WO2020054288A1 - Conductive material and connection structure - Google Patents

Conductive material and connection structure Download PDF

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Publication number
WO2020054288A1
WO2020054288A1 PCT/JP2019/031425 JP2019031425W WO2020054288A1 WO 2020054288 A1 WO2020054288 A1 WO 2020054288A1 JP 2019031425 W JP2019031425 W JP 2019031425W WO 2020054288 A1 WO2020054288 A1 WO 2020054288A1
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WO
WIPO (PCT)
Prior art keywords
conductive
compound
solder
electrode
conductive material
Prior art date
Application number
PCT/JP2019/031425
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French (fr)
Japanese (ja)
Inventor
士輝 宋
将大 伊藤
周治郎 定永
賢次 大橋
Original Assignee
積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2020503064A priority Critical patent/JP7280864B2/en
Publication of WO2020054288A1 publication Critical patent/WO2020054288A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin

Definitions

  • the present invention relates to a conductive material containing conductive particles having solder on the outer surface of the conductive part. Further, the present invention relates to a connection structure using the conductive material.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder.
  • the anisotropic conductive material is used to obtain various connection structures.
  • connection using the anisotropic conductive material for example, connection between a flexible printed board and a glass substrate (FOG (Film @ on @ Glass)), connection between a semiconductor chip and a flexible printed board (COF (Chip @ on @ Film)), semiconductor The connection between the chip and the glass substrate (COG (Chip @ on @ Glass)), the connection between the flexible printed board and the glass epoxy substrate (FOB (Film @ on @ Board)), and the like can be given.
  • the anisotropic conductive material for example, an anisotropic conductive material containing conductive particles is placed on the glass epoxy board. I do.
  • the flexible printed circuit boards are laminated and heated and pressed. Thereby, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
  • Patent Document 1 As an example of the anisotropic conductive material, Patent Document 1 listed below discloses (A) conductive particles containing a metal having a melting point of 220 ° C. or less, (B) a thermosetting resin, and (C) flux activity. And a conductive adhesive composition comprising the agent. In the conductive adhesive composition, the flux activator (C) has an average particle size of 10 ⁇ m or less.
  • the flux includes a solid flux that is solid when blended with a conductive material, and a liquid flux that is liquid when blended with a conductive material.
  • the liquid flux when only the liquid flux is used, when the content of the liquid flux in the conductive material is increased, the flux reacts with the thermosetting compound in the conductive material, and the storage stability of the conductive material is reduced. There is. Further, the liquid flux can be highly filled in the conductive material, and the solder can be efficiently aggregated on the electrode. As a result, when only a liquid flux is used as the conductive material, it is difficult to increase the storage stability of the conductive material, although it is possible to highly fill the liquid flux and increase the cohesiveness of the solder.
  • An object of the present invention is to improve the storage stability of a conductive material effectively, to fill a conductive material with a high flux, and to effectively increase the cohesiveness of solder at the time of conductive connection. It is to provide a conductive material which can be used. Another object of the present invention is to provide a connection structure using the above conductive material.
  • a conductive material including a solid salt with a second compound having an amino group, and a liquid compound which is a reaction product of a third compound having a carboxyl group and a fourth compound having an amino group.
  • a weight ratio of the content of the solid salt to the content of the liquid compound is 2 or more and 20 or less.
  • the first compound and the third compound are the same compound.
  • the second compound and the fourth compound are the same compound.
  • the average particle diameter of the solid salt is 0.01 ⁇ m or more and 10 ⁇ m or less.
  • the thermosetting component includes a thermosetting compound, and the content of the flux is 1 part by weight or more based on 100 parts by weight of the thermosetting compound. 50 parts by weight or less.
  • the content of the flux is 0.05% by weight or more and 20% by weight or less in 100% by weight of the conductive material.
  • the conductive particles have an average particle size of 0.01 ⁇ m or more and 50 ⁇ m or less.
  • the conductive material is a conductive paste.
  • a first connection target member having a first electrode on a surface
  • a second connection target member having a second electrode on a surface
  • the first connection target member A connection portion connecting the second connection target member, wherein the material of the connection portion is the conductive material described above, and the first electrode and the second electrode are formed of the conductive material.
  • a connection structure is provided that is electrically connected by the particles.
  • the conductive material according to the present invention includes a plurality of conductive particles having solder on the outer surface of the conductive part, a thermosetting component, and a flux.
  • the flux is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a second compound having an amino group.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to one embodiment of the present invention.
  • FIGS. 2A to 2C are cross-sectional views illustrating steps of an example of a method for 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 modification of the connection structure.
  • FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used for a conductive material.
  • FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used for a conductive material.
  • FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for a conductive material.
  • the conductive material according to the present invention includes a plurality of conductive particles having solder on the outer surface of the conductive portion, a thermosetting component, and a flux.
  • the flux is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a second compound having an amino group.
  • the storage stability of the conductive material can be effectively improved, the conductive material can be filled with a high flux, and the conductive connection can be further improved.
  • the cohesiveness of the solder at the time can be effectively increased.
  • the electrodes when the electrodes are electrically connected, a plurality of conductive particles can be efficiently arranged on the electrodes (lines) and should be connected.
  • the solder can be efficiently aggregated between the upper and lower electrodes.
  • electrical connection between horizontally adjacent electrodes that should not be connected can be prevented, and insulation reliability can be improved.
  • the flux is mainly incorporated into the conductive material in order to remove the oxide present on the surface of the solder and the surface of the electrode in the conductive particles and to prevent the formation of the oxide.
  • the conductive material can be highly filled with the flux.
  • the solid flux and the liquid flux are used in combination, it is easier to highly fill the conductive material with the flux than when the solid flux is used alone. For this reason, in the present invention, oxides present on the surface of the solder, the surface of the electrodes, and the like in the conductive particles can be effectively removed, and the formation of the oxides can be effectively prevented.
  • the flux can be highly filled in the conductive material, the cohesiveness of the solder at the time of conductive connection can be effectively improved.
  • the solid flux and the liquid flux are used in combination, the reaction between the thermosetting compound and the flux in the conductive material can be effectively suppressed. As a result, the storage stability of the conductive material can be effectively increased.
  • the flux can be filled in the conductive material at a higher level than in the case where only the solid flux is used. Sex can be effectively improved.
  • the solid flux and the liquid flux are used in combination, the storage stability of the conductive material can be effectively improved as compared with the case where only the liquid flux is used.
  • the present invention it is possible to prevent displacement between electrodes.
  • the electrode of the first connection target member and the electrode of the second connection target member are connected. Even in a state where the alignment is shifted, the electrode can be connected by correcting the shift (self-alignment effect).
  • the conductive material is preferably liquid at 25 ° C. It is preferred that The conductive material is preferably a conductive paste at 25 ° C.
  • the viscosity ( ⁇ 25) at 25 ° C. of the conductive material is preferably 20 Pa from the viewpoint of further filling the conductive material with the flux and further effectively increasing the cohesiveness of the solder during the conductive connection.
  • -S or more more preferably 30 Pa-s or more, preferably 500 Pa-s or less, more preferably 300 Pa-s or less.
  • the viscosity ( ⁇ 25) can be appropriately adjusted depending on the types and amounts of the components.
  • the viscosity ( ⁇ 25) can be measured, for example, using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
  • E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
  • the conductive material can be used as a conductive paste and a conductive film.
  • the conductive paste is preferably an anisotropic conductive paste, and the conductive film is preferably an anisotropic conductive film.
  • the conductive material is preferably a conductive paste from the viewpoint of further filling the conductive material with the flux and more effectively increasing the cohesiveness of the solder during the conductive connection.
  • the conductive material is suitably used for electrical connection of electrodes.
  • the conductive material is preferably a circuit connecting material.
  • (meth) acryl means one or both of “acryl” and “methacryl”
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”.
  • the conductive material includes conductive particles.
  • the conductive particles electrically connect the electrodes of the connection target member.
  • the conductive particles have solder on the outer surface of the conductive part.
  • the conductive particles may be solder particles formed by solder.
  • the solder particles have solder on the outer surface of the conductive part. In the solder particles, both the central portion and the outer surface portion of the conductive portion are formed of solder.
  • the solder particles are particles in which both the central portion and the conductive outer surface are solder.
  • the conductive particles may have base particles and a conductive part disposed on the surface of the base particles. In this case, the conductive particles have solder on the outer surface of the conductive part.
  • the conductive particles have solder on the outer surface of the conductive part.
  • the base particles may be solder particles formed of solder.
  • the conductive particles may be solder particles in which both the base particles and the outer surface of the conductive portion are solder.
  • the conductive particles are preferably solder particles formed by solder.
  • FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used for a conductive material.
  • the conductive particles 21 shown in FIG. 4 are solder particles.
  • the conductive particles 21 are entirely formed of solder.
  • the conductive particles 21 do not have the base particles in the core and are not core-shell particles.
  • both the central part and the outer surface part of the conductive part are formed by solder.
  • FIG. 5 is a cross-sectional view showing a second example of the conductive particles usable for the conductive material.
  • the conductive particles 31 shown in FIG. 5 include base particles 32 and a conductive part 33 disposed on the surface of the base particles 32.
  • the conductive portion 33 covers the surface of the base particles 32.
  • the conductive particles 31 are coated particles in which the surfaces of the base particles 32 are coated with the conductive portions 33.
  • the conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion).
  • the conductive particles 31 include a second conductive portion 33A between the base particles 32 and the solder portion 33B. Accordingly, the conductive particles 31 include the base particles 32, the second conductive portions 33A disposed on the surface of the base particles 32, and the solder portions 33B disposed on the outer surface of the second conductive portions 33A.
  • FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for a conductive material.
  • the conductive part 33 of the conductive particle 31 in FIG. 5 has a two-layer structure.
  • the conductive particles 41 shown in FIG. 6 have a solder part 42 as a single-layer conductive part.
  • the conductive particles 41 include the base particles 32 and the solder portions 42 arranged on the surface of the base particles 32.
  • the base particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the base particles are preferably base particles excluding metal particles, more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the base particles may be base particles excluding inorganic particles.
  • the base particles may be core-shell particles including a core and a shell disposed on a surface of the core.
  • the core may be an organic core, and the shell may be an inorganic shell.
  • the base particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles. By using these preferred base particles, the effects of the present invention are more effectively exhibited, and conductive particles more suitable for electrical connection between electrodes can be obtained.
  • the conductive particles are arranged between the electrodes, and then the conductive particles are compressed by pressing.
  • the base particles are resin particles or organic-inorganic hybrid particles
  • the conductive particles are likely to be deformed at the time of the press bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction reliability between the electrodes is further improved.
  • the material of the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polyalkylene terephthalate and polycarbonate , Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene oxide, polyacetal, Polyimide, polyamide imide, polyetheretherketone, polyether Terusuruhon, divinylbenzene polymers, divinylbenzene copolymers, and poly
  • the material of the resin particles is an ethylenically unsaturated group. Is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of
  • the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer. And a crosslinkable monomer.
  • non-crosslinkable monomer examples include styrene-based monomers such as styrene and ⁇ -methylstyrene; carboxyl-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, and
  • Unsaturated hydrocarbons; and halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene.
  • crosslinkable monomer examples include tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, and dipentane.
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method.
  • the method include a method of performing suspension polymerization in the presence of a radical polymerization initiator, and a method of performing polymerization by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • the base particles are inorganic particles or organic-inorganic hybrid particles other than metal particles
  • examples of the inorganic substance for forming the base particles include silica, alumina, barium titanate, zirconia, and carbon black. .
  • the inorganic substance is not a metal.
  • the particles formed of the silica are not particularly limited. For example, after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, baking is optionally performed. Particles obtained by performing the method are exemplified.
  • examples of the organic-inorganic hybrid particles include, for example, organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core.
  • the core is an organic core.
  • the shell is an inorganic shell.
  • the base particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core. .
  • Examples of the material of the organic core include the above-described materials of the resin particles.
  • Examples of the material of the inorganic shell include the inorganic substances described above as the material of the base particles.
  • the material of the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed by forming a metal alkoxide into a shell by a sol-gel method on the surface of the core, and then firing the shell.
  • the metal alkoxide is preferably a silane alkoxide. It is preferable that the inorganic shell is formed of a silane alkoxide.
  • the base particles are metal particles
  • examples of the metal as a material of the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the base particles are preferably not metal particles.
  • the average particle diameter of the base particles is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, and still more preferably 3 ⁇ m or more, preferably Is 100 ⁇ m or less, more preferably 60 ⁇ m or less, further preferably 50 ⁇ m or less, particularly preferably 40 ⁇ m or less.
  • the average particle diameter of the base particles is equal to or larger than the lower limit, the contact area between the conductive particles and the electrodes is increased, so that the reliability of conduction between the electrodes is further increased, and the connection via the conductive particles is performed. The connection resistance between the electrodes can be reduced more effectively.
  • the conductive portion is formed on the surface of the base material particles, it is difficult to aggregate, and it is difficult to form the aggregated conductive particles.
  • the average particle diameter of the base particles is equal to or less than the upper limit, the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes connected via the conductive particles is more effectively reduced. Can be.
  • the average particle diameter of the base particles is 0.005 ⁇ m or more and 40 ⁇ m or less.
  • the average particle diameter of the base particles is in the range of 0.005 ⁇ m or more and 40 ⁇ m or less, the distance between the electrodes can be reduced, and even if the thickness of the conductive portion is increased, the small conductive particles Can be obtained.
  • the particle diameter of the base particles indicates a diameter when the base particles are truly spherical, and indicates a maximum diameter when the base particles are not true spherical.
  • the average particle diameter of the base particles is preferably a number average particle diameter.
  • the average particle diameter of the base particles is determined using a particle size distribution measuring device or the like.
  • the average particle diameter of the base particles is preferably obtained by observing 50 arbitrary base particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the average particle diameter of the base particles in the conductive particles, for example, the measurement can be performed as follows.
  • the resin is added to “Technobit 4000” manufactured by Kulzer Co., Ltd. so that the content of the conductive particles becomes 30% by weight, and dispersed to prepare an embedded resin for conductive particle inspection.
  • the cross section of the conductive particles is cut out using an ion milling apparatus (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the resin for inspection.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • FE-SEM field emission scanning electron microscope
  • the method for forming the conductive portion on the surface of the base particles and the method for forming the solder portion on the surface of the base particles or the surface of the second conductive portion are not particularly limited.
  • a method of forming the conductive portion and the solder portion for example, a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption, And a method of coating the surface of the base particles with a metal powder or a paste containing the metal powder and a binder.
  • the method of forming the conductive portion and the solder portion is preferably a method using electroless plating, electroplating, or physical collision.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
  • a sheeter composer manufactured by Tokuju Kosakusho is used.
  • the melting point of the base particles is preferably higher than the melting points of the conductive part and the solder part.
  • the melting point of the base particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, further preferably higher than 400 ° C, particularly preferably higher than 450 ° C. Note that the melting point of the base particles may be lower than 400 ° C.
  • the melting point of the base particles may be 160 ° C. or lower.
  • the softening point of the base particles is preferably 260 ° C. or higher. The softening point of the base particles may be less than 260 ° C.
  • the conductive particles may have a single-layer solder portion.
  • the conductive particles may have a plurality of layers of conductive portions (solder portions, second conductive portions). That is, in the conductive particles, two or more conductive portions may be laminated. When the conductive portion has two or more layers, it is preferable that the conductive particles have solder on an outer surface portion of the conductive portion.
  • the solder is preferably a metal having a melting point of 450 ° C. or lower (a low melting point metal).
  • the solder part is preferably a metal layer having a melting point of 450 ° C. or lower (low-melting metal layer).
  • the low melting point metal layer is a layer containing a low melting point metal.
  • the solder and the solder particles in the conductive particles are preferably metal particles having a melting point of 450 ° C. or lower (low-melting metal particles).
  • the low melting point metal particles are particles containing a low melting point metal.
  • the low-melting-point metal refers to a metal having a melting point of 450 ° C. or less.
  • the melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
  • the melting point of the low melting point metal and the melting point of the solder particles can be determined by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimeter
  • EXSTAR DSC7020 manufactured by SII and the like can be mentioned.
  • the solder in the conductive particles preferably contains tin.
  • the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably. Is 70% by weight or more, particularly preferably 90% by weight or more.
  • the tin content was measured using a high-frequency inductively coupled plasma emission spectrometer ("ICP-AES” manufactured by Horiba, Ltd.) or an X-ray fluorescence analyzer ("EDX-800HS” manufactured by Shimadzu, Ltd.). Can be measured.
  • ICP-AES high-frequency inductively coupled plasma emission spectrometer
  • EDX-800HS X-ray fluorescence analyzer
  • the solder is melted and joined to the electrodes, and the solder conducts between the electrodes. For example, since the solder and the electrode are likely to make surface contact, not point contact, the connection resistance is reduced.
  • the use of conductive particles having solder on the outer surface of the conductive portion increases the bonding strength between the solder and the electrode, so that peeling of the solder and the electrode is more unlikely to occur, and the conduction reliability is effectively improved. Become higher.
  • the solder portion and the low-melting-point metal forming the solder are not particularly limited.
  • the low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy.
  • the low melting point metal is preferably tin, a tin-silver alloy, a tin-silver-copper alloy, a tin-bismuth alloy, or a tin-indium alloy because of its excellent wettability to the electrode. More preferably, it is a tin-bismuth alloy or a tin-indium alloy.
  • the material forming the solder is preferably a filler material having a liquidus of 450 ° C. or less based on JIS Z3001: welding terminology.
  • the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium, and the like.
  • the solder in the conductive particles may be nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium. , Cobalt, bismuth, manganese, chromium, molybdenum, palladium and the like. From the viewpoint of further increasing the bonding strength between the solder and the electrode in the solder portion or the conductive particles, the solder in the conductive particles preferably contains nickel, copper, antimony, aluminum, or zinc.
  • the content of these metals for increasing the bonding strength is preferably 0% in 100% by weight of the solder in the conductive particles. 0.0001% by weight or more, preferably 1% by weight or less.
  • the melting point of the second conductive part is higher than the melting point of the solder part.
