably 50°C or higher , preferably above 100°C. It is preferable that the said 2nd electroconductive part contains metal. The metal constituting the second conductive portion is not particularly limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and alloys thereof. Moreover, tin-doped indium oxide (ITO) can also be used as said metal. The above metals may be used alone or in combination of two or more. The above-mentioned second conductive part 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. It is preferable that an electroconductive particle has a nickel layer, a palladium layer, a copper layer, or a gold layer, It is more preferable to have a nickel layer or a gold layer, It is still more preferable to have a copper layer. By using the conductive particles having these preferable conductive parts to connect the electrodes, the connection resistance between the electrodes is further reduced. Also, solder portions can be formed more easily on the surfaces of the preferred conductive portions. The thickness of the solder portion is preferably at least 0.005 μm, more preferably at least 0.01 μm, preferably at most 10 μm, more preferably at most 1 μm, and still more preferably at most 0.3 μm. Sufficient electroconductivity is acquired as the thickness of a solder part is more than the said minimum and below the said upper limit, and electroconductive particle does not become hard too much, and electroconductive particle can fully deform|transform at the time of connection between electrodes. The thickness of the conductive portion (thickness of the entire conductive portion) is preferably at least 0.005 μm, more preferably at least 0.01 μm, and preferably at most 10 μm, more preferably at most 1 μm, and still more preferably at most 0.5 μm. More preferably, it is 0.3 μm or less. The thickness of the above-mentioned conductive part is the thickness of all the conductive layers when the conductive part is multi-layered. Sufficient electroconductivity is acquired as the thickness of an electroconductive part is more than the said minimum and below the said upper limit, and electroconductive particle does not become hard too much, and electroconductive particle can fully deform|transform at the time of connection between electrodes. When the aforementioned conductive portion is formed of multiple layers, the thickness of the outermost conductive layer is preferably at least 0.001 μm, more preferably at least 0.01 μm, and preferably at most 0.5 μm, more preferably at most 0.1 μm. When the thickness of the outermost conductive layer is not less than the above lower limit and not more than the above upper limit, the coating by the outermost conductive layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between electrodes becomes further low. . Also, in the case where the outermost layer is a gold layer, the thinner the gold layer, the lower the cost. The thickness of the said electroconductive part can be measured by observing the cross-section of electroconductive particle using a field emission scanning electron microscope (FE-SEM), for example. The obtained electroconductive particle was added to "Technovit 4000" by Kulzer company so that the content might become 30 weight%, and it was dispersed, and the embedding resin for electroconductive particle inspection was produced. Using an ion milling device (manufactured by Hitachi High-Technologies, "IM4000"), the cross section of the conductive particle was cut out so as to pass through the vicinity of the center of the conductive particle dispersed in the embedding resin for inspection. Furthermore, it is preferable to use a field emission scanning electron microscope (FE-SEM), set the image magnification to 50,000 times, randomly select 50 conductive particles, and observe the conductive part of each conductive particle. It is preferable to measure the thickness of the electroconductive part in the obtained electroconductive particle, and make it the thickness of an electroconductive part by arithmetic mean. The average particle diameter of the above-mentioned conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, and more preferably 50 μm or less. 40 μm or less, preferably 30 μm or less. If the average particle size of the above-mentioned conductive particles is more than the above-mentioned lower limit and below the above-mentioned upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and it is easy to arrange more solder in the conductive particles between the electrodes, and conduction. The reliability is further improved. The "average particle diameter" of the said electroconductive particle shows the number average particle diameter. The average particle diameter of electroconductive particle can be calculated|required by observing arbitrary 50 electroconductive particles with an electron microscope or an optical microscope, for example, and calculating an average value. Furthermore, in the state of the conductive particles alone before being mixed with the thermosetting component and the flux, and in the state of the conductive particles in the conductive material after being mixed with the thermosetting component and the flux, the conductive particles The average particle size is generally the same. The shape of the said electroconductive particle is not specifically limited. The shape of the said electroconductive particle may be spherical, and the shape other than a spherical shape, such as a flat shape, may be sufficient. In 100% by weight of the above-mentioned conductive material, the content of the above-mentioned conductive particles is preferably at least 1% by weight, more preferably at least 2% by weight, further preferably at least 10% by weight, especially preferably at least 20% by weight, most preferably at least 20% by weight. It is 30% by weight or more, and is preferably 90% by weight or less, more preferably 80% by weight or less, further preferably 60% by weight or less, especially preferably 50% by weight or less. If the content of the above-mentioned conductive particles is more than the above-mentioned lower limit and below the above-mentioned upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and it is easy to arrange more solder in the conductive particles between the electrodes, and the conduction reliability can be improved. further up. From the viewpoint of further improving conduction reliability, the content of the above-mentioned electroconductive particles is preferably large. (Thermosetting compound) The above-mentioned thermosetting compound is a compound that can be cured by heating. Examples of the thermosetting compounds include: oxetane compounds, epoxy compounds, episulfide compounds, (meth)acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, Ester compounds, polysiloxane compounds and polyimide compounds, etc. From the viewpoint of further optimizing the curability and viscosity of the conductive material, and further improving conduction reliability and connection reliability, epoxy compounds or episulfide compounds are preferred, and epoxy compounds are more preferred. The above-mentioned conductive material preferably includes an epoxy compound. The said thermosetting compound may use only 1 type, and may use 2 or more types together. From the viewpoint of effectively improving the heat resistance of the cured product and effectively reducing the dielectric constant of the cured product, the above-mentioned thermosetting compound preferably includes a thermosetting compound having a nitrogen atom, and more preferably includes a thermosetting compound having a nitrogen atom. A thermosetting compound with three 𠯤 skeletons. Examples of the above-mentioned thermosetting compound having a three-skeleton include tris-triglycidyl ether, etc., such as the TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC -L, TEPIC-PAS, TEPIC-VL, TEPIC-UC), etc. An aromatic epoxy compound is mentioned as said epoxy compound. Preferred are crystalline epoxy compounds such as resorcinol-type epoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, and benzophenone-type epoxy compounds. Preferably, it is an epoxy compound that is solid at normal temperature (23° C.) and whose melting temperature is not higher than the melting point of solder. The melting temperature is preferably below 100°C, more preferably below 80°C, more preferably above 40°C. By using the above-mentioned preferable epoxy compound, the position of the first connection object member and the second connection object member can be suppressed when the acceleration occurs due to high viscosity or impact such as transportation in the step of laminating the connection object members Moreover, the viscosity of the conductive material can be greatly reduced by the heat during hardening, and the solder can be coagulated efficiently. In 100% by weight of the above-mentioned conductive material, the content of the above-mentioned thermosetting compound is preferably at least 20% by weight, more preferably at least 40% by weight, further preferably at least 50% by weight, and more preferably at most 99% by weight , more preferably 98% by weight or less, further preferably 90% by weight or less, especially preferably 80% by weight or less. From the viewpoint of further improving the impact resistance, the content of the above-mentioned thermosetting compound is preferably large. (Thermosetting agent) The said thermosetting agent can thermoset the said thermosetting compound. Examples of the thermosetting agent include imidazole curing agents, phenolic curing agents, mercaptan curing agents, amine curing agents, acid anhydride curing agents, thermal cation initiators, and thermal radical generators. The said thermosetting agent may use only 1 type, and may use 2 or more types together. The imidazole curing agent is not particularly limited, and examples thereof include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl -2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl second-trimellitate and 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl second-tri-isocyanuric acid adduct, etc. The mercaptan curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. . The solubility parameter of the above-mentioned mercaptan curing agent is preferably not less than 9.5, and is preferably not more than 12. The above solubility parameters were calculated by the Fedors method. For example, the solubility parameter of trimethylolpropane tri-3-mercaptopropionate is 9.6, and that of dipentaerythritol hexa-3-mercaptopropionate is 11.4. The amine curing agent is not particularly limited, and examples thereof include hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis(3-aminopropyl)-2 , 4,8,10-tetraspiro[5.5]undecane, bis(4-aminocyclohexyl)methane, m-phenylenediamine and diaminodiphenylsulfone, etc. Examples of the thermal cationic initiator include iodonium-based cationic hardeners, oxonium-based cationic hardeners, and perium-based cationic hardeners. Bis(4-tert-butylphenyl)iodonium hexafluorophosphate and the like are exemplified as the above-mentioned iodine-based cationic curing agent. Examples of the above-mentioned oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate and the like. Examples of the above-mentioned permeic acid-based cation curing agent include tris-p-cresyl percited hexafluorophosphate, and the like. It does not specifically limit as said thermal radical generating agent, An azo compound, an organic peroxide, etc. are mentioned. As said azo compound, azobisisobutyronitrile (AIBN) etc. are mentioned. Examples of the organic peroxide include di-tert-butyl peroxide, methyl ethyl ketone peroxide, and the like. The reaction initiation temperature of the above thermosetting agent is preferably at least 50°C, more preferably at least 70°C, still more preferably at least 80°C, preferably at most 250°C, more preferably at most 200°C, and still more preferably at least 200°C. It is not higher than 150°C, especially preferably not higher than 140°C. If the reaction initiation temperature of the said thermosetting agent is more than the said minimum and below the said upper limit, the solder in electroconductive particle will be arrange|positioned more efficiently on an electrode. The reaction initiation temperature of the above-mentioned thermosetting agent is more preferably 80°C or higher and 140°C or lower. From the viewpoint of disposing the solder in the conductive particles on the electrodes more efficiently, the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder in the conductive particles, more preferably 5°C higher above, and more preferably 10°C or more. The reaction initiation temperature of the above-mentioned thermosetting agent refers to the temperature at which the peak of heat generation begins to rise as measured by DSC (differential scanning calorimeter, differential scanning calorimeter). The content of the above-mentioned thermosetting agent is not particularly limited. The content of the thermosetting agent is preferably at least 0.01 part by weight, more preferably at least 1 part by weight, and preferably at most 200 parts by weight, more preferably at most 100 parts by weight, based on 100 parts by weight of the thermosetting compound. , and more preferably 75 parts by weight or less. When content of a thermosetting agent is more than the said minimum, it becomes easy to fully harden a conductive material. If the content of the thermosetting agent is below the above upper limit, excess thermosetting agent that does not participate in hardening will not easily remain after curing, and the heat resistance of the cured product will further increase. (Flux) The conductive material described above contains flux. By using the flux, the solder in the conductive particles can be more efficiently arranged on the electrode. Also, in the present invention, the above-mentioned flux is a combination of an acid having the effect of cleaning the metal surface and a base having the effect of neutralizing the acid, and is a salt of these acids and bases. If the above-mentioned flux, which is a salt of a specific acid and alkali, is solid at 25°C, the storage stability of the conductive material becomes high, and excellent solder can be exhibited even if it is left for a long time after placing the conductive material on the member to be connected. Agglomeration, so it can provide a conductive material that can exhibit high conduction reliability. The above flux is preferably a salt of acid and alkali and is solid at 25°C. The aforementioned flux is, for example, a salt of an organic compound having a carboxyl group and a compound having an amine group, preferably a salt of an organic compound having a carboxyl group and an organic compound having an amine group. In addition, from the viewpoint of effectively improving the storage stability of the conductive material, exhibiting excellent solder agglomeration and high conduction reliability even after placing the conductive material on the member to be connected for a long period of time, as a specific The above-mentioned flux which is a salt of an acid and a base is preferably solid at 25°C. The above fluxes may be used alone or in combination of two or more. The aforementioned flux can be obtained, for example, by neutralizing a carboxylic acid or carboxylic acid anhydride and an amino group-containing compound. The above-mentioned flux is preferably a neutralization reactant of carboxylic acid or carboxylic acid anhydride and the compound containing amino groups. Examples of the aforementioned carboxylic acid or carboxylic anhydride include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and malic acid as aliphatic carboxylic acids, and cyclohexyl as cyclic aliphatic carboxylic acids. Carboxylic acid, 1,4-cyclohexyldicarboxylic acid, aromatic carboxylic acid isophthalic acid, terephthalic acid, trimellitic acid, ethylenediaminetetraacetic acid, and their anhydrides, etc. In order to further enhance the flux effect, it is preferable that the above-mentioned acid and the above-mentioned organic compound having a carboxyl group have a plurality of carboxyl groups. As an organic compound which has several carboxyl groups, a dicarboxylic acid, a tricarboxylic acid, etc. are mentioned. In addition, the above-mentioned acid and the above-mentioned organic compound having a carboxyl group preferably have an alkyl group in order to easily form a salt, and the total number of carbon atoms of the alkyl group and carboxyl group is preferably 4 or more and preferably 8 or less. In order to obtain the above-mentioned reactants, esters of carboxylic acids may also be used. Examples of esters of carboxylic acids include alkyl esters of the above-mentioned carboxylic acids, and the like. Examples of the alkyl group of the above-mentioned alkyl ester of carboxylic acid include an alkyl group having 1 to 4 carbon atoms, and the number of carbon atoms in the alkyl group is preferably 3 or less, more preferably 2 or less. Examples of the amine group-containing compound not having an aromatic skeleton among the above-mentioned amine group-containing compounds include diethanolamine, triethanolamine, methyldiethanolamine, ethyldiethanolamine, cyclohexylamine, and dicyclohexylamine. As the amino group-containing compound having an aromatic skeleton among the above-mentioned amino group-containing compounds, benzylamine, benzhydrylamine, 2-methylbenzylamine, 3-methylbenzylamine and 4 - tert-butylbenzylamine and the like. Examples of secondary amines include: N-methylbenzylamine, N-ethylbenzylamine, N-phenylbenzylamine, N-tert-butylbenzylamine, and N-isopropylbenzylamine Wait. Examples of tertiary amines include N,N-dimethylbenzylamine, imidazole compounds, and triazole compounds. From the viewpoint of effectively improving the storage stability of conductive materials and making it difficult for components other than conductive particles to move during connection between electrodes, the above-mentioned amine-containing compound is preferably an aromatic amine compound or an aliphatic aliphatic compound. Cyclic amine compounds. The activation temperature (melting point) of the above flux is preferably above 40°C, more preferably above 50°C. Storage stability will become higher as the activation temperature of the said flux is more than the said minimum. From the viewpoint of disposing the solder in the conductive particles on the electrodes more efficiently, the melting point of the above-mentioned flux is preferably at least -50°C, more preferably the melting point of the solder in the above-mentioned conductive particles. The melting point of the solder is -30°C or higher, and preferably the melting point of the solder in the above-mentioned conductive particles is +50°C or lower, more preferably the melting point of the solder in the above-mentioned conductive particles is +30°C or lower. Reach the melting point of the solder in the above-mentioned conductive particles. If the melting point of the flux is not less than the above-mentioned lower limit and not more than the above-mentioned upper limit, the effect of the flux will be exhibited more effectively, and the solder will be placed on the electrodes more efficiently. From the viewpoint of disposing the solder in the conductive particles on the electrodes more efficiently, the melting point of the flux is preferably lower than the reaction initiation temperature of the thermosetting agent, more preferably at least 5°C lower, and furthermore It is preferably lower than 10°C. The above flux can be dispersed in the conductive material, and can also be attached to the surface of the conductive particles. In conductive materials at 25°C, the above flux exists as a solid. When flux is added to the conductive material in a uniformly molten state, the viscosity of the conductive material may increase due to a reaction between the thermosetting component and a part of the flux. In addition, there are cases where, if a conductive material is placed on the member to be connected and the conductive material