  • the melting point of the second conductive portion is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, still more preferably higher than 450 ° C, particularly preferably higher than 500 ° C, Most preferably above 600 ° C. Since the above-mentioned solder part has a low melting point, it melts at the time of conductive connection. It is preferable that the second conductive portion does not melt at the time of conductive connection.
  • the conductive particles are preferably used by melting solder, preferably used by melting the solder portion, used without melting the solder portion and without melting the second conductive portion. Preferably. Since the melting point of the second conductive part is higher than the melting point of the solder part, only the solder part can be melted without melting the second conductive part at the time of conductive connection.
  • the absolute value of the difference between the melting point of the solder part and the melting point of the second conductive part exceeds 0 ° C., preferably 5 ° C. or more, more preferably 10 ° C. or more, still more preferably 30 ° C. or more, and particularly preferably. Is at least 50 ° C, most preferably at least 100 ° C.
  • the second conductive portion preferably contains a 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, cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. One of the above metals may be used alone, or two or more thereof may be used in combination.
  • the second conductive portion is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer, a gold layer or a copper layer, and further preferably a copper layer.
  • the conductive particles preferably have a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably have a nickel layer, a gold layer or a copper layer, and further preferably have a copper layer.
  • the thickness of the solder part is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 0.3 ⁇ m or less.
  • the thickness of the solder portion is equal to or more than the lower limit and equal to or less than the upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. I do.
  • the average particle diameter of the conductive particles is preferably 0.01 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less. And more preferably 50 ⁇ m or less, particularly preferably 40 ⁇ m or less.
  • the average particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the solder in the conductive particles can be disposed between the electrodes. It is easy to arrange many, and the conduction reliability is further improved.
  • the average particle diameter of the conductive particles is more preferably a number average particle diameter.
  • the average particle size of the conductive particles can be determined, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing a laser diffraction particle size distribution measurement.
  • the CV value of the particle size of the conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less.
  • the CV value of the particle diameter is equal to or more than the lower limit and equal to or less than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrode.
  • the CV value of the particle size of the conductive particles may be less than 5%.
  • the CV value (coefficient of variation) of the particle diameter of the conductive particles can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of the particle size of the conductive particles Dn: Average value of the particle size of the conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the shape of the conductive particles may be spherical, may be other than spherical, or may be flat or the like.
  • the content of the conductive particles is preferably 1% by weight or more, more preferably 2% by weight or more, further preferably 10% by weight or more, particularly preferably 20% by weight or more, and most preferably. It is at least 30% by weight, preferably at most 80% by weight, more preferably at most 60% by weight, further preferably at most 50% by weight.
  • the conductive particles can be more efficiently arranged on the electrodes, and more conductive particles can be arranged between the electrodes. It is easy and the conduction reliability is further improved. From the viewpoint of further improving conduction reliability, it is preferable that the content of the conductive particles is large.
  • the conductive material according to the present invention contains a thermosetting component.
  • the thermosetting component preferably contains a thermosetting compound.
  • the conductive material may include a thermosetting compound and a thermosetting agent as thermosetting components.
  • the conductive material preferably contains a thermosetting compound and a thermosetting agent as thermosetting components.
  • the conductive material preferably contains a curing accelerator as a thermosetting component.
  • thermosetting component thermosetting compound
  • the conductive material according to the present invention preferably contains a thermosetting compound.
  • the thermosetting compound is a compound that can be cured by heating.
  • the thermosetting compound is not particularly limited. Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. From the viewpoint of further improving the curability and viscosity of the conductive material and further enhancing the conduction reliability, an epoxy compound or an episulfide compound is preferable, and an epoxy compound is more preferable.
  • the conductive material preferably contains an epoxy compound. Only one kind of the thermosetting compound may be used, or two or more kinds thereof may be used in combination.
  • the epoxy compound is a compound having at least one epoxy group.
  • examples of the epoxy compound include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolak epoxy compound, a biphenyl epoxy compound, a biphenyl novolak epoxy compound, a biphenol epoxy compound, and a naphthalene epoxy compound.
  • An epoxy compound and an epoxy compound having a triazine nucleus in a skeleton are exemplified.
  • One of the above epoxy compounds may be used alone, or two or more thereof may be used in combination.
  • the epoxy compound is liquid or solid at normal temperature (23 ° C.).
  • the melting temperature of the epoxy compound is preferably equal to or lower than the melting point of the solder.
  • thermosetting component preferably contains an epoxy compound, and the thermosetting compound is an epoxy compound. It is preferred to include.
  • thermosetting compound preferably includes a thermosetting compound having a polyether skeleton.
  • thermosetting compound having a polyether skeleton examples include a compound having a glycidyl ether group at both terminals of an alkyl chain having 3 to 12 carbon atoms, and a polyether skeleton having a polyether skeleton having 2 to 4 carbon atoms.
  • examples include polyether type epoxy compounds having a structural unit in which 2 to 10 are continuously bonded.
  • thermosetting compound preferably contains a thermosetting compound having an isocyanuric skeleton.
  • thermosetting compound having an isocyanuric skeleton examples include a triisocyanurate type epoxy compound, and a TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, manufactured by Nissan Chemical Industries, Ltd.). TEPIC-PAS, TEPIC-VL, and TEPIC-UC).
  • thermosetting compound preferably has high heat resistance, and is more preferably a novolak-type epoxy compound. Novolak-type epoxy compounds have relatively high heat resistance.
  • the content of the thermosetting compound is preferably 5% by weight or more, more preferably 8% by weight or more, further preferably 10% by weight or more, and preferably 99% by weight or less, It is more preferably at most 90% by weight, further preferably at most 80% by weight, particularly preferably at most 70% by weight.
  • the content of the thermosetting compound is not less than the lower limit and not more than the upper limit, the solder in the conductive particles is more efficiently arranged on the electrodes, and the insulation reliability between the electrodes is more effectively improved. And the reliability of conduction between the electrodes can be more effectively increased. From the viewpoint of more effectively improving the impact resistance, the content of the thermosetting compound is preferably higher.
  • the content of the epoxy compound is preferably 5% by weight or more, more preferably 8% by weight or more, further preferably 10% by weight or more, and preferably 99% by weight or less, more preferably Is at most 90% by weight, more preferably at most 80% by weight, particularly preferably at most 70% by weight.
  • the content of the epoxy compound is equal to or more than the lower limit and equal to or less than the upper limit, the solder in the conductive particles is more efficiently arranged on the electrodes, and the insulation reliability between the electrodes is more effectively increased. And the reliability of conduction between the electrodes can be more effectively improved. From the viewpoint of further improving the impact resistance, the content of the epoxy compound is preferably higher.
  • thermosetting component thermosetting agent
  • the conductive material preferably contains a thermosetting agent.
  • the conductive material preferably contains a thermosetting agent together with the thermosetting compound.
  • the thermosetting agent thermosets the thermosetting compound.
  • the thermosetting agent is not particularly limited. Examples of the thermal curing agent include an imidazole curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a thermal cationic curing agent, and a thermal radical generator.
  • the thermosetting agent may be used alone or in combination of two or more.
  • the thermal curing agent is preferably an imidazole curing agent, a thiol curing agent, or an amine curing agent.
  • the thermosetting agent is a latent curing agent.
  • the latent curing agent is a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent.
  • the thermosetting agent may be coated with a polymer material such as a polyurethane resin or a polyester resin.
  • the imidazole curing agent is not particularly limited.
  • Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6 -[2'-Methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2-paratolyl-4-methyl-5 -Hydroxymethylimidazole, 2-methatoryl-4-
  • the thiol curing agent is not particularly limited.
  • Examples of the thiol curing agent include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.
  • the amine curing agent is not particularly limited.
  • examples of the amine curing agent include hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane, bis (4 -Aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone and the like.
  • the acid anhydride curing agent is not particularly limited, and any acid anhydride used as a curing agent for a thermosetting compound such as an epoxy compound can be widely used.
  • the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylbutenyltetrahydrophthalic anhydride.
  • Bifunctional such as phthalic anhydride, maleic anhydride, nadic anhydride, methylnadic anhydride, glutaric anhydride, succinic anhydride, glycerin bis trimellitic anhydride monoacetate, and ethylene glycol bis trimellitic anhydride Acid anhydride curing agent, trifunctional acid anhydride curing agent such as trimellitic anhydride, and pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, and polyazelain anhydride Acid anhydride of 4 or more functional groups Curing agents.
  • the thermal cation initiator is not particularly limited.
  • Examples of the thermal cation initiator include an iodonium-based cation curing agent, an oxonium-based cation curing agent, and a sulfonium-based cation curing agent.
  • Examples of the above-mentioned iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate.
  • Examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate.
  • Examples of the sulfonium-based cationic curing agent include tri-p-tolylsulfonium hexafluorophosphate.
  • the thermal radical generator is not particularly limited.
  • Examples of the thermal radical generator include an azo compound and an organic peroxide.
  • Examples of the azo compound include azobisisobutyronitrile (AIBN).
  • Examples of the organic peroxide include di-tert-butyl peroxide and methyl ethyl ketone peroxide.
  • the reaction initiation temperature of the thermosetting agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 150 ° C. or lower.
  • the temperature is particularly preferably 140 ° C. or lower.
  • the reaction start temperature of the thermosetting agent Is particularly preferably from 80 ° C to 140 ° C.
  • the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder particles, more preferably higher by 5 ° C. or more. Preferably, the temperature is higher by 10 ° C. or more.
  • the reaction start temperature of the thermosetting agent means a temperature at which a heat generation peak starts to rise in DSC.
  • the content of the 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, preferably at most 200 parts by weight, more preferably at most 200 parts by weight, based on 100 parts by weight of the thermosetting compound. 100 parts by weight or less, more preferably 75 parts by weight or less.
  • the content of the thermosetting agent is equal to or more than the above lower limit, it is easy to sufficiently cure the conductive material.
  • the content of the thermosetting agent is equal to or less than the above upper limit, the surplus thermosetting agent not involved in the curing after the curing hardly remains, and the heat resistance of the cured product is further increased.
  • the conductive material may include a curing accelerator.
  • the curing accelerator is not particularly limited.
  • the curing accelerator preferably acts as a curing catalyst in the reaction between the thermosetting compound and the thermosetting agent.
  • the curing accelerator preferably acts as a curing catalyst in the reaction with the thermosetting compound. Only one kind of the curing accelerator may be used, or two or more kinds may be used in combination.
  • Examples of the curing accelerator include phosphonium salts, tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, amine complex compounds, and phosphonium ylides.
  • an imidazole compound an isocyanurate of the imidazole compound, dicyandiamide, a derivative of dicyandiamide, a melamine compound, a derivative of a melamine compound, diaminomaleonitrile, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine , Bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide and other amine compounds, 1,8-diazabicyclo [5,4,0] undecene-7,3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, boron trifluoride, boron trifluoride-amine complex compound, and triphenylphosphine, tricyclohexylphosphine, tributylphosphine Emissions and organophosphorus compounds such as
  • the phosphonium salt is not particularly limited.
  • Examples of the phosphonium salt include tetra-n-butylphosphonium bromide, tetra-n-butyl phosphonium OO diethyldithiophosphoric acid, methyltributyl-phosphonium dimethyl phosphate, tetra-n-butyl phosphonium benzotriazole, tetra-n-butyl phosphonium tetrafluoroborate, and tetra-n-butyl And phosphonium tetraphenyl borate.
  • the curing accelerator is an imidazole compound. And more preferably a boron trifluoride-amine complex compound.
  • the content of the curing accelerator is appropriately selected so that the thermosetting compound cures favorably.
  • the content of the curing accelerator with respect to 100 parts by weight of the thermosetting compound is preferably 0.5 parts by weight or more, more preferably 0.8 parts by weight or more, preferably 10 parts by weight or less, more preferably 8 parts by weight or less. Not more than parts by weight.
  • the thermosetting compound can be favorably cured.
  • the content of the curing accelerator is not less than the lower limit and not more than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the upper and lower electrodes to be connected can be arranged. Can be more effectively improved.
  • the conductive material according to the present invention includes a flux. By using the flux, the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
  • the flux includes a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a third compound having an amino group. And a liquid compound which is a reaction product with the compound of No. 4.
  • the solid salt of the first compound having a carboxyl group and the second compound having an amino group is a solid at 25 ° C.
  • the liquid compound which is a reaction product of the third compound having a carboxyl group and the fourth compound having an amino group is liquid at 25 ° C.
  • the solid salt of the first compound having a carboxyl group and the second compound having an amino group is preferably a solid in a conductive material at 25 ° C.
  • the liquid compound that is a reaction product of the third compound having a carboxyl group and the fourth compound having an amino group is preferably a liquid in a conductive material at 25 ° C.
  • the first compound and the third compound have an effect of cleaning the surface of the metal. It is preferable that the second compound has an action of neutralizing the first compound. It is preferable that the fourth compound has an action of neutralizing the third compound. It is preferable that the second compound and the fourth compound have an action of neutralizing the first compound or the third compound.
  • the solid salt is preferably a solid, and is preferably a neutralized reaction product of the first compound and the second compound.
  • the solid salt is preferably a salt generated by a neutralization reaction.
  • the neutralization reaction is preferably performed at a heating temperature of 25 ° C. to 60 ° C. and a heating time of 5 minutes to 30 minutes.
  • the liquid compound is preferably a liquid, and is preferably a reaction product of the third compound and the fourth compound.
  • the liquid compound is different from the solid salt.
  • the liquid compound is preferably a compound generated by a reaction (dehydration reaction), and preferably has an amide bond.
  • the reaction (dehydration reaction) is preferably performed at a heating temperature of 100 ° C. to 200 ° C. and a heating time of 5 minutes to 5 hours.
  • the weight ratio of the content of the solid salt to the content of the liquid compound is preferably 2 or more, more preferably 4 or more, and preferably 20 or less. More preferably, it is 10 or less.
  • the weight ratio (content of the solid salt / content of the liquid compound) is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively improved, and The flux can be more highly filled, and the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
  • the first compound and the third compound are preferably organic compounds having a carboxyl group.
  • the first compound and the third compound include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, and malic acid, which are aliphatic carboxylic acids.
  • cyclohexylcarboxylic acid, 1,4-cyclohexyldicarboxylic acid which is a cyclic aliphatic carboxylic acid, isophthalic acid, terephthalic acid, trimellitic acid, and ethylenediaminetetraacetic acid, which are aromatic carboxylic acids.
  • the first compound and the third compound are preferably glutaric acid, azelaic acid, or malic acid.
  • the storage stability of the conductive material can be more effectively improved, and the conductive material can be more highly filled with flux.
  • the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
  • the first compound and the third compound may be the same compound or different compounds. From the viewpoint of more effectively improving the storage stability of the conductive material, the viewpoint of further filling the conductive material with flux, and the viewpoint of more effectively increasing the cohesiveness of the solder during the conductive connection, It is preferable that the first compound and the third compound are the same compound.
  • the second compound and the fourth compound are preferably organic compounds having an amino group.
  • the second compound and the fourth compound include diethanolamine, triethanolamine, methyldiethanolamine, ethyldiethanolamine, cyclohexylamine, dicyclohexylamine, benzylamine, benzhydrylamine, 2-methylbenzylamine, and 3-methylbenzylamine. , 4-tert-butylbenzylamine, N-methylbenzylamine, N-ethylbenzylamine, N-phenylbenzylamine, N-tert-butylbenzylamine, N-isopropylbenzylamine, N, N-dimethylbenzylamine, imidazole And triazole compounds.
  • the second compound and the fourth compound are preferably benzylamine, 2-methylbenzylamine, or 3-methylbenzylamine.
  • the storage stability of the conductive material can be more effectively improved, and the conductive material can be charged with a higher flux.
  • the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
  • the second compound and the fourth compound may be the same compound or different compounds. From the viewpoint of more effectively improving the storage stability of the conductive material, the viewpoint of further filling the conductive material with flux, and the viewpoint of more effectively increasing the cohesiveness of the solder during the conductive connection, Preferably, the second compound and the fourth compound are the same compound.
  • the flux may be dispersed in a conductive material or may adhere to the surface of the conductive particles. From the viewpoint of more effectively increasing the flux effect, it is preferable that the flux adheres to the surface of the conductive particles.
  • the average particle size of the solid salt is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the average particle size of the solid salt is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively enhanced.
  • the ratio of the average particle diameter of the solid salt to the average particle diameter of the conductive particles is preferably 0.1 or more, and more preferably 0 or more. .2 or more, preferably 1 or less, more preferably 0.5 or less.
  • the ratio average particle diameter of solid salt / average particle diameter of conductive particles
  • the solid salt can be more effectively brought into contact with the conductive particles.
  • the flux performance during heating can be further improved.
  • the average particle size of the solid salt indicates a number average particle size.
  • the average particle size of the solid salt can be determined by observing 50 arbitrary solid salts with an electron microscope and calculating the average value of the particle size of each solid salt.
  • the particle size of the solid salt indicates the diameter when the solid salt is spherical, and indicates the maximum particle size when the solid salt is not spherical.
  • the content of the flux is preferably at least 1 part by weight, more preferably at least 10 parts by weight, preferably at most 50 parts by weight, more preferably at most 40 parts by weight, based on 100 parts by weight of the thermosetting compound. It is.
  • the content of the flux is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively increased, and the cohesiveness of the solder at the time of conductive connection is more effectively increased. be able to. Since the conductive material according to the present invention satisfies the above-described preferred embodiments, it is possible to highly fill a flux of 50 parts by weight or more.
  • the content of the flux in 100% by weight of the conductive material is preferably 0.05% by weight or more, more preferably 5% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less.
  • the storage stability of the conductive material can be more effectively increased, and the cohesiveness of the solder at the time of conductive connection is more effectively increased. be able to.
  • an oxide film is more difficult to be formed on the surfaces of the solder and the electrode in the conductive particles, and further, the solder and the electrode in the conductive particles The oxide film formed on the surface can be more effectively removed. Since the conductive material according to the present invention satisfies the above-described preferred embodiment, it can be highly filled with a flux of 20% by weight or more.
  • the conductive material may include a filler.