is kept in contact with the air for a long time, the moisture in the air will promote the reaction between the flux and the thermosetting compound, or the flux will React with the surface of the solder to generate metal ions, etc., which will adversely affect the agglomeration of the solder or the insulation between adjacent electrodes. In contrast, if the above-mentioned flux exists in a conductive material at 25°C as a solid, only the surface of the flux will be affected by the above-mentioned effects, so it can exhibit higher storage stability, or higher conduction after long-term storage sex, insulation. In addition, when the above-mentioned flux exists in a conductive material at 25°C as a solid, and the above-mentioned flux melts at a temperature lower than the melting point of the solder, in the case of the conductive material being a paste, it can be used for the conductive material. Gives thixotropy at room temperature (23°C). Thereby, precipitation of electroconductive particles can be prevented, shape retention after coating can be realized, and electroconductive material can be further prevented from flowing out to unnecessary places. When the conductive material is a film, since the above-mentioned flux is solid, the liquid component in the conductive material can be reduced, so the cuttability of the film can be improved, and bleeding from the cut surface can be suppressed. In addition, when the above-mentioned flux melts at a temperature lower than the melting point of the solder, the flux is in a molten state if it is below the melting point of the solder, so the melt viscosity of the conductive material is sufficiently reduced, and better solder aggregation can be exhibited. sex. Furthermore, when the above-mentioned flux melts at a temperature lower than the melting point of the solder, if the temperature is higher than the melting point of the solder, the flux melts into the thermosetting compound or thermosetting agent, and further, the thermosetting The compound or thermosetting agent reacts with the carboxyl group and amine group of the flux, so that the flux components are taken into the hardening system. Thereby, high insulation can be exhibited between adjacent electrodes, thereby preventing electrode corrosion. In conductive materials at 25°C, the average particle size of the flux is preferably below 30 μm. When the average particle size of the flux is in the above range, the flux can be present in the conductive material in a state that does not react with the resin, and the storage stability of the conductive material can be further improved. For the same reason, the average particle size of the flux is preferably 0.1 μm or more. The "average particle size" of the above-mentioned flux indicates the number average particle size. The average particle size of the flux is obtained by observing, for example, 50 arbitrary conductive particles with an electron microscope or an optical microscope, and calculating the average value. Furthermore, if in the state of the flux single agent before mixing with the conductive particles and the thermosetting component and in the state of the flux in the conductive material after mixing with the conductive particles and the thermosetting component, the flux If there is no difference in the average particle size, the average particle size can be evaluated by using a single flux before mixing with conductive particles and thermosetting components. Also, in a conductive material at 25°C, the ratio of the average particle size of the flux to the average particle size of the conductive particles (average particle size of the flux/average particle size of the conductive particles) is preferably 3 or less, and more preferably Preferably, it is 1 or less, More preferably, it is 0.2 or less. If the said ratio is below the said upper limit, a flux can be made to contact electroconductive particle efficiently, and the flux performance at the time of heating can be improved more. For the same reason, the ratio (average particle diameter of solder flux/average particle diameter of conductive particles) is preferably at least 0.005, more preferably at least 0.01, and still more preferably at least 0.02. In 100% by weight of the above-mentioned conductive material, the content of the above-mentioned flux is preferably at least 0.5% by weight, and preferably at most 30% by weight, more preferably at most 25% by weight. (Insulating Particles) From the viewpoint of precisely controlling the distance between members to be connected by the cured material of the conductive material and the distance between members to be connected by the solder in the conductive particles, The above-mentioned conductive material preferably contains insulating particles. In the said conductive material, the said insulating particle does not need to adhere to the surface of an electroconductive particle. In the said electrically-conductive material, it is preferable that the said insulating particle exists separately from electroconductive particle. The average particle diameter of the above-mentioned insulating particles is preferably at least 10 μm, more preferably at least 20 μm, further preferably at least 25 μm, more preferably at most 100 μm, more preferably at most 75 μm, and more preferably at most 75 μm. Below 50 μm. If the average particle diameter of the above-mentioned insulating particles is more than the above-mentioned lower limit and not more than the above-mentioned upper limit, the distance between the members to be connected by the cured product of the conductive material, and the objects to be connected by the solder in the conductive particles The spacing between components has become more modest. The "average particle diameter" of the above-mentioned insulating particles means a number average particle diameter. The average particle diameter of insulating particle|grains is calculated|required by observing 50 arbitrary electroconductive particles with an electron microscope or an optical microscope, for example, and calculating an average value. Furthermore, the insulating properties in the state of insulating particles alone before mixing with conductive particles, thermosetting components and flux and in the conductive material after mixing with conductive particles, thermosetting components and flux In the state of particles, the average particle diameter of the insulating particles is generally the same. As a material of the said insulating particle, an insulating resin, an insulating inorganic substance, etc. are mentioned. As said insulating resin, the above-mentioned resin mentioned as resin for forming the resin particle which can be used as a base material particle is mentioned. Examples of the above-mentioned insulating inorganic substance include those listed above as the inorganic substance for forming inorganic particles that can be used as substrate particles. Specific examples of the insulating resin used as a material for the insulating particles include: polyolefins, (meth)acrylate polymers, (meth)acrylate copolymers, block polymers, thermoplastic resins, thermoplastic Cross-linked resins, thermosetting resins, water-soluble resins, etc. As said polyolefins, polyethylene, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, etc. are mentioned. As said (meth)acrylate polymer, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, etc. are mentioned. Examples of the above block polymer include: polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, and SBS type styrene-butadiene block copolymer, and Such hydrides, etc. As said thermoplastic resin, a vinyl polymer, a vinyl copolymer, etc. are mentioned. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methylcellulose. Among them, water-soluble resin is preferred, and polyvinyl alcohol is more preferred. The content of the insulating particles in 100% by weight of the conductive material is preferably at least 0.1% by weight, more preferably at least 0.5% by weight, and preferably at most 10% by weight, more preferably at most 5% by weight. The above-mentioned conductive material may not contain insulating particles. If the content of the insulating particles is more than the above-mentioned lower limit and below the above-mentioned upper limit, the distance between the members to be connected by the cured product of the conductive material and the distance between the members to be connected by the solder in the conductive particles Spacing becomes more modest. (Other Components) The above conductive material may contain, for example, fillers, extenders, softeners, plasticizers, polymerization catalysts, hardening catalysts, colorants, antioxidants, heat stabilizers, light stabilizers, ultraviolet ray Various additives such as absorbents, lubricants, antistatic agents and flame retardants. (Connection Structure and Manufacturing Method of Connection Structure) The connection structure of the present invention includes a first connection object member having at least one first electrode on its surface, a second connection object member having at least one second electrode on its surface, and a connection object connected to the above-mentioned The connection part of the 1st connection object member and the said 2nd connection object member. In the connection structure of this invention, the material of the said connection part is the said conductive material, and the said connection part is formed with the said conductive material. In the connection structure of this invention, the said 1st electrode and the said 2nd electrode are electrically connected by the solder part in the said connection part. The manufacturing method of the above-mentioned connection structure includes the following steps: using the above-mentioned conductive material, disposing the above-mentioned conductive material on the surface of the first connection object member having at least one first electrode on the surface; On the opposite surface, arrange the second connection object member with at least one second electrode on the surface in such a way that the first electrode and the second electrode face each other; heat the conductive material to the melting point of the solder in the conductive particles As described above, the connection portion connecting the first connection object member and the second connection object member is formed by the cured product of the conductive material, and the first electrode and the second electrode are connected by the solder portion in the connection portion. electrical connection. Preferably, the conductive material is heated to a temperature equal to or higher than the hardening temperature of the thermosetting component and the thermosetting compound. In the connection structure of the present invention and the manufacturing method of the above-mentioned connection structure, since a specific conductive material is used, the solder in the plurality of conductive particles is easy to gather between the first electrode and the second electrode, and it is possible to efficiently Solder is placed on the electrodes (wires). In addition, part of the solder is less likely to be placed in the area (space) where no electrode is formed, and the amount of solder placed in the area where no electrode is formed can be significantly reduced. Therefore, the conduction reliability between the first electrode and the second electrode can be improved. Furthermore, electrical connection between electrodes adjacent in the lateral direction where connection is prohibited can be prevented, and insulation reliability can be improved. In addition, in order to efficiently arrange the solder among the plurality of conductive particles on the electrodes and significantly reduce the amount of solder disposed in the region where electrodes are not formed, it is preferable to use a conductive paste instead of a conductive film. The thickness of the solder portion between the electrodes is preferably at least 10 μm, more preferably at least 20 μm, and is preferably at most 100 μm, more preferably at most 80 μm. The solder wetting area on the surface of the electrode (the area in contact with the solder in 100% of the exposed area of the electrode, relative to the above-mentioned first electrode before forming the above-mentioned connection part and the above-mentioned first electrode to be electrically connected to the above-mentioned first electrode 2. The exposed area of the electrode (100%) is preferably 50% or more, more preferably 70% or more, and preferably 100% or less. In the method of manufacturing a connection structure according to the present invention, it is preferable not to apply pressure in the step of arranging the second connection object member and the step of forming the connection portion, and to apply the weight of the second connection object member to the The above-mentioned conductive material; or preferably pressurized in at least one of the step of arranging the above-mentioned second connection object member and the step of forming the above-mentioned connection part, and in the step of arranging the above-mentioned second connection object member and forming the above-mentioned connection Part of the steps In these two steps, the pressurized pressure is less than 1 MPa. Aggregation of the solder in the conductive particles was significantly promoted by not applying a pressure of 1 MPa or more. From the viewpoint of suppressing the warping of the member to be connected, in the method of manufacturing the connected structure of the present invention, at least one of the step of arranging the second member to be connected and the step of forming the connecting portion may be added. In addition, in the step of arranging the above-mentioned second connection object member and the step of forming the above-mentioned connection part, the pressure of the pressurization does not reach 1 MPa. In the case of applying pressure, the pressure may be applied only in the step of arranging the above-mentioned second connection object member, or may be applied only in the step of forming the above-mentioned connection part, or may be performed in the step of arranging the above-mentioned second connection object member. Pressurization is performed in the two steps of the step of forming the above-mentioned connecting portion. The pressurized pressure is less than 1 MPa including the case where no pressurization is performed. When pressurizing, the pressurizing pressure is preferably at most 0.9 MPa, more preferably at most 0.8 MPa. Compared with the case where the pressurized pressure exceeds 0.8 MPa, when the pressurized pressure is 0.8 MPa or less, the aggregation of the solder in the conductive particles is more remarkably promoted. In the method of manufacturing a connection structure according to the present invention, it is preferable not to apply pressure in the step of arranging the second connection object member and the step of forming the connection portion, and to apply the weight of the second connection object member to the The above-mentioned conductive material is preferably such that a pressure exceeding the weight of the second connection object member is not applied to the above-mentioned conductive material in the step of arranging the second connection object member and the step of forming the connection portion. In such cases, the uniformity of the amount of solder in the plurality of solder portions can be further improved. Furthermore, the thickness of the solder part can be made thicker more effectively, and the solder in the plurality of conductive particles can be more easily gathered between the electrodes, and the solder in the plurality of conductive particles can be more efficiently arranged on the electrodes (lines). . In addition, part of the solder in the plurality of conductive particles is less likely to be arranged in the region (interval) where electrodes are not formed, and the amount of solder in the conductive particles arranged in the region where electrodes are not formed can be further reduced. Therefore, the conduction reliability between electrodes can be further improved. Furthermore, electrical connection between electrodes adjacent in the lateral direction where connection is prohibited can be further prevented, and insulation reliability can be further improved. Furthermore, the inventors of the present invention have also found that if the weight of the second connection object member is applied to the conductive material without applying pressure in the step of arranging the second connection object member and the step of forming the connection portion, Then, before forming the connection part, the solder arranged in the area (space) where no electrodes are formed is more likely to gather between the first electrode and the second electrode, and a plurality of conductive particles can be more efficiently arranged on the electrodes (lines) In the solder. In the present invention, a combination of a configuration using conductive paste instead of a conductive film and a configuration in which the weight of the second connection object member is applied to the conductive paste without applying pressure is necessary to obtain the effect of the present invention at a higher level. has great significance. Furthermore, WO2008/023452A1 describes that, from the point of view of pushing the solder powder to efficiently move to the electrode surface, it is suitable to pressurize with a specific pressure at the time of bonding; and it also describes the point of view of forming a solder region more reliably. For example, the pressing pressure is set to 0 MPa or more, preferably 1 MPa or more; it is further described that the pressure applied to the adhesive tape may be 0 MPa, or it may be adjusted by the weight of the member placed on the adhesive tape. The tape applies specific pressure. Although WO2008/023452A1 describes that the pressure intentionally applied to the adhesive tape can be 0 MPa, there is no description about the difference in effect between the case of applying a pressure exceeding 0 MPa and the case of setting it to 0 MPa. In addition, WO2008/023452A1 does not have any understanding of the importance of using a paste-like conductive paste instead of a film-like conductive paste. In addition, if a conductive paste is used instead of a conductive film, it is easy to adjust the thickness of the connection part and the solder part according to the coating amount of the conductive paste. On the other hand, in the case of a conductive film, there is a problem that in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film with a different thickness or to prepare a conductive film with a specific thickness. Also, compared with the conductive paste, the conductive film tends to fail to reduce the melt viscosity of the conductive film sufficiently at the melting temperature of the solder, and tends to hinder the agglomeration of the solder. Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. Fig. 1 is a cross-sectional view schematically showing a connection structure obtained by using a conductive material according to an embodiment of the present invention. The connection structure 1 shown in FIG. 1 is provided with the 1st connection object member 2, the 2nd connection object member 3, and the connection part 4 which connects the 1st connection object member 2 and the 2nd connection object member 3. As shown in FIG. The connecting portion 4 is formed of the above-mentioned conductive material. In this embodiment, the conductive material contains solder particles as conductive particles. The connecting portion 4 has a solder portion 4A in which a plurality of solder particles are gathered and bonded to each other, and a hardened portion 4B in which a thermosetting component is thermally cured. In this embodiment, in order to form 4 A of solder parts, solder particle is used as electroconductive particle. Both the central part of the solder particle and the outer surface of the conductive part are formed of solder. The 1st connection object member 2 has the some 1st electrode 2a on the surface (upper surface). The 2nd connection object member 3 has the some 2nd electrode 3a on the surface (lower surface). The first electrode 2a and the second electrode 3a are electrically connected by the solder portion 4A. Therefore, the first connection object member 2 and the second connection object member 3 are electrically connected by the solder portion 4A. In addition, in the connection part 4, the solder does not exist in the region (cured part part 4B part) different from the solder part 4A gathered between the 1st electrode 2a and the 2nd electrode 3a. There is no solder separated from the solder portion 4A in a region (hardened portion 4B portion) different from the solder portion 4A. Furthermore, if it is a small amount, solder may exist in a region (hardened part 4B part) different from the solder part 4A gathered between the 1st electrode 2a and the 2nd electrode 3a. As shown in Fig. 1, in the connection structure 1, a plurality of solder particles are gathered between the first electrode 2a and the second electrode 3a, and after the plurality of solder particles are melted, the molten material of the solder particles wets and spreads on the surface of the electrodes. After curing, the solder portion 4A is formed. Therefore, the connection area between 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts and the 2nd electrode 3a becomes large. That is, compared with the case where the outer surface of the conductive portion is made of conductive particles made of metals such as nickel, gold, or copper, by using solder particles, the solder portion 4A and the first electrode 2a, and the solder portion 4A and the second electrode The contact area of 3a becomes larger. Therefore, the conduction reliability and connection reliability of the connection structure 1 become high. Moreover, in the connection structure 1 shown in FIG. 1, the whole solder part 4A is located in the opposing area|region between 1st, 2nd electrode 2a, 3a. The connection structure 1X of the modification shown in FIG. 3 is different from the connection structure 1 shown in FIG. 1 only in the connection part 4X. The connecting portion 4X has a solder portion 4XA and a cured portion 4XB. Like the connection structure 1X, most of the solder portion 4XA is located in the region where the first and second electrodes 2a and 3a face each other, and a part of the solder portion 4XA faces sideways from the region where the first and second electrodes 2a and 3a face each other. Fang sticks out. The solder portion 4XA protruding laterally from the area where the first and second electrodes 2a, 3a face each other is a part of the solder portion 4XA, not solder separated from the solder portion 4XA. Furthermore, in this embodiment, the amount of the solder separated from the solder part can be reduced, but the solder separated from the solder part may also exist in the hardened part. If the amount of solder particles used is reduced, the connection structure 1 can be easily obtained. When the usage-amount of a solder particle increases, it becomes easy to obtain connection structure 1X. From the viewpoint of further improving conduction reliability, it is preferable to observe the first electrode 2a and the second electrode 2a along the lamination direction of the first electrode 2a, the connection part 4, 4X and the second electrode 3a in the connection structure 1, 1X. In the case of the facing part of the electrode 3a, the area of the facing part of the first electrode 2a and the second electrode 3a is 50% or more (more preferably 60% or more, more preferably 70% or more, especially 80% of the area of the facing part of the first electrode 2a and the second electrode 3a % or more, preferably more than 90%), the solder portions 4A, 4XA in the connection portions 4, 4X are arranged. From the viewpoint of further improving conduction reliability, it is preferable that when the opposing portion of the first electrode and the second electrode is viewed along the lamination direction of the first electrode, the connection portion, and the second electrode, the second electrode 50% or more (more preferably 60% or more, further preferably 70% or more, especially preferably 80% or more, most preferably 90% or more) of the area of 100% of the opposing portion of the first electrode and the above-mentioned second electrode The solder part in the above-mentioned connecting part is arranged. From the viewpoint of further improving conduction reliability, it is preferable to view the opposing direction of the first electrode and the second electrode in a direction perpendicular to the lamination direction of the first electrode, the connection portion, and the second electrode. In some cases, 60% or more (more preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, especially preferably 95% or more, most preferably 99% or more of the solder portion in the above-mentioned connecting portion above) is disposed at the opposing portion of the first electrode and the second electrode. Next, an example of the method of manufacturing the connection structure 1 using the electrically-conductive material which concerns on one embodiment of this invention is demonstrated. First, the 1st connection object member 2 which has the 1st electrode 2a on the surface (upper surface) is prepared. Next, as shown in FIG. 2( a ), a conductive material 11 including a thermosetting component 11B, a plurality of solder particles 11A, and a specific flux is disposed on the surface of the first connection object member 2 (first step). The conductive material used contains a thermosetting compound and a thermosetting agent as a thermosetting component 11B. The conductive material 11 is arranged on the surface of the first connection object member 2 on which the first electrode 2a is provided. After the conductive material 11 is arranged, the solder particles 11A are arranged on both the first electrode 2a (line) and the region (space) where the first electrode 2a is not formed. The method of arranging the conductive material 11 is not particularly limited, and examples thereof include coating with a dispenser, screen printing, and spray coating with an inkjet device. Moreover, the 2nd connection object member 3 which has the 2nd electrode 3a on the surface (lower surface) is prepared. Then, as shown in FIG. 2(b), the second connection object is arranged on the surface of the conductive material 11 on the surface of the first connection object member 2 that is opposite to the first connection object member 2 side of the conductive material 11. Build 3 (step 2). On the surface of the conductive material 11, the second connection object member 3 is arranged from the side of the second electrode 3a. At this time, the 1st electrode 2a and the 2nd electrode 3a are made to oppose. Next, the conductive material 11 is heated to a temperature equal to or higher than the melting point of the solder particles 11A (third step). Preferably, the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (binder). During this heating, the solder particles 11A present in the region where no electrodes are formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect). When using a conductive paste instead of a conductive film, 11 A of solder particles gather efficiently between the 1st electrode 2a and the 2nd electrode 3a. Also, the solder particles 11A are melted and bonded to each other. Also, the thermosetting component 11B is thermally cured. As a result, as shown in FIG. 2( c ), the connection portion 4 connecting the first connection object member 2 and the second connection object member 3 is formed from the conductive material 11 . The connection part 4 is formed of the conductive material 11, the solder part 4A is formed by bonding a plurality of solder particles 11A, and the cured part 4B is formed by thermosetting of the thermosetting component 11B. If the solder particles 11A move sufficiently, from the start of the movement of the solder particles 11A not located between the first electrode 2a and the second electrode 3a until the movement of the solder particles 11A between the first electrode 2a and the second electrode 3a is completed, It does not matter if the temperature is not kept constant during this period. In this embodiment, it is preferable not to pressurize in the said 2nd process and the said 3rd process. In this case, the weight of the second connection object member 3 is applied to the conductive material 11 . Therefore, when forming the connection part 4, 11 A of solder particles gather efficiently between the 1st electrode 2a and the 2nd electrode 3a. Furthermore, when the pressure is applied in at least one of the second step and the third step, the tendency for the solder particles to gather between the first electrode and the second electrode to be suppressed tends to increase. Also, in this embodiment, since no pressure is applied, when the first connection object member coated with the conductive material is overlapped with the second connection object member, even if the first connection object member and the second connection object member are overlapped. In the case where the electrodes of the first connection object member and the electrodes of the second connection object member are overlapped in a state where they are not aligned, the deviation can also be corrected so that the electrodes of the first connection object member and the electrodes of the second connection object member connection (self-orientation effect). The reason for this is that the molten solder that gathers itself between the electrode of the first connection object member and the electrode of the second connection object member, if the solder between the electrode of the first connection object member and the electrode of the second connection object member When the contact area of the solder and other components of the conductive material is minimized, the energy becomes