  • the filler may be an organic filler or an inorganic filler. By adding the filler, the conductive particles can be uniformly aggregated on all the electrodes of the substrate.
  • the conductive material preferably does not contain the filler or contains the filler at 5% by weight or less.
  • the thermosetting compound is used, the smaller the filler content, the more easily the conductive particles move on the electrode.
  • the content of the filler is preferably 0% by weight (not included) or more, preferably 5% by weight or less, more preferably 2% by weight or less, and further more preferably 1% by weight or less. It is.
  • the content of the filler is equal to or more than the lower limit and equal to or less than the upper limit, the conductive particles are more efficiently arranged on the electrode.
  • the conductive material may be, if necessary, for example, a filler, a bulking agent, a softener, a plasticizer, a thickener, a thixo agent, a leveling agent, a polymerization catalyst, a curing catalyst, a coloring agent, an antioxidant, and a heat stabilizer.
  • various additives such as light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and flame retardants.
  • connection structure includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connection portion connecting the second connection target member.
  • the material of the connection portion is the above-described conductive material.
  • the connection portion is a cured product of the above-described conductive material.
  • the first electrode and the second electrode are electrically connected by the conductive particles.
  • connection structure since the specific conductive material is used, the solder in the conductive particles easily collects between the first electrode and the second electrode, and the solder is efficiently placed on the electrodes (lines). It can be arranged in a way. Further, it is difficult for a part of the solder to be arranged in the region (space) where the electrode is not formed, and the amount of the solder arranged in the region where the electrode is not formed can be considerably reduced. Therefore, conduction reliability between the first electrode and the second electrode can be improved. In addition, electrical connection between horizontally adjacent electrodes that should not be connected can be prevented, and insulation reliability can be improved.
  • the conductive material is not a conductive film, but a conductive film. It is preferable to use a conductive paste.
  • the thickness of the solder portion between the electrodes is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less.
  • the solder wet area on the surface of the electrode is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more, and preferably 70% or more. Is 100% or less.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to one embodiment of the present invention.
  • connection structure 1 shown in FIG. 1 includes a first connection target member 2, a second connection target member 3, and a connection connecting the first connection target member 2 and the second connection target member 3.
  • Unit 4 The connection part 4 is formed of the above-described conductive material.
  • the conductive material includes conductive particles, a thermosetting component, and a flux.
  • the conductive particles are solder particles.
  • the thermosetting component contains a thermosetting compound and a thermosetting agent.
  • a conductive paste is used as the conductive material.
  • connection portion 4 has a solder portion 4A in which a plurality of solder particles are gathered and joined to each other, and a cured product portion 4B in which a thermosetting component is thermoset.
  • the first connection target member 2 has a plurality of first electrodes 2a on the surface (upper surface).
  • the second connection target member 3 has a plurality of second electrodes 3a on the surface (lower surface).
  • the first electrode 2a and the second electrode 3a are electrically connected by the solder 4A. Therefore, the first connection target member 2 and the second connection target member 3 are electrically connected by the solder portion 4A.
  • no solder exists in a region (cured material portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a.
  • there is no solder separated from the solder portion 4A In a region different from the solder portion 4A (cured material portion 4B portion), there is no solder separated from the solder portion 4A. If the amount is small, the solder may be present in a region (cured material portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a.
  • connection structure 1 a plurality of solder particles gather between the first electrode 2a and the second electrode 3a, and after the plurality of solder particles have melted, Solidifies after the electrode surface wets and spreads to form the solder portion 4A. Therefore, the connection area between the solder portion 4A and the first electrode 2a and the connection area between the solder portion 4A and the second electrode 3a are increased. That is, by using the solder particles, the solder portion 4A, the first electrode 2a, and the solder are compared with the case where the outer surface portion of the conductive portion is made of conductive particles of a metal such as nickel, gold, or copper. The contact area between the portion 4A and the second electrode 3a increases. For this reason, conduction reliability and connection reliability in the connection structure 1 are improved. Note that, generally, the flux contained in the conductive material is gradually deactivated by heating.
  • connection structure 1 shown in FIG. 1 all of the solder portions 4A are located in opposing regions between the first and second electrodes 2a and 3a.
  • the connection structure 1X of the modification shown in FIG. 3 differs from the connection structure 1 shown in FIG. 1 only in the connection portion 4X.
  • the connection part 4X has a solder part 4XA and a cured material part 4XB.
  • most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a face each other, and a part of the solder portion 4XA is formed in the first and second electrodes.
  • the electrodes 2a and 3a may protrude laterally from the facing regions.
  • solder portion 4XA protruding laterally from the region where the first and second electrodes 2a and 3a face each other is a part of the solder portion 4XA and is not a solder separated from the solder portion 4XA.
  • the amount of the solder separated from the solder portion can be reduced, but the solder separated from the solder portion may be present in the cured product portion.
  • connection structure 1X If the amount of the solder particles used is reduced, it becomes easier to obtain the connection structure 1. Increasing the amount of the solder particles facilitates obtaining the connection structure 1X.
  • connection structures 1 and 1X when the opposing portions of the first electrode 2a and the second electrode 3a are viewed in the stacking direction of the first electrode 2a, the connection portions 4 and 4X, and the second electrode 3a.
  • the solder portions 4A and 4XA in the connection portions 4 and 4X are arranged at 50% or more of the area of 100% of the area where the first electrode 2a and the second electrode 3a face each other.
  • conduction reliability can be further improved.
  • the solder portion in the connection portion is arranged in 50% or more of 100% of the area of the portion facing the second electrode.
  • the solder part in the connection part is arranged in 60% or more of the area of 100% of the part facing the second electrode.
  • the solder portion in the connection portion is arranged in 70% or more of 100% of the area of the portion facing the second electrode.
  • the solder portion in the connection portion is arranged at 80% or more of the area of 100% of the portion facing the second electrode.
  • the solder part in the connection part is arranged in 90% or more of the area 100% of the part facing the second electrode.
  • the first electrode It is preferable that 60% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other.
  • the first electrode It is more preferable that 70% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other.
  • the first electrode It is further preferable that 90% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other.
  • the first electrode It is particularly preferable that 95% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other.
  • the first electrode When a portion where the first electrode and the second electrode face each other is viewed in a direction orthogonal to a laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode Most preferably, 99% or more of the solder part in the connection part is arranged in a part where the electrode and the second electrode face each other.
  • the solder portion in the connection portion satisfies the above preferred embodiment, conduction reliability can be further improved.
  • FIG. 2 illustrates an example of a method for manufacturing the connection structure 1 using the conductive material according to one embodiment of the present invention.
  • the first connection target member 2 having the first electrode 2a on the surface (upper surface) is prepared.
  • a conductive material 11 including a thermosetting component 11B and a plurality of solder particles 11A is disposed on the surface of the first connection target member 2 (first).
  • the conductive material 11 includes a thermosetting compound, a thermosetting agent, and a flux as the thermosetting component 11B.
  • the conductive material 11 is arranged on the surface of the first connection target member 2 on which the first electrode 2a is provided. After disposing the conductive material 11, the solder particles 11A are disposed both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed. Note that the conductive material may be disposed only on the surface of the first electrode.
  • the method for arranging the conductive material 11 is not particularly limited, and examples thereof include application using a dispenser, screen printing, and ejection using an inkjet device.
  • a second connection target member 3 having the second electrode 3a on the surface (lower surface) is prepared.
  • the second connection target member 3 is arranged (second step).
  • the second connection target member 3 is arranged on the surface of the conductive material 11 from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a face each other.
  • the conductive material 11 is heated above the melting point of the solder particles 11A (third step).
  • the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (thermosetting compound).
  • the solder particles 11A existing in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect).
  • the conductive paste is used instead of the conductive film, the solder particles 11A more effectively gather between the first electrode 2a and the second electrode 3a. Further, the solder particles 11A are melted and joined to each other.
  • the thermosetting component 11B is thermoset. As a result, as shown in FIG.
  • connection portion 4 connecting the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11.
  • the connection portion 4 is formed by the conductive material 11
  • the solder portion 4A is formed by joining the plurality of solder particles 11A
  • the cured product portion 4B is formed by thermosetting the thermosetting component 11B. If the solder particles 11A move sufficiently, the movement of the solder particles 11A not located between the first electrode 2a and the second electrode 3a starts, and then the first electrode 2a and the second electrode 2a move. The temperature does not need to be kept constant until the movement of the solder particles 11A between the solder particles 3a and 3a is completed.
  • the weight of the second connection target member 3 is added to the conductive material 11. For this reason, when the connection part 4 is formed, the solder particles 11A gather more effectively between the first electrode 2a and the second electrode 3a. If pressure is applied in at least one of the second step and the third step, the action of the solder particles 11A trying to gather between the first electrode 2a and the second electrode 3a. Tend to be inhibited.
  • the alignment between the electrode of the first connection target member and the electrode of the second connection target member is shifted.
  • the first connection target member and the second connection target member may be overlapped.
  • the deviation can be corrected and the electrode of the first connection target member and the electrode of the second connection target member can be connected (self-alignment effect). This is because the molten solder that has self-agglomerated between the electrode of the first member to be connected and the electrode of the second member to be connected is formed between the electrode of the first member to be connected and the second member to be connected.
  • the viscosity of the conductive material at the melting point of the solder is preferably 50 Pa ⁇ s or less, more preferably 10 Pa ⁇ s or less, further preferably 1 Pa ⁇ s or less, preferably 0.1 Pa ⁇ s or more, and more preferably 0.1 Pa ⁇ s or more. 2 Pa ⁇ s or more.
  • the viscosity is equal to or less than the upper limit, the solder in the conductive particles can be efficiently aggregated.
  • the viscosity is equal to or higher than the lower limit, voids at the connection portion can be suppressed, and protrusion of the conductive material to portions other than the connection portion can be suppressed.
  • the viscosity of the conductive material at the melting point of the solder is determined by using a strain control (manufactured by RELOGICA) or the like, with a strain control of 1 rad, a frequency of 1 Hz, a heating rate of 20 ° C./min, and a measurement temperature range of 25 ° C. to 200 ° C. (If the melting point exceeds 200 ° C., the upper limit of the temperature is taken as the melting point of the solder). From the measurement results, the viscosity at the melting point (° C.) of the solder is evaluated.
  • a strain control manufactured by RELOGICA
  • connection structure 1 shown in FIG. 1 is obtained.
  • the second step and the third step may be performed continuously. After performing the second step, the obtained laminated body of the first connection target member 2, the conductive material 11, and the second connection target member 3 is moved to a heating unit, and the third connection target member 2, the conductive material 11, and the second connection target member 3 are moved to the heating unit.
  • a step may be performed. In order to perform the heating, the laminate may be arranged on a heating member, or the laminate may be arranged in a heated space.
  • the heating temperature in the third step is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, preferably 450 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower.
  • the heating temperature in the third step is equal to or higher than the lower limit and equal to or lower than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the upper and lower electrodes to be connected can be connected. Can be more effectively improved.
  • a heating method in the third step a method of heating the entire connection structure using a reflow oven or using an oven above the melting point of the solder in the conductive particles and the curing temperature of the thermosetting component, And a method of locally heating only the connection portion of the connection structure.
  • Examples of instruments used for the method of locally heating include a hot plate, a heat gun for applying hot air, a soldering iron, and an infrared heater.
  • the metal beneath the connection part is a metal with high thermal conductivity, and other places where heating is not preferable are made of a material with low thermal conductivity such as fluororesin.
  • the upper surface of the hot plate is formed.
  • the first and second connection target members are not particularly limited.
  • the first and second connection target members specifically include electronic components such as a semiconductor chip, a semiconductor package, an LED chip, an LED package, a capacitor and a diode, a resin film, a printed board, a flexible printed board, and a flexible board.
  • Electronic components such as a flat cable, a rigid flexible substrate, a circuit board such as a glass epoxy substrate and a glass substrate, and the like.
  • the first and second connection target members are electronic components.
  • At least one of the first connection target member and the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. It is preferable that at least one of the first connection target member and the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board.
  • a resin film, a flexible printed board, a flexible flat cable, and a rigid flexible board have properties of high flexibility and relatively light weight.
  • Examples of the electrodes provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode.
  • the electrode When the electrode is an aluminum electrode, the electrode may be an electrode formed only of aluminum, or may be an electrode in which an aluminum layer is laminated on a surface of a metal oxide layer.
  • the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal element include Sn, Al, and Ga.
  • the first electrode and the second electrode are arranged in an area array or a peripheral.
  • the solder in the conductive particles can be more effectively aggregated on the electrodes.
  • the area array refers to a structure in which electrodes are arranged in a grid on the surface of the connection target member where the electrodes are arranged.
  • the peripheral is a structure in which an electrode is arranged on an outer peripheral portion of a connection target member.
  • the solder may be aggregated along the direction perpendicular to the comb, whereas in the area array or the peripheral structure, the surface where the electrodes are arranged is entirely covered. It is necessary that the solder coheres uniformly. Therefore, in the conventional method, the amount of solder tends to be non-uniform, whereas in the method of the present invention, the solder can be uniformly agglomerated over the entire surface.
  • Thermosetting component (thermosetting compound): Thermosetting compound 1: "DEN-431” manufactured by Dow Chemical Company, epoxy resin Thermosetting compound 2: "jER152” manufactured by Mitsubishi Chemical Corporation, epoxy resin
  • Thermosetting component thermosetting agent: Thermosetting agent 1: "BF3-MEA” manufactured by Tokyo Kasei Kogyo Co., Ltd., boron trifluoride-monoethylamine complex
  • Thermosetting agent 2 "2PZ-CN” manufactured by Shikoku Kasei Kogyo Co., 1-cyanoethyl-2-phenylimidazole
  • Conductive particles Conductive particles 1: Solder particles, “SnAg3Cu0.5 (ST-2)” manufactured by Mitsui Kinzoku Mining (average particle size 2.2 ⁇ m)
  • Conductive particles 2 solder particles, “SnAg3Cu0.5 (DS-10)” manufactured by Mitsui Mining & Smelting Co., Ltd. (average particle diameter 13 ⁇ m)
  • Flux 1 solid salt of glutaric acid and benzylamine, average particle size 1 ⁇ m
  • Method for preparing flux 1 24 g of water as a reaction solvent and 13.212 g of glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle and dissolved at room temperature until uniform. Thereafter, 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for about 5 minutes to obtain a mixed solution. The obtained mixture was put in a refrigerator at 5 ° C to 10 ° C and left overnight. The precipitated crystals were separated by filtration, washed with water, and dried under vacuum. Flux 1 was obtained by heating the dried crystals at 140 ° C. for 15 minutes to completely melt them and gradually reprecipitating them at 25 ° C. over 30 minutes.
  • Flux 2 Liquid compound which is a reaction product of glutaric acid and benzylamine
  • Method for preparing flux 2 13.212 g of glutaric acid (manufactured by Wako Pure Chemical Industries) and 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries) are placed in a three-necked flask, and heated at 120 ° C. for 3 hours to react. Flux 2 was obtained.
  • Flux 3 solid salt of succinic acid and benzylamine, average particle diameter 10 ⁇ m
  • Flux 3 production method 24 g of water as a reaction solvent and 11.809 g of succinic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle and dissolved at room temperature until uniform. Thereafter, 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for about 5 minutes to obtain a mixed solution. The obtained mixture was put in a refrigerator at 5 ° C to 10 ° C and left overnight. The precipitated crystals were separated by filtration, washed with water, and dried under vacuum. The dried crystal was heated at 190 ° C. for 10 minutes to completely melt it, and gradually reprecipitated at 25 ° C. for 30 minutes to obtain flux 3.
  • Flux 4 Liquid compound which is a reaction product of succinic acid and benzylamine
  • Method for preparing flux 4 In a three-necked flask, 11.809 g of succinic acid (manufactured by Wako Pure Chemical Industries) and 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries) were added, and heated at 200 ° C. for 2 hours to react. Flux 4 was obtained.
  • Flux 5 solid salt of malic acid and benzylamine, average particle size 5 ⁇ m
  • Method for preparing flux 5 24 g of water as a reaction solvent and 13.409 g of malic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle and dissolved at room temperature until uniform. Thereafter, 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for about 5 minutes to obtain a mixed solution. The obtained mixture was put in a refrigerator at 5 ° C to 10 ° C and left overnight. The precipitated crystals were separated by filtration, washed with water, and dried under vacuum. The dried crystal was heated at 180 ° C. for 15 minutes to completely melt it, and was gradually reprecipitated at 25 ° C. for 30 minutes to obtain flux 5.
  • Flux 6 liquid compound which is a reaction product of malic acid and benzylamine
  • Method for preparing flux 6 13.409 g of malic acid (manufactured by Wako Pure Chemical Industries) and 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries) were placed in a three-necked flask, and reacted by heating at 150 ° C. for 3 hours. Flux 6 was obtained.
  • the average particle size of the solid salt was calculated from the average value by measuring the particle size of 50 arbitrary solid salts using a scanning electron microscope (“S-4300SEN” manufactured by Hitachi, Ltd.).
  • a glass epoxy substrate (FR-4 substrate) (first connection target member) having a copper electrode pattern (copper electrode thickness: 12 ⁇ m) having an L / S of 50 ⁇ m / 50 ⁇ m and an electrode length of 3 mm on the upper surface was prepared.
  • a flexible printed circuit board (second connection target member) having a copper electrode pattern (copper electrode thickness: 12 ⁇ m) having an L / S of 50 ⁇ m / 50 ⁇ m and an electrode length of 3 mm on the lower surface was prepared.
  • the overlapping area of the glass epoxy substrate and the flexible printed board was 1.5 cm ⁇ 3 mm, and the number of connected electrodes was 75 pairs.
  • a conductive material (anisotropic conductive paste) immediately after production is applied by screen printing using a metal mask so as to have a thickness of 100 ⁇ m on the electrodes of the glass epoxy substrate, A conductive material (anisotropic conductive paste) layer was formed.
  • the flexible printed circuit board was laminated on the upper surface of the conductive material (anisotropic conductive paste) layer so that the electrodes faced each other. At this time, no pressurization was performed. The weight of the flexible printed board is added to the conductive material (anisotropic conductive paste) layer.