stable. Therefore, the force of the aligned connection structure acts to realize the connection structure having the minimum area. At this time, it is preferable that the conductive material is not hardened, and that the viscosity of the components other than the conductive particles of the conductive material is sufficiently low at the temperature and within the time. In this way, the connection structure 1 shown in FIG. 1 is obtained. In addition, the above-mentioned second step and the above-mentioned third step may be performed continuously. In addition, after performing the above-mentioned second step, the obtained laminate of the first connection object member 2, the conductive material 11, and the second connection object member 3 may be moved to a heating section to perform the above-mentioned third step. In order to carry out the above-mentioned heating, the above-mentioned laminated body may be arranged on a heating member, or the above-mentioned laminated body may be arranged in a heated space. The heating temperature in the third step is preferably at least 140°C, more preferably at least 160°C, preferably at most 450°C, more preferably at most 250°C, further preferably at most 200°C. As the heating method in the above-mentioned third step, a method of heating the entire connection structure in a reflow furnace or an oven to a temperature above the melting point of the solder and above the hardening temperature of the thermosetting compound, or only for the connection structure A method of locally heating the connecting part of the body. Examples of devices used in the local heating method include a heating plate, a heat gun for blowing hot air, a soldering iron, and an infrared heater. In addition, when using a heating plate for local heating, it is preferable to use a metal with high thermal conductivity to form the upper surface of the heating plate directly below the connection part, and to use a material with low thermal conductivity such as fluororesin for other parts that are not easy to be heated. Form the upper surface of the heating plate. The above-mentioned first and second connection object members are not particularly limited. Specific examples of the first and second connection object members include electronic components such as semiconductor chips, semiconductor components, LED chips, LED components, capacitors, and diodes, resin films, printed circuit boards, flexible printed circuit boards, Electronic components such as flexible flat cables, rigid-flex substrates, glass epoxy substrates, and circuit substrates such as glass substrates. It is preferable that the said 1st, 2nd connection object member is an electronic component. Preferably, at least one of the first connection object member and the second connection object member is a semiconductor chip, a resin film, a flexible printed circuit board, a rigid flexible circuit board, or a flexible flat cable, more preferably a resin film, a flexible printed circuit board , flexible flat cable or rigid-flex substrate. The second connection target member is preferably a semiconductor chip, a resin film, a flexible printed circuit board, a rigid-flexible substrate, or a flexible flat cable, more preferably a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid-flexible substrate. Resin films, flexible printed circuit boards, flexible flat cables, and rigid-flexible substrates have properties of high flexibility and relatively light weight. When performing the connection of such a connection object member using a conductive film, there exists a tendency for the solder in electroconductive particle to gather on an electrode hard. On the other hand, by using a conductive paste, even if a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible substrate is used, the solder in the conductive particles can be efficiently gathered on the electrode, thereby sufficiently improving Conduction reliability between electrodes. In the case of using resin film, flexible printed circuit board, flexible flat cable or rigid flexible substrate, compared with the case of using other connection object members such as semiconductor chips, the inter-electrode gap achieved by not applying pressure can be obtained more effectively. The effect of improving the conduction reliability. The forms of the above-mentioned connection object members include peripheral or surface array, and the like. As a feature of each member, in the case of a peripheral substrate, electrodes exist only on the outer peripheral portion of the substrate. In the case of a surface array substrate, electrodes exist within the surface. Examples of electrodes provided on the member to be connected include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes, and tungsten electrodes. When the above-mentioned member to be connected is a flexible printed circuit board, the above-mentioned electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode or a copper electrode. When the member to be connected is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. Furthermore, when the above-mentioned electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode formed by laminating an aluminum layer on the surface of a metal oxide layer. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element, zinc oxide doped with a trivalent metal element, and the like. Sn, Al, Ga, etc. are mentioned as said trivalent metal element. Hereinafter, an Example and a comparative example are given, and this invention is demonstrated concretely. The present invention is not limited to the following examples. Thermosetting compound 1: Resorcinol-type epoxy compound, "Epolight TDC-LC" manufactured by Kyoeisha Chemical Co., Ltd., epoxy equivalent 120 g/eq Thermosetting compound 2: Highly reactive epoxy compound, ADEKA Co., Ltd. Co., Ltd., "EP-3300S", epoxy equivalent 165 g/eq Thermosetting agent 1: Trimethylolpropane tris(3-mercaptopropionate), manufactured by SC Organic Chemicals Co., Ltd., "TMMP" Thermosetting agent 2 : Dipentaerythritol hexa(3-mercaptopropionate), SC Organic Chemical Co., Ltd., "DPMP" Latent epoxy thermosetting agent 1: T&K TOKA Co., Ltd., "FUJICURE 7000" Preparation method of flux 1: Fill a three-necked flask 160 g of acetone and 32 g of glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto, and dissolved at room temperature to a homogeneous state. Thereafter, 26 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and stirred at room temperature for 2 hours after completion of the dropwise addition. The precipitated white crystals were fractionated by filtration, washed with acetone, and vacuum-dried to obtain flux 1 . The average particle size was measured for arbitrary 50 particles using a scanning electron microscope (manufactured by Hitachi, Ltd., "S-4300SEN"), and the average value was calculated. In addition, the melting point is an endothermic peak measured using DSC (manufactured by Seiko Instruments, "DSC6200"). Preparation method of flux 2: The white crystal obtained by the same method as flux 1 was pulverized with a mortar until the average particle size became 10 μm, and flux 2 was obtained. Preparation method of flux 3: White crystals obtained by the same method as flux 1 were pulverized with a mortar until the average particle diameter became 1 μm, and flux 3 was obtained. Preparation method of flux 4: The white crystals obtained by the same method as flux 1 were crushed with a mortar until the average particle diameter became 0.05 μm, and flux 4 was obtained. Preparation method of flux 5: 160 g of acetone and 31 g of cyclohexanecarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a three-necked flask, and dissolved at room temperature to a uniform state. Thereafter, 24 g of cyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 hours after completion of the dropwise addition. The precipitated white crystals were fractionated by filtration, washed with acetone, and vacuum-dried. Thereafter, it was pulverized with a mortar until the average particle diameter became 10 μm, and flux 5 was obtained. Preparation method of flux 6: Add 160 g of acetone and 35 g of adipic acid (manufactured by Wako Pure Chemical Industries, Ltd.) into a three-necked flask, and dissolve them until they are uniform at room temperature. Thereafter, 26 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and stirred at room temperature for 2 hours after completion of the dropwise addition. The precipitated white crystals were fractionated by filtration, washed with acetone, and vacuum-dried. Thereafter, it was pulverized with a mortar until the average particle diameter became 10 μm, and flux 6 was obtained. Preparation method of flux 7: In a three-necked flask, add 26.8 g of triethanolamine to 12.6 g of citric acid monohydrate, and dissolve the citric acid while stirring in an oil bath at 120°C. The obtained triethanolamine citrate (flux 7) was liquid at 25°C. The production method of flux 8: Add 37.25 g of triethanolamine to 35.0 g of terephthalic acid in a three-neck flask, and dissolve the glutaric acid while stirring in an oil bath at 120°C. The obtained triethanolamine glutarate (flux 8) was semi-solid at 25°C. Furthermore, regarding the flux that is solid at 25°C, in the state of a single flux before mixing with conductive particles and a thermosetting component, and in a conductive material after mixing with conductive particles and a thermosetting component In the state of the flux, the average particle size of the flux is the same. Solder particle 1 (SnBi solder particle, melting point 139°C, manufactured by Mitsui Kinzoku Co., Ltd., "DS-10", average particle size (median diameter: 12 μm)) Solder particle 2 (SAC solder particle, melting point 217°C, manufactured by Mitsui Kinzoku Corporation , "DS-10", average particle diameter (median diameter 12 μm)) Preparation method of solder particle 3: Add 160 g of acetone and 32 g of glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) to a three-necked flask, and Dissolve to a homogeneous state at room