  • 2A second connection structure was obtained in the same manner as in the production of the first connection structure except that the above-mentioned glass epoxy substrate and flexible printed circuit board having different L / S were used.
  • 3A third connection structure was obtained in the same manner as in the production of the first connection structure except that the above-mentioned glass epoxy substrate and flexible printed circuit board having different L / S were used.
  • the flux in the obtained conductive material is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group. It was confirmed whether or not a liquid compound which was a reaction product with the fourth compound having an amino group was contained. The existence state of the flux was determined based on the following criteria.
  • Viscosity increase rate ( ⁇ 2 / ⁇ 1) is 1.5 or less ⁇ : Viscosity increase rate ( ⁇ 2 / ⁇ 1) exceeds 1.5 and 2.0 or less ⁇ : Viscosity increase rate ( ⁇ 2 / ⁇ 1) is 2.0 Exceed
  • solder placement accuracy on electrodes In the obtained first, second, and third connection structures, a portion where the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode is As a result, the ratio X of the area where the solder portion in the connection portion was arranged in 100% of the area of the portion where the first electrode and the second electrode face each other was evaluated.
  • the placement accuracy (solder cohesion) of the solder on the electrode was determined according to the following criteria.
  • 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% X: Ratio X is less than 50%
  • connection resistance per connection between the upper and lower electrodes is set to 4 It was measured by the terminal method. The average value of the connection resistance was calculated.
  • connection resistance The average value of the connection resistance is 50 m ⁇ or less ⁇ : The average value of the connection resistance is more than 50 m ⁇ and 70 m ⁇ or less ⁇ : The average value of the connection resistance is more than 70 m ⁇ and 100 m ⁇ or less ⁇ : The average value of the connection resistance exceeds 100 m ⁇ , or Poor connection
  • ⁇ The average value of the connection resistance is 10 7 ⁇ or more.
  • ⁇ The average value of the connection resistance is 10 6 ⁇ or more and less than 10 7 ⁇ .
  • ⁇ The average value of the connection resistance is 10 5 ⁇ or more and less than 10 6 ⁇ . Average value is less than 10 5 ⁇

Abstract

Provided is a conductive material, the storage stability of which can be efficiently increased and which can be densely filled with flux, and which can also efficiently increase solder coalescing properties during conductive connection. This conductive material comprises a plurality of conductive particles having solder on the outer surface portions of conductive parts, a thermosetting component, and flux, wherein the flux contains solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a liquid compound which is a reactant of a third compound having a carboxyl group and a fourth compound having an amino group.

Description

導電材料及び接続構造体Conductive material and connection structure
　本発明は、導電部の外表面部分にはんだを有する導電性粒子を含む導電材料に関する。また、本発明は、上記導電材料を用いた接続構造体に関する。 The present invention relates to a conductive material containing conductive particles having solder on the outer surface of the conductive part. Further, the present invention relates to a connection structure using the conductive material.
　異方性導電ペースト及び異方性導電フィルム等の異方性導電材料が広く知られている。上記異方性導電材料では、バインダー中に導電性粒子が分散されている。 異 方 性 Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder.
　上記異方性導電材料は、各種の接続構造体を得るために使用されている。上記異方性導電材料による接続としては、例えば、フレキシブルプリント基板とガラス基板との接続（ＦＯＧ（Ｆｉｌｍ　ｏｎ　Ｇｌａｓｓ））、半導体チップとフレキシブルプリント基板との接続（ＣＯＦ（Ｃｈｉｐ　ｏｎ　Ｆｉｌｍ））、半導体チップとガラス基板との接続（ＣＯＧ（Ｃｈｉｐ　ｏｎ　Ｇｌａｓｓ））、並びにフレキシブルプリント基板とガラスエポキシ基板との接続（ＦＯＢ（Ｆｉｌｍ　ｏｎ　Ｂｏａｒｄ））等が挙げられる。 The anisotropic conductive material is used to obtain various connection structures. As the connection using the anisotropic conductive material, for example, connection between a flexible printed board and a glass substrate (FOG (Film @ on @ Glass)), connection between a semiconductor chip and a flexible printed board (COF (Chip @ on @ Film)), semiconductor The connection between the chip and the glass substrate (COG (Chip @ on @ Glass)), the connection between the flexible printed board and the glass epoxy substrate (FOB (Film @ on @ Board)), and the like can be given.
　上記異方性導電材料により、例えば、フレキシブルプリント基板の電極とガラスエポキシ基板の電極とを電気的に接続する際には、ガラスエポキシ基板上に、導電性粒子を含む異方性導電材料を配置する。次に、フレキシブルプリント基板を積層して、加熱及び加圧する。これにより、異方性導電材料を硬化させて、導電性粒子を介して電極間を電気的に接続して、接続構造体を得る。 When the electrode of the flexible printed board and the electrode of the glass epoxy board are electrically connected by the anisotropic conductive material, for example, an anisotropic conductive material containing conductive particles is placed on the glass epoxy board. I do. Next, the flexible printed circuit boards are laminated and heated and pressed. Thereby, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
　上記異方性導電材料の一例として、下記の特許文献１には、（Ａ）融点が２２０℃以下である金属を含む導電性粒子と、（Ｂ）熱硬化性樹脂と、（Ｃ）フラックス活性剤とを含む導電性接着剤組成物が開示されている。上記導電性接着剤組成物では、上記（Ｃ）フラックス活性剤の平均粒子径は１０μｍ以下である。 As an example of the anisotropic conductive material, Patent Document 1 listed below discloses (A) conductive particles containing a metal having a melting point of 220 ° C. or less, (B) a thermosetting resin, and (C) flux activity. And a conductive adhesive composition comprising the agent. In the conductive adhesive composition, the flux activator (C) has an average particle size of 10 μm or less.
ＷＯ２０１２／１０２０７７Ａ１WO2012 / 102077A1
　従来の導電材料では、導電性粒子の電極（ライン）上への移動速度が遅く、接続されるべき上下の電極間にはんだを効率的に凝集させることが困難な場合がある。結果として、電極間の導通信頼性及び絶縁信頼性が低くなり易い。 で は With conventional conductive materials, the speed of moving the conductive particles onto the electrodes (lines) is low, and it may be difficult to efficiently aggregate the solder between the upper and lower electrodes to be connected. As a result, the reliability of conduction between the electrodes and the reliability of insulation tend to be low.
　電極上にはんだを効率的に凝集させる方法としては、導電材料中のフラックスの配合量を増加させる方法等が挙げられる。上記フラックスとしては、導電材料に配合する際に固体である固体フラックスと、導電材料に配合する際に液体である液体フラックスとがある。 方法 As a method of efficiently aggregating the solder on the electrode, there is a method of increasing the amount of the flux in the conductive material. The flux includes a solid flux that is solid when blended with a conductive material, and a liquid flux that is liquid when blended with a conductive material.
　しかしながら、本発明者らは、固体フラックスと液体フラックスとにおいて、以下の課題があることを見出した。 However, the present inventors have found that the solid flux and the liquid flux have the following problems.
　固体フラックスのみを用いる場合に、導電材料中における固体フラックスの含有量を増加させると、導電材料の粘度が大幅に上昇し、導電材料として使用が困難になることがある。導電材料中に固体フラックスを高充填することは困難であり、電極上にはんだを効率的に凝集させることは困難である。また、固体フラックスは、導電材料中の熱硬化性化合物との反応性が低いため、導電材料の保存安定性を高めることができる。結果として、導電材料に固体フラックスのみを用いる場合には、導電材料の保存安定性を高めることはできるものの、固体フラックスを高充填すること、及びはんだの凝集性を高めることは困難である。 (4) When only the solid flux is used, if the content of the solid flux in the conductive material is increased, the viscosity of the conductive material is significantly increased, and it may be difficult to use the conductive material as the conductive material. It is difficult to highly fill a conductive material with a solid flux, and it is difficult to efficiently aggregate solder on an electrode. In addition, since the solid flux has low reactivity with the thermosetting compound in the conductive material, the storage stability of the conductive material can be improved. As a result, when only a solid flux is used as the conductive material, the storage stability of the conductive material can be improved, but it is difficult to fill the solid flux with a high amount and to increase the cohesiveness of the solder.
　また、液体フラックスのみを用いる場合に、導電材料中における液体フラックスの含有量を増加させると、フラックスと導電材料中の熱硬化性化合物とが反応して、導電材料の保存安定性が低下することがある。また、液体フラックスは、導電材料中に高充填することができ、電極上にはんだを効率的に凝集させることができる。結果として、導電材料に液体フラックスのみを用いる場合には、液体フラックスを高充填すること、及びはんだの凝集性を高めることはできるものの、導電材料の保存安定性を高めることは困難である。 In addition, when only the liquid flux is used, when the content of the liquid flux in the conductive material is increased, the flux reacts with the thermosetting compound in the conductive material, and the storage stability of the conductive material is reduced. There is. Further, the liquid flux can be highly filled in the conductive material, and the solder can be efficiently aggregated on the electrode. As a result, when only a liquid flux is used as the conductive material, it is difficult to increase the storage stability of the conductive material, although it is possible to highly fill the liquid flux and increase the cohesiveness of the solder.
　従来の導電材料では、導電材料の保存安定性を高めることと、導電材料中にフラックスを高充填することと、導電接続時のはんだの凝集性を高めることとの、これらの全ての要求を満足させることは困難である。 Conventional conductive materials meet all of these requirements: to increase the storage stability of the conductive material, to fill the conductive material with a high flux, and to increase the cohesion of the solder during conductive connection. It is difficult to do that.
　本発明の目的は、導電材料の保存安定性を効果的に高めることができ、導電材料中にフラックスを高充填することができ、さらに、導電接続時のはんだの凝集性を効果的に高めることができる導電材料を提供することである。また、本発明の目的は、上記導電材料を用いた接続構造体を提供することである。 An object of the present invention is to improve the storage stability of a conductive material effectively, to fill a conductive material with a high flux, and to effectively increase the cohesiveness of solder at the time of conductive connection. It is to provide a conductive material which can be used. Another object of the present invention is to provide a connection structure using the above conductive material.
　本発明の広い局面によれば、導電部の外表面部分にはんだを有する複数の導電性粒子と、熱硬化性成分と、フラックスとを含み、前記フラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物を含む、導電材料が提供される。 According to a wide aspect of the present invention, a plurality of conductive particles having solder on the outer surface portion of the conductive portion, a thermosetting component, and a flux, wherein the flux has a first compound having a carboxyl group A conductive material is provided, including a solid salt with a second compound having an amino group, and a liquid compound which is a reaction product of a third compound having a carboxyl group and a fourth compound having an amino group.
　本発明に係る導電材料のある特定の局面では、前記固体塩の含有量の、前記液体化合物の含有量に対する重量比が、２以上２０以下である。 In a specific aspect of the conductive material according to the present invention, a weight ratio of the content of the solid salt to the content of the liquid compound is 2 or more and 20 or less.
　本発明に係る導電材料のある特定の局面では、前記第１の化合物と前記第３の化合物とが、同一の化合物である。 で は In a specific aspect of the conductive material according to the present invention, the first compound and the third compound are the same compound.
　本発明に係る導電材料のある特定の局面では、前記第２の化合物と前記第４の化合物とが、同一の化合物である。 で は In a specific aspect of the conductive material according to the present invention, the second compound and the fourth compound are the same compound.
　本発明に係る導電材料のある特定の局面では、前記固体塩の平均粒子径が、０．０１μｍ以上１０μｍ以下である。 で は In a specific aspect of the conductive material according to the present invention, the average particle diameter of the solid salt is 0.01 μm or more and 10 μm or less.
　本発明に係る導電材料のある特定の局面では、前記熱硬化性成分が、熱硬化性化合物を含み、前記熱硬化性化合物１００重量部に対して、前記フラックスの含有量が、１重量部以上５０重量部以下である。 In a specific aspect of the conductive material according to the present invention, the thermosetting component includes a thermosetting compound, and the content of the flux is 1 part by weight or more based on 100 parts by weight of the thermosetting compound. 50 parts by weight or less.
　本発明に係る導電材料のある特定の局面では、導電材料１００重量％中、前記フラックスの含有量が、０．０５重量％以上２０重量％以下である。 で は In a specific aspect of the conductive material according to the present invention, the content of the flux is 0.05% by weight or more and 20% by weight or less in 100% by weight of the conductive material.
　本発明に係る導電材料のある特定の局面では、前記導電性粒子の平均粒子径が、０．０１μｍ以上５０μｍ以下である。 で は In a specific aspect of the conductive material according to the present invention, the conductive particles have an average particle size of 0.01 μm or more and 50 μm or less.
　本発明に係る導電材料のある特定の局面では、前記導電材料が、導電ペーストである。 で は In a specific aspect of the conductive material according to the present invention, the conductive material is a conductive paste.
　本発明の広い局面によれば、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、前記第１の接続対象部材と、前記第２の接続対象部材とを接続している接続部とを備え、前記接続部の材料が、上述した導電材料であり、前記第１の電極と前記第２の電極とが、前記導電性粒子により電気的に接続されている、接続構造体が提供される。 According to a broad aspect of the present invention, a first connection target member having a first electrode on a surface, a second connection target member having a second electrode on a surface, the first connection target member, A connection portion connecting the second connection target member, wherein the material of the connection portion is the conductive material described above, and the first electrode and the second electrode are formed of the conductive material. A connection structure is provided that is electrically connected by the particles.
　本発明に係る導電材料は、導電部の外表面部分にはんだを有する複数の導電性粒子と、熱硬化性成分と、フラックスとを含む。本発明に係る導電材料では、上記フラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物を含む。本発明に係る導電材料では、上記の構成が備えられているので、導電材料の保存安定性を効果的に高めることができ、導電材料中にフラックスを高充填することができ、さらに、導電接続時のはんだの凝集性を効果的に高めることができる。 The conductive material according to the present invention includes a plurality of conductive particles having solder on the outer surface of the conductive part, a thermosetting component, and a flux. In the conductive material according to the present invention, the flux is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a second compound having an amino group. And a liquid compound which is a reaction product with the compound of No. 4. In the conductive material according to the present invention, since the above-described configuration is provided, the storage stability of the conductive material can be effectively improved, the conductive material can be filled with a high flux, and the conductive connection can be further improved. The cohesiveness of the solder at the time can be effectively increased.
図１は、本発明の一実施形態に係る導電材料を用いて得られる接続構造体を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to one embodiment of the present invention. 図２（ａ）～（ｃ）は、本発明の一実施形態に係る導電材料を用いて、接続構造体を製造する方法の一例の各工程を説明するための断面図である。FIGS. 2A to 2C are cross-sectional views illustrating steps of an example of a method for manufacturing a connection structure using a conductive material according to an embodiment of the present invention. 図３は、接続構造体の変形例を示す断面図である。FIG. 3 is a cross-sectional view showing a modification of the connection structure. 図４は、導電材料に使用可能な導電性粒子の第１の例を示す断面図である。FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used for a conductive material. 図５は、導電材料に使用可能な導電性粒子の第２の例を示す断面図である。FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used for a conductive material. 図６は、導電材料に使用可能な導電性粒子の第３の例を示す断面図である。FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for a conductive material.
　以下、本発明の詳細を説明する。 Hereinafter, the details of the present invention will be described.
　（導電材料）
　本発明に係る導電材料は、導電部の外表面部分にはんだを有する複数の導電性粒子と、熱硬化性成分と、フラックスとを含む。本発明に係る導電材料では、上記フラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物を含む。 (Conductive material)
The conductive material according to the present invention includes a plurality of conductive particles having solder on the outer surface of the conductive portion, a thermosetting component, and a flux. In the conductive material according to the present invention, the flux is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a second compound having an amino group. And a liquid compound which is a reaction product with the compound of No. 4.
　本発明に係る導電材料では、上記の構成が備えられているので、導電材料の保存安定性を効果的に高めることができ、導電材料中にフラックスを高充填することができ、さらに、導電接続時のはんだの凝集性を効果的に高めることができる。 In the conductive material according to the present invention, since the above-described configuration is provided, the storage stability of the conductive material can be effectively improved, the conductive material can be filled with a high flux, and the conductive connection can be further improved. The cohesiveness of the solder at the time can be effectively increased.
　本発明では、上記の構成が備えられているので、電極間を電気的に接続した場合に、複数の導電性粒子を電極（ライン）上に効率的に配置することができ、接続されるべき上下の電極間にはんだを効率的に凝集させることができる。また、複数の導電性粒子の一部が、電極が形成されていない領域（スペース）に配置され難く、電極が形成されていない領域に配置される導電性粒子の量をかなり少なくすることができる。従って、電極間の導通信頼性を高めることができる。しかも、接続されてはならない横方向に隣接する電極間の電気的な接続を防ぐことができ、絶縁信頼性を高めることができる。 In the present invention, since the above configuration is provided, when the electrodes are electrically connected, a plurality of conductive particles can be efficiently arranged on the electrodes (lines) and should be connected. The solder can be efficiently aggregated between the upper and lower electrodes. Further, it is difficult for some of the plurality of conductive particles to be arranged in the region (space) where the electrode is not formed, and the amount of the conductive particle arranged in the region where the electrode is not formed can be considerably reduced. . Therefore, the reliability of conduction between the electrodes can be improved. In addition, electrical connection between horizontally adjacent electrodes that should not be connected can be prevented, and insulation reliability can be improved.
　フラックスは、主として、導電性粒子におけるはんだの表面及び電極の表面等に存在する酸化物を除去したり、該酸化物の形成を防止したりするために導電材料中に配合されている。本発明では、固体のフラックスと液体のフラックスとを併用しているので、導電材料中にフラックスを高充填することができる。本発明では、固体のフラックスと液体のフラックスとを併用しているので、固体フラックスを単独で用いる場合と比べて、導電材料中にフラックスを高充填することが容易である。このため、本発明では、導電性粒子におけるはんだの表面及び電極の表面等に存在する酸化物を効果的に除去することができ、該酸化物の形成を効果的に防止することができる。本発明では、導電材料中にフラックスを高充填することができるので、導電接続時のはんだの凝集性を効果的に高めることができる。 (4) The flux is mainly incorporated into the conductive material in order to remove the oxide present on the surface of the solder and the surface of the electrode in the conductive particles and to prevent the formation of the oxide. In the present invention, since the solid flux and the liquid flux are used in combination, the conductive material can be highly filled with the flux. In the present invention, since the solid flux and the liquid flux are used in combination, it is easier to highly fill the conductive material with the flux than when the solid flux is used alone. For this reason, in the present invention, oxides present on the surface of the solder, the surface of the electrodes, and the like in the conductive particles can be effectively removed, and the formation of the oxides can be effectively prevented. According to the present invention, since the flux can be highly filled in the conductive material, the cohesiveness of the solder at the time of conductive connection can be effectively improved.
　本発明では、固体のフラックスと液体のフラックスとを併用しているので、導電材料中における熱硬化性化合物とフラックスとの反応を効果的に抑制することができる。結果として、導電材料の保存安定性を効果的に高めることができる。 According to the present invention, since the solid flux and the liquid flux are used in combination, the reaction between the thermosetting compound and the flux in the conductive material can be effectively suppressed. As a result, the storage stability of the conductive material can be effectively increased.
　本発明では、固体のフラックスと液体のフラックスとを併用しているので、固体フラックスのみを用いる場合と比較して、導電材料中にフラックスを高充填することができ、導電接続時のはんだの凝集性を効果的に高めることができる。また、本発明では、固体のフラックスと液体のフラックスとを併用しているので、液体フラックスのみを用いる場合と比較して、導電材料の保存安定性を効果的に高めることができる。 In the present invention, since the solid flux and the liquid flux are used in combination, the flux can be filled in the conductive material at a higher level than in the case where only the solid flux is used. Sex can be effectively improved. In addition, in the present invention, since the solid flux and the liquid flux are used in combination, the storage stability of the conductive material can be effectively improved as compared with the case where only the liquid flux is used.
　本発明では、上記の構成が備えられているので、導電材料の保存安定性を高めることと、導電材料中にフラックスを高充填することと、導電接続時のはんだの凝集性を高めることとの、これらの全ての要求を満足させることができる。 In the present invention, since the above configuration is provided, it is possible to improve the storage stability of the conductive material, to fill the conductive material with a high flux, and to increase the cohesiveness of the solder during the conductive connection. , All of these requirements can be satisfied.
　さらに、本発明では、電極間の位置ずれを防ぐことができる。本発明では、導電材料を上面に配置した第１の接続対象部材に、第２の接続対象部材を重ね合わせる際に、第１の接続対象部材の電極と第２の接続対象部材の電極とのアライメントがずれた状態でも、そのずれを補正して電極同士を接続させることができる（セルフアライメント効果）。 Furthermore, in the present invention, it is possible to prevent displacement between electrodes. In the present invention, when the second connection target member is superimposed on the first connection target member on which the conductive material is disposed on the upper surface, the electrode of the first connection target member and the electrode of the second connection target member are connected. Even in a state where the alignment is shifted, the electrode can be connected by correcting the shift (self-alignment effect).
　導電材料中にフラックスをより一層高充填する観点、及び導電接続時のはんだの凝集性をより一層効果的に高める観点からは、上記導電材料は、２５℃で液状であることが好ましく、導電ペーストであることが好ましい。上記導電材料は、２５℃で導電ペーストであることが好ましい。 From the viewpoint of further filling the conductive material with the flux, and from the viewpoint of more effectively increasing the cohesiveness of the solder during conductive connection, the conductive material is preferably liquid at 25 ° C. It is preferred that The conductive material is preferably a conductive paste at 25 ° C.
　導電材料中にフラックスをより一層高充填する観点、及び導電接続時のはんだの凝集性をより一層効果的に高める観点からは、上記導電材料の２５℃での粘度（η２５）は、好ましくは２０Ｐａ・ｓ以上、より好ましくは３０Ｐａ・ｓ以上であり、好ましくは５００Ｐａ・ｓ以下、より好ましくは３００Ｐａ・ｓ以下である。上記粘度（η２５）は、配合成分の種類及び配合量により適宜調整することができる。 The viscosity (η25) at 25 ° C. of the conductive material is preferably 20 Pa from the viewpoint of further filling the conductive material with the flux and further effectively increasing the cohesiveness of the solder during the conductive connection. -S or more, more preferably 30 Pa-s or more, preferably 500 Pa-s or less, more preferably 300 Pa-s or less. The viscosity (η25) can be appropriately adjusted depending on the types and amounts of the components.
　上記粘度（η２５）は、例えば、Ｅ型粘度計（東機産業社製「ＴＶＥ２２Ｌ」）等を用いて、２５℃及び５ｒｐｍの条件で測定することができる。 The viscosity (η25) can be measured, for example, using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
　上記導電材料は、導電ペースト及び導電フィルム等として使用され得る。上記導電ペーストは異方性導電ペーストであることが好ましく、上記導電フィルムは異方性導電フィルムであることが好ましい。導電材料中にフラックスをより一層高充填する観点、及び導電接続時のはんだの凝集性をより一層効果的に高める観点からは、上記導電材料は、導電ペーストであることが好ましい。上記導電材料は、電極の電気的な接続に好適に用いられる。上記導電材料は、回路接続材料であることが好ましい。 The conductive material can be used as a conductive paste and a conductive film. The conductive paste is preferably an anisotropic conductive paste, and the conductive film is preferably an anisotropic conductive film. The conductive material is preferably a conductive paste from the viewpoint of further filling the conductive material with the flux and more effectively increasing the cohesiveness of the solder during the conductive connection. The conductive material is suitably used for electrical connection of electrodes. The conductive material is preferably a circuit connecting material.
　以下、導電材料に含まれる各成分を説明する。なお、本明細書中において、「（メタ）アクリル」は「アクリル」と「メタクリル」との一方又は双方を意味し、「（メタ）アクリレート」は「アクリレート」と「メタクリレート」との一方又は双方を意味する。 Hereinafter, each component contained in the conductive material will be described. In this specification, “(meth) acryl” means one or both of “acryl” and “methacryl”, and “(meth) acrylate” means one or both of “acrylate” and “methacrylate”. Means
　（導電性粒子）
　上記導電材料は、導電性粒子を含む。上記導電性粒子は、接続対象部材の電極間を電気的に接続する。上記導電性粒子は、導電部の外表面部分にはんだを有する。上記導電性粒子は、はんだにより形成されたはんだ粒子であってもよい。上記はんだ粒子は、はんだを導電部の外表面部分に有する。上記はんだ粒子は、中心部分及び導電部の外表面部分のいずれもがはんだにより形成されている。上記はんだ粒子は、中心部分及び導電性の外表面のいずれもがはんだである粒子である。上記導電性粒子は、基材粒子と、該基材粒子の表面上に配置された導電部とを有していてもよい。この場合に、上記導電性粒子は、導電部の外表面部分に、はんだを有する。 (Conductive particles)
The conductive material includes conductive particles. The conductive particles electrically connect the electrodes of the connection target member. The conductive particles have solder on the outer surface of the conductive part. The conductive particles may be solder particles formed by solder. The solder particles have solder on the outer surface of the conductive part. In the solder particles, both the central portion and the outer surface portion of the conductive portion are formed of solder. The solder particles are particles in which both the central portion and the conductive outer surface are solder. The conductive particles may have base particles and a conductive part disposed on the surface of the base particles. In this case, the conductive particles have solder on the outer surface of the conductive part.
　上記導電性粒子は、導電部の外表面部分にはんだを有する。上記基材粒子は、はんだにより形成されたはんだ粒子であってもよい。上記導電性粒子は、基材粒子及び導電部の外表面部分のいずれもがはんだであるはんだ粒子であってもよい。 The conductive particles have solder on the outer surface of the conductive part. The base particles may be solder particles formed of solder. The conductive particles may be solder particles in which both the base particles and the outer surface of the conductive portion are solder.
　なお、上記はんだ粒子を用いた場合と比べて、はんだにより形成されていない基材粒子と、該基材粒子の表面上に配置されたはんだ部とを備える導電性粒子を用いた場合には、電極上に導電性粒子が集まり難くなる。さらに、導電性粒子同士のはんだ接合性が低いために、電極上に移動した導電性粒子が電極外に移動しやすくなる傾向があり、電極間の位置ずれの抑制効果も低くなる傾向がある。従って、上記導電性粒子は、はんだにより形成されたはんだ粒子であることが好ましい。 In addition, compared to the case of using the above solder particles, when using conductive particles including a base particle not formed by solder and a solder portion disposed on the surface of the base particle, It becomes difficult for conductive particles to collect on the electrodes. Furthermore, since the solderability between the conductive particles is low, the conductive particles that have moved onto the electrodes tend to move easily outside the electrodes, and the effect of suppressing the displacement between the electrodes tends to decrease. Therefore, the conductive particles are preferably solder particles formed by solder.
　次に図面を参照しつつ、導電性粒子の具体例を説明する。 Next, specific examples of the conductive particles will be described with reference to the drawings.
　図４は、導電材料に使用可能な導電性粒子の第１の例を示す断面図である。 FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used for a conductive material.
　図４に示す導電性粒子２１は、はんだ粒子である。導電性粒子２１は、全体がはんだにより形成されている。導電性粒子２１は、基材粒子をコアに有さず、コアシェル粒子ではない。導電性粒子２１は、中心部分及び導電部の外表面部分のいずれもがはんだにより形成されている。 導電 The conductive particles 21 shown in FIG. 4 are solder particles. The conductive particles 21 are entirely formed of solder. The conductive particles 21 do not have the base particles in the core and are not core-shell particles. In the conductive particles 21, both the central part and the outer surface part of the conductive part are formed by solder.
　図５は、導電材料に使用可能な導電性粒子の第２の例を示す断面図である。 FIG. 5 is a cross-sectional view showing a second example of the conductive particles usable for the conductive material.
　図５に示す導電性粒子３１は、基材粒子３２と、基材粒子３２の表面上に配置された導電部３３とを備える。導電部３３は、基材粒子３２の表面を被覆している。導電性粒子３１は、基材粒子３２の表面が導電部３３により被覆された被覆粒子である。 導電 The conductive particles 31 shown in FIG. 5 include base particles 32 and a conductive part 33 disposed on the surface of the base particles 32. The conductive portion 33 covers the surface of the base particles 32. The conductive particles 31 are coated particles in which the surfaces of the base particles 32 are coated with the conductive portions 33.
　導電部３３は、第２の導電部３３Ａと、はんだ部３３Ｂ（第１の導電部）とを有する。導電性粒子３１は、基材粒子３２と、はんだ部３３Ｂとの間に、第２の導電部３３Ａを備える。従って、導電性粒子３１は、基材粒子３２と、基材粒子３２の表面上に配置された第２の導電部３３Ａと、第２の導電部３３Ａの外表面上に配置されたはんだ部３３Ｂとを備える。 (4) The conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion). The conductive particles 31 include a second conductive portion 33A between the base particles 32 and the solder portion 33B. Accordingly, the conductive particles 31 include the base particles 32, the second conductive portions 33A disposed on the surface of the base particles 32, and the solder portions 33B disposed on the outer surface of the second conductive portions 33A. And
　図６は、導電材料に使用可能な導電性粒子の第３の例を示す断面図である。 FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for a conductive material.
　図５における導電性粒子３１の導電部３３は２層構造を有する。図６に示す導電性粒子４１は、単層の導電部として、はんだ部４２を有する。導電性粒子４１は、基材粒子３２と、基材粒子３２の表面上に配置されたはんだ部４２とを備える。 導電 The conductive part 33 of the conductive particle 31 in FIG. 5 has a two-layer structure. The conductive particles 41 shown in FIG. 6 have a solder part 42 as a single-layer conductive part. The conductive particles 41 include the base particles 32 and the solder portions 42 arranged on the surface of the base particles 32.
　以下、導電性粒子の他の詳細について説明する。 Hereinafter, other details of the conductive particles will be described.
　（基材粒子）
　上記基材粒子としては、樹脂粒子、金属粒子を除く無機粒子、有機無機ハイブリッド粒子及び金属粒子等が挙げられる。上記基材粒子は、金属粒子を除く基材粒子であることが好ましく、樹脂粒子、金属粒子を除く無機粒子又は有機無機ハイブリッド粒子であることがより好ましい。上記基材粒子は、無機粒子を除く基材粒子であってもよい。上記基材粒子は、コアと、該コアの表面上に配置されたシェルとを備えるコアシェル粒子であってもよい。上記コアが有機コアであってもよく、上記シェルが無機シェルであってもよい。 (Base particles)
Examples of the base particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The base particles are preferably base particles excluding metal particles, more preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles. The base particles may be base particles excluding inorganic particles. The base particles may be core-shell particles including a core and a shell disposed on a surface of the core. The core may be an organic core, and the shell may be an inorganic shell.
　上記基材粒子は、樹脂粒子又は有機無機ハイブリッド粒子であることがさらに好ましく、樹脂粒子であってもよく、有機無機ハイブリッド粒子であってもよい。これらの好ましい基材粒子の使用により、本発明の効果がより一層効果的に発揮され、電極間の電気的な接続により一層適した導電性粒子が得られる。 The base particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles. By using these preferred base particles, the effects of the present invention are more effectively exhibited, and conductive particles more suitable for electrical connection between electrodes can be obtained.
　上記導電性粒子を用いて電極間を接続する際には、上記導電性粒子を電極間に配置した後、圧着することにより上記導電性粒子を圧縮させる。基材粒子が樹脂粒子又は有機無機ハイブリッド粒子であると、上記圧着の際に上記導電性粒子が変形しやすく、導電性粒子と電極との接触面積が大きくなる。このため、電極間の導通信頼性がより一層高くなる。 に は When connecting the electrodes using the conductive particles, the conductive particles are arranged between the electrodes, and then the conductive particles are compressed by pressing. When the base particles are resin particles or organic-inorganic hybrid particles, the conductive particles are likely to be deformed at the time of the press bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction reliability between the electrodes is further improved.
　上記樹脂粒子の材料として、種々の樹脂が好適に用いられる。上記樹脂粒子の材料としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリイソブチレン、ポリブタジエン等のポリオレフィン樹脂；ポリメチルメタクリレート、ポリメチルアクリレート等のアクリル樹脂；ポリアルキレンテレフタレート、ポリカーボネート、ポリアミド、フェノールホルムアルデヒド樹脂、メラミンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂、フェノール樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ポリスルホン、ポリフェニレンオキサイド、ポリアセタール、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルスルホン、ジビニルベンゼン重合体、ジビニルベンゼン系共重合体、及び、エチレン性不飽和基を有する種々の重合性単量体を１種もしくは２種以上重合させて得られる重合体等が挙げられる。上記ジビニルベンゼン系共重合体としては、ジビニルベンゼン－スチレン共重合体及びジビニルベンゼン－（メタ）アクリル酸エステル共重合体等が挙げられる。 種 々 Various resins are suitably used as the material of the resin particles. Examples of the material of the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polyalkylene terephthalate and polycarbonate , Polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polysulfone, polyphenylene oxide, polyacetal, Polyimide, polyamide imide, polyetheretherketone, polyether Terusuruhon, divinylbenzene polymers, divinylbenzene copolymers, and polymers such as obtained by a variety of polymerizable monomer having an ethylenically unsaturated group is polymerized with one or more thereof. Examples of the divinylbenzene-based copolymer include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylate copolymer.
　導電材料に適した任意の圧縮特性を有する樹脂粒子を設計及び合成することができ、かつ樹脂粒子の硬度を好適な範囲に容易に制御できるので、上記樹脂粒子の材料は、エチレン性不飽和基を複数有する重合性単量体を１種又は２種以上重合させた重合体であることが好ましい。 Since the resin particles having any compression characteristics suitable for the conductive material can be designed and synthesized, and the hardness of the resin particles can be easily controlled to a suitable range, the material of the resin particles is an ethylenically unsaturated group. Is preferably a polymer obtained by polymerizing one or more polymerizable monomers having a plurality of
　上記樹脂粒子を、エチレン性不飽和基を有する重合性単量体を重合させて得る場合には、上記エチレン性不飽和基を有する重合性単量体としては、非架橋性の単量体と架橋性の単量体とが挙げられる。 When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer. And a crosslinkable monomer.
　上記非架橋性の単量体としては、例えば、スチレン、α－メチルスチレン等のスチレン系単量体；（メタ）アクリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート化合物；２－ヒドロキシエチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリオキシエチレン（メタ）アクリレート、グリシジル（メタ）アクリレート等の酸素原子含有（メタ）アクリレート化合物；（メタ）アクリロニトリル等のニトリル含有単量体；酢酸ビニル、酪酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等の酸ビニルエステル化合物；エチレン、プロピレン、イソプレン、ブタジエン等の不飽和炭化水素；トリフルオロメチル（メタ）アクリレート、ペンタフルオロエチル（メタ）アクリレート、塩化ビニル、フッ化ビニル、クロルスチレン等のハロゲン含有単量体等が挙げられる。 Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and α-methylstyrene; carboxyl-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, and the like Oxygen atom-containing (meth) acrylate compounds; nitrile-containing monomers such as (meth) acrylonitrile; acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; ethylene, propylene, isoprene, butadiene, etc. Unsaturated hydrocarbons; and halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene.
　上記架橋性の単量体としては、例えば、テトラメチロールメタンテトラ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、（ポリ）テトラメチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート等の多官能（メタ）アクリレート化合物；トリアリル（イソ）シアヌレート、トリアリルトリメリテート、ジビニルベンゼン、ジアリルフタレート、ジアリルアクリルアミド、ジアリルエーテル、γ－（メタ）アクリロキシプロピルトリメトキシシラン、トリメトキシシリルスチレン、ビニルトリメトキシシラン等のシラン含有単量体等が挙げられる。 Examples of the crosslinkable monomer include tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, and dipentane. Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylate compounds such as acrylate, (poly) tetramethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate; triallyl (iso) cia And silane-containing monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, and vinyltrimethoxysilane. No.