temperature. Then, after adding 100 g of solder particles 1 and stirring for 15 minutes, 26 g of benzylamine (manufactured by Wako Pure Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, and stirred at room temperature for 2 hours after the dropwise addition was completed. The flux precipitates to the surface of the solder particles. Thereafter, the solder particles were washed once with acetone, and vacuum-dried to obtain solder particles 3 . (Examples 1-17 and Comparative Examples 1-2) (1) Preparation of anisotropic conductive paste The ingredients shown in the following Tables 1 and 2 are blended in the amounts shown in the following Tables 1 and 2 to obtain anisotropic conductive pastes. Anisotropic conductive paste. The flux was present in the obtained anisotropic conductive paste in the states shown in Tables 1 and 2. (2) Fabrication of connection structure (area array) As the first member to be connected, prepare the following semiconductor wafer, which is arranged in an area array at a pitch of 400 μm on the surface of the semiconductor wafer body (size 5×5 mm, thickness 0.4 mm). A copper electrode with a diameter of 250 μm and a thickness of 10 μm is configured. The number of copper electrodes is 100 pieces in total of 10 pieces×10 pieces per semiconductor wafer. As the second connection object member, prepare the following glass epoxy substrate. On the surface of the glass epoxy substrate body (dimensions 20×20 mm, thickness 1.2 mm, material FR-4), it is compared with the electrode of the first connection object member. A gold electrode was arranged so as to form the same pattern, and a solder resist film was formed in a region where the gold electrode was not arranged. The step difference between the surface of the copper electrode and the surface of the solder resist film was 15 μm, and the solder resist film protruded from the copper electrode. The anisotropic conductive paste immediately after production was coated on the upper surface of the glass epoxy substrate so as to have a thickness of 50 μm to form an anisotropic conductive paste layer. After standing at 23° C. and 50% RH for 2 hours, a semiconductor wafer was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes faced each other. The above weight of the semiconductor wafer is applied to the anisotropic conductive paste layer. From this state, the temperature of the anisotropic conductive paste layer reaches the melting point of the solder after 5 seconds after the start of heating (139°C in Examples 1-9, 12-17 and Comparative Examples 1 and 2, Example 10 , 11 is 217 ℃) way to heat. Furthermore, the temperature of the anisotropic conductive paste layer reaches the melting point of the solder + 21° C. (160° C. in Examples 1 to 9, 12 to 17 and Comparative Examples 1 and 2, and 160° C. in Example 10) 15 seconds after the start of heating , 11 at 238°C) and hold for 5 minutes to harden the anisotropic conductive paste layer to obtain a connection structure. No pressure was applied during heating. (Evaluation) (1) Viscosity The viscosity (η25) of the anisotropic conductive paste at 25°C was measured at 25°C and 5 rpm using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "TVE22L"). (2) Storage stability The anisotropic conductive paste was put into a syringe, and it stored at 23 degreeC for 24 hours. After storage, use an E-type viscometer ("TVE22L" manufactured by Toki Sangyo Co., Ltd.) to measure the viscosity (η25) of the anisotropic conductive paste at 25°C under the conditions of 25°C and 5 rpm. Storage stability was judged based on the following criteria. [Criteria for judging storage stability] ○○: The viscosity after storage is within ±25% of the viscosity before storage ○: Less than the standard of ○○, the viscosity after storage is within ±50% of the viscosity before storage△: Less than The standard of ○○ and ○, the viscosity after storage is within ±75% of the viscosity before storage ×: less than the standard of ○○, ○ and △ (3) The thickness of the solder part is obtained by cross-sectioning the obtained connection structure Observe and evaluate the thickness of the solder portion located between the upper and lower electrodes. (4) Arrangement accuracy of the solder on the electrodes 1 The following ratio X is evaluated. The ratio X is obtained by observing the first electrode and the second electrode along the lamination direction of the first electrode, the connection part, and the second electrode in the obtained connection structure. For the facing part of the electrodes, the ratio of the area of the solder part in the connection part to the area of 100% of the facing part of the first electrode and the second electrode. The placement accuracy of the solder on the electrodes is judged according to the following criteria1. [Criteria for judging the placement accuracy of solder on the electrode 1] ○○: Ratio X is 70% or more ○: Ratio X is 60% or more and less than 70% △: Ratio X is 50% or more and less than 60% ×: Ratio X is less than 50% (5) Arrangement accuracy of solder on electrodes 2 Evaluate the ratio Y as follows. The ratio Y is in the lamination direction of the first electrode, the connection part, and the second electrode in the connection structure obtained. When viewing the facing portion of the first electrode and the second electrode in the perpendicular direction, the ratio of the solder portion arranged in the connecting portion of the facing portion of the first electrode and the second electrode out of 100% of the solder portion in the connecting portion . The placement accuracy of the solder on the electrodes is judged according to the following criteria2. [Criteria for judging the placement accuracy of solder on the electrode 2] ○○: Ratio Y is 99% or more ○: Ratio Y is 90% or more and less than 99% △: Ratio Y is 70% or more and less than 90% ×: The ratio Y is less than 70% (6) Conduction reliability between the upper and lower electrodes For the obtained connection structures (n=15), the connection resistance of each connection part between the upper and lower electrodes was measured by the 4-terminal method. . Calculate the average value of the connection resistance. Furthermore, the connection resistance can be obtained by measuring the voltage when a predetermined current is passed based on the relationship of voltage=current×resistance. Conduction reliability was judged based on the following criteria. Among them, if there is one case in which n=15 is not conducted between the upper and lower electrodes, it is judged as "×". [Judgement criteria for conduction reliability] ○○: The average value of the connection resistance is 50 mΩ or less ○: The average value of the connection resistance exceeds 50 mΩ and is 70 mΩ or less △: The average value of the connection resistance exceeds 70 mΩ and is 100 mΩ or less ×: The average value of the connection resistance exceeds 100 mΩ or poor connection occurs. (7) Insulation reliability between electrodes adjacent in the lateral direction is measured at 85°C and humidity of 85% for the obtained connection structures (n=15 pieces). After standing in the environment for 100 hours, apply 15 V between electrodes adjacent in the lateral direction, and measure the resistance value at 25 points. Insulation reliability was judged based on the following criteria. Among them, it was judged as “×” when conduction between electrodes adjacent in the lateral direction occurred in one case among n=15. [Criteria for judging insulation reliability] ○○○: The average value of the connection resistance is 10 14 Ω or more ○○: The average value of the connection resistance is 10 8 Ω or more and less than 10 14 Ω ○: The average value of the connection resistance is 10 Ω 6 Ω or more and less than 10 8 Ω △: The average value of the connection resistance is 10 5 Ω or more and less than 10 6 Ω ×: The average value of the connection resistance is less than 10 5 Ω Details and results are shown in Table 1 below ,2. [Table 1]
Figure 106102877-A0304-0001
[Table 2]
Figure 106102877-A0304-0002

1‧‧‧連接構造體 1X‧‧‧連接構造體 2‧‧‧第1連接對象構件 2a‧‧‧第1電極 3‧‧‧第2連接對象構件 3a‧‧‧第2電極 4‧‧‧連接部 4X‧‧‧連接部 4A‧‧‧焊料部 4XA‧‧‧焊料部 4B‧‧‧硬化物部 4XB‧‧‧硬化物部 11‧‧‧導電材料 11A‧‧‧焊料粒子(導電性粒子) 11B‧‧‧熱硬化性成分 21‧‧‧導電性粒子(焊料粒子) 31‧‧‧導電性粒子 32‧‧‧基材粒子 33‧‧‧導電部(具有焊料之導電部) 33A‧‧‧第2導電部 33B‧‧‧焊料部 41‧‧‧導電性粒子 42‧‧‧焊料部1‧‧‧connection structure 1X‧‧‧connection structure 2‧‧‧The first connection object component 2a‧‧‧1st electrode 3‧‧‧The second connection target member 3a‧‧‧Second electrode 4‧‧‧connection part 4X‧‧‧Connection 4A‧‧‧Solder Department 4XA‧‧‧Solder Department 4B‧‧‧hardening department 4XB‧‧‧hardened parts department 11‧‧‧Conductive materials 11A‧‧‧Solder particles (conductive particles) 11B‧‧‧thermosetting components 21‧‧‧Conductive particles (solder particles) 31‧‧‧Conductive particles 32‧‧‧Substrate particles 33‧‧‧Conductive part (conductive part with solder) 33A‧‧‧The second conductive part 33B‧‧‧Solder Department 41‧‧‧Conductive particles 42‧‧‧Solder Department

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所獲得之連接構造體的剖視圖。 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而製造連接構造體之方法之一例之各步驟的剖視圖。 圖3係表示連接構造體之變化例之剖視圖。 圖4係表示可用於導電材料之導電性粒子之第1例的剖視圖。 圖5係表示可用於導電材料之導電性粒子之第2例的剖視圖。 圖6係表示可用於導電材料之導電性粒子之第3例的剖視圖。Fig. 1 is a cross-sectional view schematically showing a connection structure obtained by using a conductive material according to an embodiment of the present invention. 2( a ) to ( c ) are sectional views for explaining each step of an example of a method of manufacturing a connection structure using a conductive material according to an embodiment of the present invention. Fig. 3 is a cross-sectional view showing a modified example of the connection structure. Fig. 4 is a cross-sectional view showing a first example of conductive particles that can be used as a conductive material. Fig. 5 is a cross-sectional view showing a second example of conductive particles that can be used as a conductive material. Fig. 6 is a cross-sectional view showing a third example of conductive particles that can be used as a conductive material.