　上記エチレン性不飽和基を有する重合性単量体を、公知の方法により重合させることで、上記樹脂粒子を得ることができる。この方法としては、例えば、ラジカル重合開始剤の存在下で懸濁重合する方法、並びに非架橋の種粒子を用いてラジカル重合開始剤とともに単量体を膨潤させて重合する方法等が挙げられる。 上 記 The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of the method include a method of performing suspension polymerization in the presence of a radical polymerization initiator, and a method of performing polymerization by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
　上記基材粒子が金属粒子を除く無機粒子又は有機無機ハイブリッド粒子である場合には、基材粒子を形成するための無機物としては、シリカ、アルミナ、チタン酸バリウム、ジルコニア及びカーボンブラック等が挙げられる。上記無機物は、金属ではないことが好ましい。上記シリカにより形成された粒子としては特に限定されないが、例えば、加水分解性のアルコキシシリル基を２つ以上有するケイ素化合物を加水分解して架橋重合体粒子を形成した後に、必要に応じて焼成を行うことにより得られる粒子が挙げられる。上記有機無機ハイブリッド粒子としては、例えば、架橋したアルコキシシリルポリマーとアクリル樹脂とにより形成された有機無機ハイブリッド粒子等が挙げられる。 When the base particles are inorganic particles or organic-inorganic hybrid particles other than metal particles, examples of the inorganic substance for forming the base particles include silica, alumina, barium titanate, zirconia, and carbon black. . Preferably, the inorganic substance is not a metal. The particles formed of the silica are not particularly limited. For example, after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, baking is optionally performed. Particles obtained by performing the method are exemplified. Examples of the organic-inorganic hybrid particles include, for example, organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
　上記有機無機ハイブリッド粒子は、コアと、該コアの表面上に配置されたシェルとを有するコアシェル型の有機無機ハイブリッド粒子であることが好ましい。上記コアが有機コアであることが好ましい。上記シェルが無機シェルであることが好ましい。電極間の接続抵抗をより一層効果的に低くする観点からは、上記基材粒子は、有機コアと上記有機コアの表面上に配置された無機シェルとを有する有機無機ハイブリッド粒子であることが好ましい。 The organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core. Preferably, the core is an organic core. Preferably, the shell is an inorganic shell. From the viewpoint of lowering the connection resistance between the electrodes more effectively, the base particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core. .
　上記有機コアの材料としては、上述した樹脂粒子の材料等が挙げられる。 材料 Examples of the material of the organic core include the above-described materials of the resin particles.
　上記無機シェルの材料としては、上述した基材粒子の材料として挙げた無機物が挙げられる。上記無機シェルの材料は、シリカであることが好ましい。上記無機シェルは、上記コアの表面上で、金属アルコキシドをゾルゲル法によりシェル状物とした後、該シェル状物を焼成させることにより形成されていることが好ましい。上記金属アルコキシドはシランアルコキシドであることが好ましい。上記無機シェルはシランアルコキシドにより形成されていることが好ましい。 材料 Examples of the material of the inorganic shell include the inorganic substances described above as the material of the base particles. The material of the inorganic shell is preferably silica. The inorganic shell is preferably formed by forming a metal alkoxide into a shell by a sol-gel method on the surface of the core, and then firing the shell. The metal alkoxide is preferably a silane alkoxide. It is preferable that the inorganic shell is formed of a silane alkoxide.
　上記基材粒子が金属粒子である場合に、該金属粒子の材料である金属としては、銀、銅、ニッケル、ケイ素、金及びチタン等が挙げられる。但し、上記基材粒子は金属粒子ではないことが好ましい。 場合 When the base particles are metal particles, examples of the metal as a material of the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, the base particles are preferably not metal particles.
　上記基材粒子の平均粒子径は、好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上、より一層好ましくは０．５μｍ以上、さらに好ましくは１μｍ以上、さらに一層好ましくは３μｍ以上であり、好ましくは１００μｍ以下、より好ましくは６０μｍ以下、さらに好ましくは５０μｍ以下、特に好ましくは４０μｍ以下である。上記基材粒子の平均粒子径が、上記下限以上であると、導電性粒子と電極との接触面積が大きくなるため、電極間の導通信頼性がより一層高くなり、導電性粒子を介して接続された電極間の接続抵抗をより一層効果的に低くすることができる。さらに基材粒子の表面に導電部を形成する際に凝集し難くなり、凝集した導電性粒子が形成され難くなる。上記基材粒子の平均粒子径が、上記上限以下であると、導電性粒子が十分に圧縮されやすく、導電性粒子を介して接続された電極間の接続抵抗をより一層効果的に低くすることができる。 The average particle diameter of the base particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.5 μm or more, still more preferably 1 μm or more, and still more preferably 3 μm or more, preferably Is 100 μm or less, more preferably 60 μm or less, further preferably 50 μm or less, particularly preferably 40 μm or less. When the average particle diameter of the base particles is equal to or larger than the lower limit, the contact area between the conductive particles and the electrodes is increased, so that the reliability of conduction between the electrodes is further increased, and the connection via the conductive particles is performed. The connection resistance between the electrodes can be reduced more effectively. Further, when the conductive portion is formed on the surface of the base material particles, it is difficult to aggregate, and it is difficult to form the aggregated conductive particles. When the average particle diameter of the base particles is equal to or less than the upper limit, the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes connected via the conductive particles is more effectively reduced. Can be.
　上記基材粒子の平均粒子径は、０．００５μｍ以上４０μｍ以下であることが特に好ましい。上記基材粒子の平均粒子径が、０．００５μｍ以上４０μｍ以下の範囲内であると、電極間の間隔をより小さくすることができ、かつ導電部の厚みを厚くしても、小さい導電性粒子を得ることができる。 平均 It is particularly preferable that the average particle diameter of the base particles is 0.005 μm or more and 40 μm or less. When the average particle diameter of the base particles is in the range of 0.005 μm or more and 40 μm or less, the distance between the electrodes can be reduced, and even if the thickness of the conductive portion is increased, the small conductive particles Can be obtained.
　上記基材粒子の粒子径は、基材粒子が真球状である場合には、直径を示し、基材粒子が真球状ではない場合には、最大径を示す。 粒子 The particle diameter of the base particles indicates a diameter when the base particles are truly spherical, and indicates a maximum diameter when the base particles are not true spherical.
　上記基材粒子の平均粒子径は、数平均粒子径であることが好ましい。上記基材粒子の平均粒子径は粒度分布測定装置等を用いて求められる。基材粒子の平均粒子径は、任意の基材粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することにより求めることが好ましい。導電性粒子において、上記基材粒子の平均粒子径を測定する場合には、例えば、以下のようにして測定できる。 平均 The average particle diameter of the base particles is preferably a number average particle diameter. The average particle diameter of the base particles is determined using a particle size distribution measuring device or the like. The average particle diameter of the base particles is preferably obtained by observing 50 arbitrary base particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the average particle diameter of the base particles in the conductive particles, for example, the measurement can be performed as follows.
　導電性粒子の含有量が３０重量％となるように、Ｋｕｌｚｅｒ社製「テクノビット４０００」に添加し、分散させて、導電性粒子検査用埋め込み樹脂を作製する。検査用埋め込み樹脂中に分散した導電性粒子の中心付近を通るようにイオンミリング装置（日立ハイテクノロジーズ社製「ＩＭ４０００」）を用いて、導電性粒子の断面を切り出す。そして、電界放射型走査型電子顕微鏡（ＦＥ－ＳＥＭ）を用いて、画像倍率を２５０００倍に設定し、５０個の導電性粒子を無作為に選択し、各導電性粒子の基材粒子を観察する。各導電性粒子における基材粒子の粒子径を計測し、それらを算術平均して基材粒子の粒子径とする。 (4) The resin is added to “Technobit 4000” manufactured by Kulzer Co., Ltd. so that the content of the conductive particles becomes 30% by weight, and dispersed to prepare an embedded resin for conductive particle inspection. The cross section of the conductive particles is cut out using an ion milling apparatus (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the resin for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 25,000 times, 50 conductive particles were randomly selected, and the base particles of each conductive particle were observed. I do. The particle diameter of the base particles in each conductive particle is measured, and the arithmetic average thereof is used as the particle diameter of the base particles.
　（導電部）
　上記基材粒子の表面上に導電部を形成する方法、並びに上記基材粒子の表面上又は上記第２の導電部の表面上にはんだ部を形成する方法は特に限定されない。上記導電部及び上記はんだ部を形成する方法としては、例えば、無電解めっきによる方法、電気めっきによる方法、物理的な衝突による方法、メカノケミカル反応による方法、物理的蒸着又は物理的吸着による方法、並びに金属粉末もしくは金属粉末とバインダーとを含むペーストを基材粒子の表面にコーティングする方法等が挙げられる。上記導電部及び上記はんだ部を形成する方法は、無電解めっき、電気めっき又は物理的な衝突による方法であることが好ましい。上記物理的蒸着による方法としては、真空蒸着、イオンプレーティング及びイオンスパッタリング等の方法が挙げられる。また、上記物理的な衝突による方法では、例えば、シーターコンポーザ（徳寿工作所社製）等が用いられる。 (Conductive part)
The method for forming the conductive portion on the surface of the base particles and the method for forming the solder portion on the surface of the base particles or the surface of the second conductive portion are not particularly limited. As a method of forming the conductive portion and the solder portion, for example, a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption, And a method of coating the surface of the base particles with a metal powder or a paste containing the metal powder and a binder. The method of forming the conductive portion and the solder portion is preferably a method using electroless plating, electroplating, or physical collision. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. In the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kosakusho) is used.
　上記基材粒子の融点は、上記導電部及び上記はんだ部の融点よりも高いことが好ましい。上記基材粒子の融点は、好ましくは１６０℃を超え、より好ましくは３００℃を超え、さらに好ましくは４００℃を超え、特に好ましくは４５０℃を超える。なお、上記基材粒子の融点は、４００℃未満であってもよい。上記基材粒子の融点は、１６０℃以下であってもよい。上記基材粒子の軟化点は２６０℃以上であることが好ましい。上記基材粒子の軟化点は２６０℃未満であってもよい。 融 点 The melting point of the base particles is preferably higher than the melting points of the conductive part and the solder part. The melting point of the base particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, further preferably higher than 400 ° C, particularly preferably higher than 450 ° C. Note that the melting point of the base particles may be lower than 400 ° C. The melting point of the base particles may be 160 ° C. or lower. The softening point of the base particles is preferably 260 ° C. or higher. The softening point of the base particles may be less than 260 ° C.
　上記導電性粒子は、単層のはんだ部を有していてもよい。上記導電性粒子は、複数の層の導電部（はんだ部，第２の導電部）を有していてもよい。すなわち、上記導電性粒子では、導電部を２層以上積層してもよい。上記導電部が２層以上の場合、上記導電性粒子は、導電部の外表面部分にはんだを有することが好ましい。 The conductive particles may have a single-layer solder portion. The conductive particles may have a plurality of layers of conductive portions (solder portions, second conductive portions). That is, in the conductive particles, two or more conductive portions may be laminated. When the conductive portion has two or more layers, it is preferable that the conductive particles have solder on an outer surface portion of the conductive portion.
　上記はんだは、融点が４５０℃以下である金属（低融点金属）であることが好ましい。上記はんだ部は、融点が４５０℃以下である金属層（低融点金属層）であることが好ましい。上記低融点金属層は、低融点金属を含む層である。上記導電性粒子におけるはんだ及び上記はんだ粒子は、融点が４５０℃以下である金属粒子（低融点金属粒子）であることが好ましい。上記低融点金属粒子は、低融点金属を含む粒子である。上記低融点金属とは、融点が４５０℃以下の金属を示す。上記低融点金属の融点は、好ましくは３００℃以下、より好ましくは１６０℃以下である。 The solder is preferably a metal having a melting point of 450 ° C. or lower (a low melting point metal). The solder part is preferably a metal layer having a melting point of 450 ° C. or lower (low-melting metal layer). The low melting point metal layer is a layer containing a low melting point metal. The solder and the solder particles in the conductive particles are preferably metal particles having a melting point of 450 ° C. or lower (low-melting metal particles). The low melting point metal particles are particles containing a low melting point metal. The low-melting-point metal refers to a metal having a melting point of 450 ° C. or less. The melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
　上記低融点金属の融点及び上記はんだ粒子の融点は、示差走査熱量測定（ＤＳＣ）により求めることができる。示差走査熱量測定（ＤＳＣ）装置としては、ＳＩＩ社製「ＥＸＳＴＡＲ　ＤＳＣ７０２０」等が挙げられる。 融 点 The melting point of the low melting point metal and the melting point of the solder particles can be determined by differential scanning calorimetry (DSC). As the differential scanning calorimeter (DSC) device, “EXSTAR DSC7020” manufactured by SII and the like can be mentioned.
　また、上記導電性粒子におけるはんだは、錫を含むことが好ましい。上記はんだ部に含まれる金属１００重量％中及び上記導電性粒子におけるはんだに含まれる金属１００重量％中、錫の含有量は、好ましくは３０重量％以上、より好ましくは４０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは９０重量％以上である。上記はんだ部及び上記導電性粒子におけるはんだに含まれる錫の含有量が、上記下限以上であると、導電性粒子と電極との導通信頼性がより一層高くなる。 は ん だ The solder in the conductive particles preferably contains tin. In 100% by weight of the metal contained in the solder part and 100% by weight of the metal contained in the solder in the conductive particles, the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably. Is 70% by weight or more, particularly preferably 90% by weight or more. When the content of tin contained in the solder in the solder portion and the conductive particles is equal to or more than the lower limit, the conduction reliability between the conductive particles and the electrode is further improved.
　なお、上記錫の含有量は、高周波誘導結合プラズマ発光分光分析装置（堀場製作所社製「ＩＣＰ－ＡＥＳ」）、又は蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ－８００ＨＳ」）等を用いて測定することができる。 The tin content was measured using a high-frequency inductively coupled plasma emission spectrometer ("ICP-AES" manufactured by Horiba, Ltd.) or an X-ray fluorescence analyzer ("EDX-800HS" manufactured by Shimadzu, Ltd.). Can be measured.
　上記はんだを導電部の外表面部分に有する導電性粒子を用いることで、はんだが溶融して電極に接合し、はんだが電極間を導通させる。例えば、はんだと電極とが点接触ではなく面接触しやすいため、接続抵抗が低くなる。また、はんだを導電部の外表面部分に有する導電性粒子の使用により、はんだと電極との接合強度が高くなる結果、はんだと電極との剥離がより一層生じ難くなり、導通信頼性が効果的に高くなる。 用 い る By using the conductive particles having the solder on the outer surface of the conductive portion, the solder is melted and joined to the electrodes, and the solder conducts between the electrodes. For example, since the solder and the electrode are likely to make surface contact, not point contact, the connection resistance is reduced. In addition, the use of conductive particles having solder on the outer surface of the conductive portion increases the bonding strength between the solder and the electrode, so that peeling of the solder and the electrode is more unlikely to occur, and the conduction reliability is effectively improved. Become higher.
　上記はんだ部及び上記はんだを構成する低融点金属は特に限定されない。該低融点金属は、錫、又は錫を含む合金であることが好ましい。該合金としては、錫－銀合金、錫－銅合金、錫－銀－銅合金、錫－ビスマス合金、錫－亜鉛合金、錫－インジウム合金等が挙げられる。電極に対する濡れ性に優れることから、上記低融点金属は、錫、錫－銀合金、錫－銀－銅合金、錫－ビスマス合金、錫－インジウム合金であることが好ましい。錫－ビスマス合金、錫－インジウム合金であることがより好ましい。 (4) The solder portion and the low-melting-point metal forming the solder are not particularly limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy. The low melting point metal is preferably tin, a tin-silver alloy, a tin-silver-copper alloy, a tin-bismuth alloy, or a tin-indium alloy because of its excellent wettability to the electrode. More preferably, it is a tin-bismuth alloy or a tin-indium alloy.
　上記はんだ（はんだ部）を構成する材料は、ＪＩＳ　Ｚ３００１：溶接用語に基づき、液相線が４５０℃以下である溶加材であることが好ましい。上記はんだの組成としては、例えば亜鉛、金、銀、鉛、銅、錫、ビスマス、インジウム等を含む金属組成が挙げられる。低融点で鉛フリーである錫－インジウム系（１１７℃共晶）、又は錫－ビスマス系（１３９℃共晶）が好ましい。すなわち、上記はんだは、鉛を含まないことが好ましく、錫とインジウムとを含むはんだ、又は錫とビスマスとを含むはんだであることが好ましい。 (4) The material forming the solder (solder portion) is preferably a filler material having a liquidus of 450 ° C. or less based on JIS Z3001: welding terminology. Examples of the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium, and the like. A tin-indium (eutectic at 117 ° C.) or tin-bismuth (eutectic at 139 ° C.), which is low melting point and lead-free, is preferred. That is, the solder preferably does not contain lead, and is preferably a solder containing tin and indium, or a solder containing tin and bismuth.
　はんだ部又は導電性粒子におけるはんだと電極との接合強度をより一層高めるために、上記導電性粒子におけるはんだは、ニッケル、銅、アンチモン、アルミニウム、亜鉛、鉄、金、チタン、リン、ゲルマニウム、テルル、コバルト、ビスマス、マンガン、クロム、モリブデン、パラジウム等の金属を含んでいてもよい。また、はんだ部又は導電性粒子におけるはんだと電極との接合強度をさらに一層高める観点からは、上記導電性粒子におけるはんだは、ニッケル、銅、アンチモン、アルミニウム又は亜鉛を含むことが好ましい。はんだ部又は導電性粒子におけるはんだと電極との接合強度をより一層高める観点からは、接合強度を高めるためのこれらの金属の含有量は、上記導電性粒子におけるはんだ１００重量％中、好ましくは０．０００１重量％以上、好ましくは１重量％以下である。 In order to further increase the bonding strength between the solder and the electrode in the solder portion or the conductive particles, the solder in the conductive particles may be nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium. , Cobalt, bismuth, manganese, chromium, molybdenum, palladium and the like. From the viewpoint of further increasing the bonding strength between the solder and the electrode in the solder portion or the conductive particles, the solder in the conductive particles preferably contains nickel, copper, antimony, aluminum, or zinc. From the viewpoint of further increasing the bonding strength between the solder and the electrode in the solder portion or the conductive particles, the content of these metals for increasing the bonding strength is preferably 0% in 100% by weight of the solder in the conductive particles. 0.0001% by weight or more, preferably 1% by weight or less.
　上記第２の導電部の融点は、上記はんだ部の融点よりも高いことが好ましい。上記第２の導電部の融点は、好ましくは１６０℃を超え、より好ましくは３００℃を超え、さらに好ましくは４００℃を超え、さらに一層好ましくは４５０℃を超え、特に好ましくは５００℃を超え、最も好ましくは６００℃を超える。上記はんだ部は融点が低いために導電接続時に溶融する。上記第２の導電部は導電接続時に溶融しないことが好ましい。上記導電性粒子は、はんだを溶融させて用いられることが好ましく、上記はんだ部を溶融させて用いられることが好ましく、上記はんだ部を溶融させてかつ上記第２の導電部を溶融させずに用いられることが好ましい。上記第２の導電部の融点が上記はんだ部の融点をよりも高いことによって、導電接続時に、上記第２の導電部を溶融させずに、上記はんだ部のみを溶融させることができる。 融 点 It is preferable that the melting point of the second conductive part is higher than the melting point of the solder part. The melting point of the second conductive portion is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, still more preferably higher than 450 ° C, particularly preferably higher than 500 ° C, Most preferably above 600 ° C. Since the above-mentioned solder part has a low melting point, it melts at the time of conductive connection. It is preferable that the second conductive portion does not melt at the time of conductive connection. The conductive particles are preferably used by melting solder, preferably used by melting the solder portion, used without melting the solder portion and without melting the second conductive portion. Preferably. Since the melting point of the second conductive part is higher than the melting point of the solder part, only the solder part can be melted without melting the second conductive part at the time of conductive connection.
　上記はんだ部の融点と上記第２の導電部との融点との差の絶対値は、０℃を超え、好ましくは５℃以上、より好ましくは１０℃以上、さらに好ましくは３０℃以上、特に好ましくは５０℃以上、最も好ましくは１００℃以上である。 The absolute value of the difference between the melting point of the solder part and the melting point of the second conductive part exceeds 0 ° C., preferably 5 ° C. or more, more preferably 10 ° C. or more, still more preferably 30 ° C. or more, and particularly preferably. Is at least 50 ° C, most preferably at least 100 ° C.
　上記第２の導電部は、金属を含むことが好ましい。上記第２の導電部を構成する金属は、特に限定されない。該金属としては、例えば、金、銀、銅、白金、パラジウム、亜鉛、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモン、ビスマス、ゲルマニウム及びカドミウム、並びにこれらの合金等が挙げられる。また、上記金属として、錫ドープ酸化インジウム（ＩＴＯ）を用いてもよい。上記金属は１種のみが用いられてもよく、２種以上が併用されてもよい。 The second conductive portion preferably contains a 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, cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. One of the above metals may be used alone, or two or more thereof may be used in combination.
　上記第２の導電部は、ニッケル層、パラジウム層、銅層又は金層であることが好ましく、ニッケル層、金層又は銅層であることがより好ましく、銅層であることがさらに好ましい。導電性粒子は、ニッケル層、パラジウム層、銅層又は金層を有することが好ましく、ニッケル層、金層又は銅層を有することがより好ましく、銅層を有することがさらに好ましい。これらの好ましい導電部を有する導電性粒子を電極間の接続に用いることにより、電極間の接続抵抗がより一層低くなる。また、これらの好ましい導電部の表面には、はんだ部をより一層容易に形成できる。 The second conductive portion is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer, a gold layer or a copper layer, and further preferably a copper layer. The conductive particles preferably have a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably have a nickel layer, a gold layer or a copper layer, and further preferably have a copper layer. By using the conductive particles having these preferable conductive portions for the connection between the electrodes, the connection resistance between the electrodes is further reduced. Further, a solder portion can be more easily formed on the surface of these preferable conductive portions.
　上記はんだ部の厚みは、好ましくは０．００５μｍ以上、より好ましくは０．０１μｍ以上であり、好ましくは１０μｍ以下、より好ましくは１μｍ以下、さらに好ましくは０．３μｍ以下である。はんだ部の厚みが、上記下限以上及び上記上限以下であると、十分な導電性が得られ、かつ導電性粒子が硬くなりすぎずに、電極間の接続の際に導電性粒子が十分に変形する。 厚 み The thickness of the solder part is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 0.3 μm or less. When the thickness of the solder portion is equal to or more than the lower limit and equal to or less than the upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. I do.
　上記導電性粒子の平均粒子径は、好ましくは０．０１μｍ以上、より好ましくは０．５μｍ以上、より一層好ましくは１μｍ以上、さらに好ましくは３μｍ以上であり、好ましくは１００μｍ以下、より好ましくは６０μｍ以下、さらに好ましくは５０μｍ以下、特に好ましくは４０μｍ以下である。上記導電性粒子の平均粒子径が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができ、電極間に導電性粒子におけるはんだを多く配置することが容易であり、導通信頼性がより一層高くなる。 The average particle diameter of the conductive particles is preferably 0.01 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, further preferably 3 μm or more, preferably 100 μm or less, more preferably 60 μm or less. And more preferably 50 μm or less, particularly preferably 40 μm or less. When the average particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the solder in the conductive particles can be disposed between the electrodes. It is easy to arrange many, and the conduction reliability is further improved.
　上記導電性粒子の平均粒子径は、数平均粒子径であることがより好ましい。導電性粒子の平均粒子径は、例えば、任意の導電性粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、平均値を算出することや、レーザー回折式粒度分布測定を行うことにより求められる。 平均 The average particle diameter of the conductive particles is more preferably a number average particle diameter. The average particle size of the conductive particles can be determined, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing a laser diffraction particle size distribution measurement.
　上記導電性粒子の粒子径のＣＶ値は、好ましくは５％以上、より好ましくは１０％以上であり、好ましくは４０％以下、より好ましくは３０％以下である。上記粒子径のＣＶ値が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができる。但し、上記導電性粒子の粒子径のＣＶ値は、５％未満であってもよい。 Ｃ The CV value of the particle size of the conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less. When the CV value of the particle diameter is equal to or more than the lower limit and equal to or less than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrode. However, the CV value of the particle size of the conductive particles may be less than 5%.
　上記導電性粒子の粒子径のＣＶ値（変動係数）は、以下のようにして測定できる。 Ｃ The CV value (coefficient of variation) of the particle diameter of the conductive particles can be measured as follows.
　ＣＶ値（％）＝（ρ／Ｄｎ）×１００
　ρ：導電性粒子の粒子径の標準偏差
　Ｄｎ：導電性粒子の粒子径の平均値 CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of the particle size of the conductive particles Dn: Average value of the particle size of the conductive particles
　上記導電性粒子の形状は特に限定されない。上記導電性粒子の形状は、球状であってもよく、球状以外の形状であってもよく、扁平状等の形状であってもよい。 形状 The shape of the conductive particles is not particularly limited. The shape of the conductive particles may be spherical, may be other than spherical, or may be flat or the like.
　導電材料１００重量％中、上記導電性粒子の含有量は、好ましくは１重量％以上、より好ましくは２重量％以上、さらに好ましくは１０重量％以上、特に好ましくは２０重量％以上、最も好ましくは３０重量％以上であり、好ましくは８０重量％以下、より好ましくは６０重量％以下、さらに好ましくは５０重量％以下である。上記導電性粒子の含有量が、上記下限以上及び上記上限以下であると、電極上に導電性粒子をより一層効率的に配置することができ、電極間に導電性粒子を多く配置することが容易であり、導通信頼性がより一層高くなる。導通信頼性をより一層高める観点からは、上記導電性粒子の含有量は多い方が好ましい。 In 100% by weight of the conductive material, the content of the conductive particles is preferably 1% by weight or more, more preferably 2% by weight or more, further preferably 10% by weight or more, particularly preferably 20% by weight or more, and most preferably. It is at least 30% by weight, preferably at most 80% by weight, more preferably at most 60% by weight, further preferably at most 50% by weight. When the content of the conductive particles is equal to or more than the lower limit and equal to or less than the upper limit, the conductive particles can be more efficiently arranged on the electrodes, and more conductive particles can be arranged between the electrodes. It is easy and the conduction reliability is further improved. From the viewpoint of further improving conduction reliability, it is preferable that the content of the conductive particles is large.
　（熱硬化性成分）
　本発明に係る導電材料は、熱硬化性成分を含む。上記熱硬化性成分は、熱硬化性化合物を含むことが好ましい。上記導電材料は、熱硬化性成分として、熱硬化性化合物と熱硬化剤とを含んでいてもよい。導電材料をより一層良好に硬化させるために、上記導電材料は、熱硬化性成分として、熱硬化性化合物と熱硬化剤とを含むことが好ましい。導電材料をより一層良好に硬化させるために、上記導電材料は、熱硬化性成分として硬化促進剤を含むことが好ましい。 (Thermosetting component)
The conductive material according to the present invention contains a thermosetting component. The thermosetting component preferably contains a thermosetting compound. The conductive material may include a thermosetting compound and a thermosetting agent as thermosetting components. In order to cure the conductive material more favorably, the conductive material preferably contains a thermosetting compound and a thermosetting agent as thermosetting components. In order to cure the conductive material more favorably, the conductive material preferably contains a curing accelerator as a thermosetting component.
　（熱硬化性成分：熱硬化性化合物）
　本発明に係る導電材料は、熱硬化性化合物を含むことが好ましい。上記熱硬化性化合物は、加熱により硬化可能な化合物である。上記熱硬化性化合物は特に限定されない。上記熱硬化性化合物としては、オキセタン化合物、エポキシ化合物、エピスルフィド化合物、（メタ）アクリル化合物、フェノール化合物、アミノ化合物、不飽和ポリエステル化合物、ポリウレタン化合物、シリコーン化合物及びポリイミド化合物等が挙げられる。導電材料の硬化性及び粘度をより一層良好にし、導通信頼性をより一層高める観点から、エポキシ化合物又はエピスルフィド化合物が好ましく、エポキシ化合物がより好ましい。上記導電材料は、エポキシ化合物を含むことが好ましい。上記熱硬化性化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Thermosetting component: thermosetting compound)
The conductive material according to the present invention preferably contains a thermosetting compound. The thermosetting compound is a compound that can be cured by heating. The thermosetting compound is not particularly limited. Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. From the viewpoint of further improving the curability and viscosity of the conductive material and further enhancing the conduction reliability, an epoxy compound or an episulfide compound is preferable, and an epoxy compound is more preferable. The conductive material preferably contains an epoxy compound. Only one kind of the thermosetting compound may be used, or two or more kinds thereof may be used in combination.
　上記エポキシ化合物は、少なくとも１個のエポキシ基を有する化合物である。上記エポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、フェノールノボラック型エポキシ化合物、ビフェニル型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、ビフェノール型エポキシ化合物、ナフタレン型エポキシ化合物、フルオレン型エポキシ化合物、フェノールアラルキル型エポキシ化合物、ナフトールアラルキル型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物、アントラセン型エポキシ化合物、アダマンタン骨格を有するエポキシ化合物、トリシクロデカン骨格を有するエポキシ化合物、ナフチレンエーテル型エポキシ化合物、及びトリアジン核を骨格に有するエポキシ化合物等が挙げられる。上記エポキシ化合物は１種のみが用いられてもよく、２種以上が併用されてもよい。 The epoxy compound is a compound having at least one epoxy group. Examples of the epoxy compound include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a phenol novolak epoxy compound, a biphenyl epoxy compound, a biphenyl novolak epoxy compound, a biphenol epoxy compound, and a naphthalene epoxy compound. , Fluorene type epoxy compound, phenol aralkyl type epoxy compound, naphthol aralkyl type epoxy compound, dicyclopentadiene type epoxy compound, anthracene type epoxy compound, epoxy compound having an adamantane skeleton, epoxy compound having a tricyclodecane skeleton, naphthylene ether type An epoxy compound and an epoxy compound having a triazine nucleus in a skeleton are exemplified. One of the above epoxy compounds may be used alone, or two or more thereof may be used in combination.
　上記エポキシ化合物は、常温（２３℃）で液状又は固体であり、上記エポキシ化合物が常温で固体である場合には、上記エポキシ化合物の溶融温度は、上記はんだの融点以下であることが好ましい。上記の好ましいエポキシ化合物を用いることで、接続対象部材を貼り合わせた段階では、粘度が高く、搬送等の衝撃により加速度が付与された際に、第１の接続対象部材と、第２の接続対象部材との位置ずれを抑制することができる。さらに、硬化時の熱により、導電材料の粘度を大きく低下させることができ、導電性粒子におけるはんだの凝集を効率よく進行させることができる。 The epoxy compound is liquid or solid at normal temperature (23 ° C.). When the epoxy compound is solid at normal temperature, the melting temperature of the epoxy compound is preferably equal to or lower than the melting point of the solder. By using the above preferred epoxy compound, at the stage where the connection target members are bonded, when the viscosity is high and acceleration is applied by an impact such as transportation, the first connection target member and the second connection target The displacement with respect to the member can be suppressed. Further, the viscosity of the conductive material can be greatly reduced by the heat at the time of curing, and the aggregation of the solder in the conductive particles can be efficiently advanced.
　絶縁信頼性をより一層効果的に高める観点、及び導通信頼性をより一層効果的に高める観点からは、上記熱硬化性成分はエポキシ化合物を含むことが好ましく、上記熱硬化性化合物はエポキシ化合物を含むことが好ましい。 From the viewpoint of more effectively improving the insulation reliability, and from the viewpoint of more effectively improving the conduction reliability, the thermosetting component preferably contains an epoxy compound, and the thermosetting compound is an epoxy compound. It is preferred to include.
　電極上に導電性粒子におけるはんだをより一層効果的に配置する観点からは、上記熱硬化性化合物は、ポリエーテル骨格を有する熱硬化性化合物を含むことが好ましい。 From the viewpoint of more effectively disposing the solder in the conductive particles on the electrode, the thermosetting compound preferably includes a thermosetting compound having a polyether skeleton.
　上記ポリエーテル骨格を有する熱硬化性化合物としては、炭素数３～１２のアルキル鎖の両末端にグリシジルエーテル基を有する化合物、並びに炭素数２～４のポリエーテル骨格を有し、該ポリエーテル骨格２～１０個が連続して結合した構造単位を有するポリエーテル型エポキシ化合物等が挙げられる。 Examples of the thermosetting compound having a polyether skeleton include a compound having a glycidyl ether group at both terminals of an alkyl chain having 3 to 12 carbon atoms, and a polyether skeleton having a polyether skeleton having 2 to 4 carbon atoms. Examples include polyether type epoxy compounds having a structural unit in which 2 to 10 are continuously bonded.
　硬化物の耐熱性をより一層効果的に高める観点からは、上記熱硬化性化合物は、イソシアヌル骨格を有する熱硬化性化合物を含むことが好ましい。 From the viewpoint of more effectively improving the heat resistance of the cured product, the thermosetting compound preferably contains a thermosetting compound having an isocyanuric skeleton.
　上記イソシアヌル骨格を有する熱硬化性化合物としてはトリイソシアヌレート型エポキシ化合物等が挙げられ、日産化学工業社製ＴＥＰＩＣシリーズ（ＴＥＰＩＣ－Ｇ、ＴＥＰＩＣ－Ｓ、ＴＥＰＩＣ－ＳＳ、ＴＥＰＩＣ－ＨＰ、ＴＥＰＩＣ－Ｌ、ＴＥＰＩＣ－ＰＡＳ、ＴＥＰＩＣ－ＶＬ、ＴＥＰＩＣ－ＵＣ）等が挙げられる。 Examples of the thermosetting compound having an isocyanuric skeleton include a triisocyanurate type epoxy compound, and a TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, manufactured by Nissan Chemical Industries, Ltd.). TEPIC-PAS, TEPIC-VL, and TEPIC-UC).
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点、接続されるべき上下の電極間の導通信頼性をより一層効果的に高める観点、及び熱硬化性化合物の変色をより一層効果的に抑制する観点からは、上記熱硬化性化合物は、高い耐熱性を有することが好ましく、ノボラック型エポキシ化合物であることがより好ましい。ノボラック型エポキシ化合物は、比較的高い耐熱性を有する。 From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrodes, from the viewpoint of more effectively improving the conduction reliability between the upper and lower electrodes to be connected, and from the discoloration of the thermosetting compound. From the viewpoint of suppressing the temperature, the thermosetting compound preferably has high heat resistance, and is more preferably a novolak-type epoxy compound. Novolak-type epoxy compounds have relatively high heat resistance.
　上記導電材料１００重量％中、上記熱硬化性化合物の含有量は、好ましくは５重量％以上、より好ましくは８重量％以上、さらに好ましくは１０重量％以上であり、好ましくは９９重量％以下、より好ましくは９０重量％以下、さらに好ましくは８０重量％以下、特に好ましくは７０重量％以下である。上記熱硬化性化合物の含有量が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置し、電極間の絶縁信頼性をより一層効果的に高めることができ、電極間の導通信頼性をより一層効果的に高めることができる。耐衝撃性をより一層効果的に高める観点からは、上記熱硬化性化合物の含有量は多い方が好ましい。 In 100% by weight of the conductive material, the content of the thermosetting compound is preferably 5% by weight or more, more preferably 8% by weight or more, further preferably 10% by weight or more, and preferably 99% by weight or less, It is more preferably at most 90% by weight, further preferably at most 80% by weight, particularly preferably at most 70% by weight. When the content of the thermosetting compound is not less than the lower limit and not more than the upper limit, the solder in the conductive particles is more efficiently arranged on the electrodes, and the insulation reliability between the electrodes is more effectively improved. And the reliability of conduction between the electrodes can be more effectively increased. From the viewpoint of more effectively improving the impact resistance, the content of the thermosetting compound is preferably higher.