1‧‧‧連接構造體 1‧‧‧connection structure

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

2a‧‧‧第1電極 2a‧‧‧1st electrode

3‧‧‧第2連接對象構件 3‧‧‧The second connection target member

3a‧‧‧第2電極 3a‧‧‧Second electrode

4‧‧‧連接部 4‧‧‧connection part

4A‧‧‧焊料部 4A‧‧‧Solder Department

4B‧‧‧硬化物部 4B‧‧‧hardening department

Claims (15)

一種導電材料,其包含:於導電部之外表面部分具有焊料之複數個導電性粒子、熱硬化性成分、及助焊劑,上述助焊劑為具有羧基之有機化合物與具有胺基之有機化合物之鹽,上述具有胺基之有機化合物為芳香族胺化合物或脂肪族脂環式胺化合物,且於25℃之導電材料中,上述助焊劑係以固體存在。 A conductive material comprising: a plurality of conductive particles having solder on the outer surface of a conductive part, a thermosetting component, and a flux, the flux being a salt of an organic compound having a carboxyl group and an organic compound having an amine group , the above-mentioned organic compound having an amine group is an aromatic amine compound or an aliphatic alicyclic amine compound, and in the conductive material at 25° C., the above-mentioned soldering flux exists as a solid. 如請求項1之導電材料,其中於未與上述導電性粒子及上述熱硬化性成分混合之狀態下,上述助焊劑單劑於25℃下為固體。 The conductive material according to claim 1, wherein the solder flux single agent is solid at 25° C. without being mixed with the conductive particles and the thermosetting component. 如請求項1之導電材料,其中上述具有胺基之有機化合物為環己基胺、苄基胺、二苯甲基胺、2-甲基苄基胺、3-甲基苄基胺、4-第三丁基苄基胺或二級胺。 Such as the conductive material of claim item 1, wherein the above-mentioned organic compound having an amino group is cyclohexylamine, benzylamine, benzhydrylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-th Tributylbenzylamine or secondary amine. 如請求項2之導電材料,其中上述具有胺基之有機化合物為環己基胺、苄基胺、二苯甲基胺、2-甲基苄基胺、3-甲基苄基胺、4-第三丁基苄基胺或二級胺。 Such as the conductive material of claim 2, wherein the above-mentioned organic compound with an amino group is cyclohexylamine, benzylamine, benzhydrylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-th Tributylbenzylamine or secondary amine. 如請求項1至4中任一項之導電材料,其中上述助焊劑之平均粒徑為30μm以下。 The conductive material according to any one of claims 1 to 4, wherein the average particle diameter of the above-mentioned flux is 30 μm or less. 如請求項1至4中任一項之導電材料,其中上述助焊劑之平均粒徑相對於上述導電性粒子之平均粒徑的比為3以下。 The conductive material according to any one of claims 1 to 4, wherein the ratio of the average particle diameter of the flux to the average particle diameter of the conductive particles is 3 or less. 如請求項1至4中任一項之導電材料,其中上述助焊劑之熔點為上述導電性粒子中之焊料之熔點-50℃以上且上述導電性粒子中之焊料之熔點+50℃以下。 The conductive material according to any one of claims 1 to 4, wherein the melting point of the flux is above the melting point of the solder in the conductive particles - 50°C and below the melting point of the solder in the conductive particles + 50°C. 如請求項1至4中任一項之導電材料,其中上述導電性粒子為焊料粒子。 The conductive material according to any one of claims 1 to 4, wherein the above-mentioned conductive particles are solder particles. 如請求項1至4中任一項之導電材料,其中上述熱硬化性成分包含具有三
Figure 106102877-A0305-02-0059-1
骨架之熱硬化性化合物。
The conductive material according to any one of claims 1 to 4, wherein the above-mentioned thermosetting component contains three
Figure 106102877-A0305-02-0059-1
The thermosetting compound of the skeleton.
如請求項1至4中任一項之導電材料,其中於上述導電性粒子之表面上附著有上述助焊劑。 The conductive material according to any one of claims 1 to 4, wherein the flux is attached to the surface of the conductive particles. 如請求項1至4中任一項之導電材料,其中上述導電性粒子之平均粒徑為1μm以上且40μm以下。 The conductive material according to any one of claims 1 to 4, wherein the average particle diameter of the above-mentioned conductive particles is not less than 1 μm and not more than 40 μm. 如請求項1至4中任一項之導電材料,其中於導電材料100重量%中, 上述導電性粒子之含量為10重量%以上且90重量%以下。 The conductive material according to any one of claims 1 to 4, wherein in 100% by weight of the conductive material, Content of the said electroconductive particle is 10 weight% or more and 90 weight% or less. 如請求項1至4中任一項之導電材料,其為導電膏。 The conductive material according to any one of claims 1 to 4, which is a conductive paste. 一種連接構造體,其包括:表面具有至少一個第1電極之第1連接對象構件、表面具有至少一個第2電極之第2連接對象構件、及連接上述第1連接對象構件與上述第2連接對象構件之連接部,上述連接部之材料為如請求項1至13中任一項之導電材料,且上述第1電極與上述第2電極係藉由上述連接部中之焊料部而電性連接。 A connection structure comprising: a first connection object member having at least one first electrode on its surface, a second connection object member having at least one second electrode on its surface, and connecting the first connection object member and the second connection object The connection part of the component, the material of the connection part is the conductive material according to any one of claims 1 to 13, and the first electrode and the second electrode are electrically connected by the solder part in the connection part. 如請求項14之連接構造體,其中於沿上述第1電極與上述連接部及上述第2電極之積層方向觀察上述第1電極與上述第2電極之相對向部分時,上述第1電極與上述第2電極之相對向部分之面積100%中之50%以上配置有上述連接部中之焊料部。 The connection structure according to claim 14, wherein when the opposing portion of the first electrode and the second electrode is viewed along the lamination direction of the first electrode, the connection portion, and the second electrode, the first electrode and the above-mentioned More than 50% of 100% of the area of the facing portion of the second electrode is provided with the solder portion in the connection portion.
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018221587A1 (en) * 2017-06-01 2018-12-06 積水化学工業株式会社 Electroconductive material and connection structure
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004202518A (en) * 2002-12-24 2004-07-22 Nof Corp Flux composition for soldering, solder paste, and method for soldering
TW201241144A (en) * 2011-01-27 2012-10-16 Hitachi Chemical Co Ltd Conductive adhesive composition, connecting body and solar battery module and fabricating method thereof
TW201447922A (en) * 2009-10-16 2014-12-16 Dexerials Corp Light-reflective conductive particle, anisotropic conductive adhesive and light-emitting device
TW201546829A (en) * 2009-09-14 2015-12-16 Dexerials Corp Light-reflective anisotropic conductive adhesive and light-emitting device

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001219294A (en) * 1999-12-03 2001-08-14 Tdk Corp Thermosetting flux for soldering and soldering method
JP3888573B2 (en) * 2001-06-29 2007-03-07 富士電機ホールディングス株式会社 Solder composition
JP3769688B2 (en) 2003-02-05 2006-04-26 独立行政法人科学技術振興機構 Terminal connection method and semiconductor device mounting method
EP2768031B1 (en) * 2005-08-04 2021-02-17 Nichia Corporation Light-emitting device
US7838984B2 (en) 2006-08-25 2010-11-23 Sumitomo Bakelite Company, Ltd. Adhesive tape, connected structure and semiconductor package
JP2010221260A (en) * 2009-03-24 2010-10-07 Mitsubishi Materials Corp Solder powder and solder paste using the same
JP5671225B2 (en) * 2009-05-22 2015-02-18 積水化学工業株式会社 Conductive fine particles, anisotropic conductive material, and conductive connection structure
US9073153B2 (en) * 2010-02-09 2015-07-07 Nordson Corporation Flux and solder material and method of making same
JP5916376B2 (en) * 2011-09-13 2016-05-11 株式会社タムラ製作所 Adhesive composition and method for connecting solar cell and wiring board using the same
JP2013256584A (en) 2012-06-12 2013-12-26 Panasonic Corp Thermosetting resin composition, flux composition, and semiconductor apparatus using the same
JP2014063846A (en) * 2012-09-20 2014-04-10 Asahi Kasei E-Materials Corp Protective layer of metal surface and method for forming the same
JP6013118B2 (en) * 2012-09-28 2016-10-25 株式会社タムラ製作所 Insulating adhesive composition and circuit board
KR101686357B1 (en) * 2013-01-17 2016-12-13 세키스이가가쿠 고교가부시키가이샤 Curable composition for electronic component and connection structure
CN104822773B (en) * 2013-05-23 2017-09-22 积水化学工业株式会社 Conductive material and connection structural bodies
JP2015216026A (en) * 2014-05-10 2015-12-03 アルプス電気株式会社 Conductive paste and wiring board
WO2015174299A1 (en) * 2014-05-14 2015-11-19 積水化学工業株式会社 Conductive paste, production method for conductive paste, connection structure, and production method for connection structure
JP6391597B2 (en) * 2014-08-29 2018-09-19 古河電気工業株式会社 Conductive adhesive composition
CN104607826B (en) * 2014-12-09 2017-02-01 华南理工大学 Cleaning-free solid-state scaling powder for aluminum low-temperature soldering and preparing method
JP6734141B2 (en) * 2015-08-19 2020-08-05 積水化学工業株式会社 Conductive material and connection structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004202518A (en) * 2002-12-24 2004-07-22 Nof Corp Flux composition for soldering, solder paste, and method for soldering
TW201546829A (en) * 2009-09-14 2015-12-16 Dexerials Corp Light-reflective anisotropic conductive adhesive and light-emitting device
TW201447922A (en) * 2009-10-16 2014-12-16 Dexerials Corp Light-reflective conductive particle, anisotropic conductive adhesive and light-emitting device
TW201241144A (en) * 2011-01-27 2012-10-16 Hitachi Chemical Co Ltd Conductive adhesive composition, connecting body and solar battery module and fabricating method thereof

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