　上記導電材料１００重量％中、上記エポキシ化合物の含有量は、好ましくは５重量％以上、より好ましくは８重量％以上、さらに好ましくは１０重量％以上であり、好ましくは９９重量％以下、より好ましくは９０重量％以下、さらに好ましくは８０重量％以下、特に好ましくは７０重量％以下である。上記エポキシ化合物の含有量が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置し、電極間の絶縁信頼性をより一層効果的に高めることができ、電極間の導通信頼性をより一層効果的に高めることができる。耐衝撃性をより一層高める観点からは、上記エポキシ化合物の含有量は多い方が好ましい。 In 100% by weight of the conductive material, the content of the epoxy compound is preferably 5% by weight or more, more preferably 8% by weight or more, further preferably 10% by weight or more, and preferably 99% by weight or less, more preferably Is at most 90% by weight, more preferably at most 80% by weight, particularly preferably at most 70% by weight. When the content of the epoxy compound is equal to or more than the lower limit and equal to or less than the upper limit, the solder in the conductive particles is more efficiently arranged on the electrodes, and the insulation reliability between the electrodes is more effectively increased. And the reliability of conduction between the electrodes can be more effectively improved. From the viewpoint of further improving the impact resistance, the content of the epoxy compound is preferably higher.
　（熱硬化性成分：熱硬化剤）
　上記導電材料は、熱硬化剤を含むことが好ましい。上記導電材料は、上記熱硬化性化合物とともに熱硬化剤を含むことが好ましい。上記熱硬化剤は、上記熱硬化性化合物を熱硬化させる。上記熱硬化剤は特に限定されない。上記熱硬化剤としては、イミダゾール硬化剤、フェノール硬化剤、チオール硬化剤、アミン硬化剤、酸無水物硬化剤、熱カチオン硬化剤及び熱ラジカル発生剤等がある。上記熱硬化剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Thermosetting component: thermosetting agent)
The conductive material preferably contains a thermosetting agent. The conductive material preferably contains a thermosetting agent together with the thermosetting compound. The thermosetting agent thermosets the thermosetting compound. The thermosetting agent is not particularly limited. Examples of the thermal curing agent include an imidazole curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a thermal cationic curing agent, and a thermal radical generator. The thermosetting agent may be used alone or in combination of two or more.
　導電材料を低温でより一層速やかに硬化可能とする観点からは、上記熱硬化剤は、イミダゾール硬化剤、チオール硬化剤、又はアミン硬化剤であることが好ましい。また、上記熱硬化性化合物と上記熱硬化剤とを混合したときの保存安定性を高める観点からは、上記熱硬化剤は、潜在性の硬化剤であることが好ましい。潜在性の硬化剤は、潜在性イミダゾール硬化剤、潜在性チオール硬化剤又は潜在性アミン硬化剤であることが好ましい。なお、上記熱硬化剤は、ポリウレタン樹脂又はポリエステル樹脂等の高分子物質で被覆されていてもよい。 (4) From the viewpoint that the conductive material can be more rapidly cured at a low temperature, the thermal curing agent is preferably an imidazole curing agent, a thiol curing agent, or an amine curing agent. Further, from the viewpoint of increasing the storage stability when the thermosetting compound and the thermosetting agent are mixed, it is preferable that the thermosetting agent is a latent curing agent. Preferably, the latent curing agent is a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent. Note that the thermosetting agent may be coated with a polymer material such as a polyurethane resin or a polyester resin.
　上記イミダゾール硬化剤は特に限定されない。上記イミダゾール硬化剤としては、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン及び２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４－ベンジル－５－ヒドロキシメチルイミダゾール、２－パラトルイル－４－メチル－５－ヒドロキシメチルイミダゾール、２－メタトルイル－４－メチル－５－ヒドロキシメチルイミダゾール、２－メタトルイル－４，５－ジヒドロキシメチルイミダゾール、２－パラトルイル－４，５－ジヒドロキシメチルイミダゾール等における１Ｈ－イミダゾールの５位の水素をヒドロキシメチル基で、かつ、２位の水素をフェニル基またはトルイル基で置換したイミダゾール化合物等が挙げられる。 The imidazole curing agent is not particularly limited. Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6 -[2'-Methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2-paratolyl-4-methyl-5 -Hydroxymethylimidazole, 2-methatoryl-4-methyl-5-h In the loxymethylimidazole, 2-methtolyl-4,5-dihydroxymethylimidazole, 2-paratoluyl-4,5-dihydroxymethylimidazole, etc., the 5-position hydrogen of 1H-imidazole is a hydroxymethyl group, and the 2-position hydrogen is Examples include an imidazole compound substituted with a phenyl group or a toluyl group.
　上記チオール硬化剤は特に限定されない。上記チオール硬化剤としては、トリメチロールプロパントリス－３－メルカプトプロピオネート、ペンタエリスリトールテトラキス－３－メルカプトプロピオネート及びジペンタエリスリトールヘキサ－３－メルカプトプロピオネート等が挙げられる。 The thiol curing agent is not particularly limited. Examples of the thiol curing agent include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.
　上記アミン硬化剤は特に限定されない。上記アミン硬化剤としては、ヘキサメチレンジアミン、オクタメチレンジアミン、デカメチレンジアミン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラスピロ［５．５］ウンデカン、ビス（４－アミノシクロヘキシル）メタン、メタフェニレンジアミン及びジアミノジフェニルスルホン等が挙げられる。 The amine curing agent is not particularly limited. Examples of the amine curing agent include hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane, bis (4 -Aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone and the like.
　上記酸無水物硬化剤は特に限定されず、エポキシ化合物等の熱硬化性化合物の硬化剤として用いられる酸無水物であれば広く用いることができる。上記酸無水物硬化剤としては、無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルブテニルテトラヒドロ無水フタル酸、フタル酸誘導体の無水物、無水マレイン酸、無水ナジック酸、無水メチルナジック酸、無水グルタル酸、無水コハク酸、グリセリンビス無水トリメリット酸モノアセテート、及びエチレングリコールビス無水トリメリット酸等の２官能の酸無水物硬化剤、無水トリメリット酸等の３官能の酸無水物硬化剤、並びに、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、メチルシクロヘキセンテトラカルボン酸無水物、及びポリアゼライン酸無水物等の４官能以上の酸無水物硬化剤等が挙げられる。 The acid anhydride curing agent is not particularly limited, and any acid anhydride used as a curing agent for a thermosetting compound such as an epoxy compound can be widely used. Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylbutenyltetrahydrophthalic anhydride. Bifunctional, such as phthalic anhydride, maleic anhydride, nadic anhydride, methylnadic anhydride, glutaric anhydride, succinic anhydride, glycerin bis trimellitic anhydride monoacetate, and ethylene glycol bis trimellitic anhydride Acid anhydride curing agent, trifunctional acid anhydride curing agent such as trimellitic anhydride, and pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, and polyazelain anhydride Acid anhydride of 4 or more functional groups Curing agents.
　上記熱カチオン開始剤は特に限定されない。上記熱カチオン開始剤としては、ヨードニウム系カチオン硬化剤、オキソニウム系カチオン硬化剤及びスルホニウム系カチオン硬化剤等が挙げられる。上記ヨードニウム系カチオン硬化剤としては、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムヘキサフルオロホスファート等が挙げられる。上記オキソニウム系カチオン硬化剤としては、トリメチルオキソニウムテトラフルオロボラート等が挙げられる。上記スルホニウム系カチオン硬化剤としては、トリ－ｐ－トリルスルホニウムヘキサフルオロホスファート等が挙げられる。 The thermal cation initiator is not particularly limited. Examples of the thermal cation initiator include an iodonium-based cation curing agent, an oxonium-based cation curing agent, and a sulfonium-based cation curing agent. Examples of the above-mentioned iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate. Examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate. Examples of the sulfonium-based cationic curing agent include tri-p-tolylsulfonium hexafluorophosphate.
　上記熱ラジカル発生剤は特に限定されない。上記熱ラジカル発生剤としては、アゾ化合物及び有機過酸化物等が挙げられる。上記アゾ化合物としては、アゾビスイソブチロニトリル（ＡＩＢＮ）等が挙げられる。上記有機過酸化物としては、ジ－ｔｅｒｔ－ブチルペルオキシド及びメチルエチルケトンペルオキシド等が挙げられる。 The thermal radical generator is not particularly limited. Examples of the thermal radical generator include an azo compound and an organic peroxide. Examples of the azo compound include azobisisobutyronitrile (AIBN). Examples of the organic peroxide include di-tert-butyl peroxide and methyl ethyl ketone peroxide.
　上記熱硬化剤の反応開始温度は、好ましくは５０℃以上、より好ましくは７０℃以上、さらに好ましくは８０℃以上であり、好ましくは２５０℃以下、より好ましくは２００℃以下、さらに好ましくは１５０℃以下、特に好ましくは１４０℃以下である。上記熱硬化剤の反応開始温度が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだがより一層効率的に配置される。電極上に導電性粒子におけるはんだをより一層効率的に配置する観点、及び接続されるべき上下の電極間の導通信頼性をより一層効果的に高める観点からは、上記熱硬化剤の反応開始温度は、８０℃以上１４０℃以下であることが特に好ましい。 The reaction initiation temperature of the thermosetting agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 150 ° C. or lower. The temperature is particularly preferably 140 ° C. or lower. When the reaction start temperature of the thermosetting agent is equal to or higher than the lower limit and equal to or lower than the upper limit, the solder in the conductive particles is more efficiently arranged on the electrode. From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrodes, and from the viewpoint of more effectively improving the reliability of conduction between the upper and lower electrodes to be connected, the reaction start temperature of the thermosetting agent Is particularly preferably from 80 ° C to 140 ° C.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記熱硬化剤の反応開始温度は、上記はんだ粒子の融点よりも、高いことが好ましく、５℃以上高いことがより好ましく、１０℃以上高いことがさらに好ましい。 From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrodes, the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder particles, more preferably higher by 5 ° C. or more. Preferably, the temperature is higher by 10 ° C. or more.
　上記熱硬化剤の反応開始温度は、ＤＳＣでの発熱ピークの立ち上がり開始の温度を意味する。 反 応 The reaction start temperature of the thermosetting agent means a temperature at which a heat generation peak starts to rise in DSC.
　上記熱硬化剤の含有量は特に限定されない。上記熱硬化性化合物１００重量部に対して、上記熱硬化剤の含有量は、好ましくは０．０１重量部以上、より好ましくは１重量部以上であり、好ましくは２００重量部以下、より好ましくは１００重量部以下、さらに好ましくは７５重量部以下である。熱硬化剤の含有量が、上記下限以上であると、導電材料を十分に硬化させることが容易である。熱硬化剤の含有量が、上記上限以下であると、硬化後に硬化に関与しなかった余剰の熱硬化剤が残存し難くなり、かつ硬化物の耐熱性がより一層高くなる。 含有 The content of the 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, preferably at most 200 parts by weight, more preferably at most 200 parts by weight, based on 100 parts by weight of the thermosetting compound. 100 parts by weight or less, more preferably 75 parts by weight or less. When the content of the thermosetting agent is equal to or more than the above lower limit, it is easy to sufficiently cure the conductive material. When the content of the thermosetting agent is equal to or less than the above upper limit, the surplus thermosetting agent not involved in the curing after the curing hardly remains, and the heat resistance of the cured product is further increased.
　（熱硬化性成分：硬化促進剤）
　上記導電材料は硬化促進剤を含んでいてもよい。上記硬化促進剤は特に限定されない。上記硬化促進剤は、上記熱硬化性化合物と上記熱硬化剤との反応において硬化触媒として作用することが好ましい。上記硬化促進剤は、上記熱硬化性化合物との反応において硬化触媒として作用することが好ましい。上記硬化促進剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Thermosetting component: curing accelerator)
The conductive material may include a curing accelerator. The curing accelerator is not particularly limited. The curing accelerator preferably acts as a curing catalyst in the reaction between the thermosetting compound and the thermosetting agent. The curing accelerator preferably acts as a curing catalyst in the reaction with the thermosetting compound. Only one kind of the curing accelerator may be used, or two or more kinds may be used in combination.
　上記硬化促進剤としては、ホスホニウム塩、三級アミン、三級アミン塩、四級オニウム塩、三級ホスフィン、クラウンエーテル錯体、アミン錯体化合物及びホスホニウムイリド等が挙げられる。具体的には、上記硬化促進剤としては、イミダゾール化合物、イミダゾール化合物のイソシアヌル酸塩、ジシアンジアミド、ジシアンジアミドの誘導体、メラミン化合物、メラミン化合物の誘導体、ジアミノマレオニトリル、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ビス（ヘキサメチレン）トリアミン、トリエタノールアミン、ジアミノジフェニルメタン、有機酸ジヒドラジド等のアミン化合物、１，８－ジアザビシクロ［５，４，０］ウンデセン－７、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、三フッ化ホウ素、三フッ化ホウ素－アミン錯体化合物、並びに、トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリブチルホスフィン及びメチルジフェニルホスフィン等の有機リン化合物等が挙げられる。 硬化 Examples of the curing accelerator include phosphonium salts, tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, amine complex compounds, and phosphonium ylides. Specifically, as the curing accelerator, an imidazole compound, an isocyanurate of the imidazole compound, dicyandiamide, a derivative of dicyandiamide, a melamine compound, a derivative of a melamine compound, diaminomaleonitrile, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine , Bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide and other amine compounds, 1,8-diazabicyclo [5,4,0] undecene-7,3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, boron trifluoride, boron trifluoride-amine complex compound, and triphenylphosphine, tricyclohexylphosphine, tributylphosphine Emissions and organophosphorus compounds such as methyl diphenyl phosphine.
　上記ホスホニウム塩は特に限定されない。上記ホスホニウム塩としては、テトラノルマルブチルホスホニウムブロマイド、テトラノルマルブチルホスホニウムＯ－Ｏジエチルジチオリン酸、メチルトリブチルホスホニウムジメチルリン酸塩、テトラノルマルブチルホスホニウムベンゾトリアゾール、テトラノルマルブチルホスホニウムテトラフルオロボレート、及びテトラノルマルブチルホスホニウムテトラフェニルボレート等が挙げられる。 The phosphonium salt is not particularly limited. Examples of the phosphonium salt include tetra-n-butylphosphonium bromide, tetra-n-butyl phosphonium OO diethyldithiophosphoric acid, methyltributyl-phosphonium dimethyl phosphate, tetra-n-butyl phosphonium benzotriazole, tetra-n-butyl phosphonium tetrafluoroborate, and tetra-n-butyl And phosphonium tetraphenyl borate.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点、及び接続されるべき上下の電極間の導通信頼性をより一層効果的に高める観点からは、上記硬化促進剤は、イミダゾール化合物であることが好ましく、三フッ化ホウ素－アミン錯体化合物であることがより好ましい。 From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrodes, and from the viewpoint of more effectively improving the conduction reliability between the upper and lower electrodes to be connected, the curing accelerator is an imidazole compound. And more preferably a boron trifluoride-amine complex compound.
　上記熱硬化性化合物が良好に硬化するように、上記硬化促進剤の含有量は適宜選択される。上記熱硬化性化合物１００重量部に対する上記硬化促進剤の含有量は、好ましくは０．５重量部以上、より好ましくは０．８重量部以上であり、好ましくは１０重量部以下、より好ましくは８重量部以下である。上記硬化促進剤の含有量が、上記下限以上及び上記上限以下であると、上記熱硬化性化合物を良好に硬化させることができる。また、上記硬化促進剤の含有量が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができ、接続されるべき上下の電極間の導通信頼性をより一層効果的に高めることができる。 含有 The content of the curing accelerator is appropriately selected so that the thermosetting compound cures favorably. The content of the curing accelerator with respect to 100 parts by weight of the thermosetting compound is preferably 0.5 parts by weight or more, more preferably 0.8 parts by weight or more, preferably 10 parts by weight or less, more preferably 8 parts by weight or less. Not more than parts by weight. When the content of the curing accelerator is not less than the lower limit and not more than the upper limit, the thermosetting compound can be favorably cured. When the content of the curing accelerator is not less than the lower limit and not more than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the upper and lower electrodes to be connected can be arranged. Can be more effectively improved.
　（フラックス）
　本発明に係る導電材料は、フラックスを含む。フラックスを用いることで、導電接続時のはんだの凝集性をより一層効果的に高めることができる。 (flux)
The conductive material according to the present invention includes a flux. By using the flux, the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
　本発明に係る導電材料では、上記フラックスは、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物を含む。 In the conductive material according to the present invention, the flux includes a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a third compound having an amino group. And a liquid compound which is a reaction product with the compound of No. 4.
　上記カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩は、２５℃で固体である。上記カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物は、２５℃で液体である。 固体 The solid salt of the first compound having a carboxyl group and the second compound having an amino group is a solid at 25 ° C. The liquid compound which is a reaction product of the third compound having a carboxyl group and the fourth compound having an amino group is liquid at 25 ° C.
　上記カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩は、２５℃の導電材料中で固体であることが好ましい。上記カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物は、２５℃の導電材料中で液体であることが好ましい。 The solid salt of the first compound having a carboxyl group and the second compound having an amino group is preferably a solid in a conductive material at 25 ° C. The liquid compound that is a reaction product of the third compound having a carboxyl group and the fourth compound having an amino group is preferably a liquid in a conductive material at 25 ° C.
　上記第１の化合物及び上記第３の化合物は、金属の表面を洗浄する効果を有していることが好ましい。上記第２の化合物は、上記第１の化合物を中和する作用を有していることが好ましい。上記第４の化合物は、上記第３の化合物を中和する作用を有していることが好ましい。上記第２の化合物及び上記第４の化合物は、上記第１の化合物又は上記第３の化合物を中和する作用を有していることが好ましい。 It is preferable that the first compound and the third compound have an effect of cleaning the surface of the metal. It is preferable that the second compound has an action of neutralizing the first compound. It is preferable that the fourth compound has an action of neutralizing the third compound. It is preferable that the second compound and the fourth compound have an action of neutralizing the first compound or the third compound.
　上記固体塩は、固体であることが好ましく、上記第１の化合物と上記第２の化合物との中和反応物であることが好ましい。上記固体塩は、中和反応により生じた塩であることが好ましい。上記中和反応の条件としては、２５℃～６０℃の加熱温度及び５分間～３０分間の加熱時間の条件であることが好ましい。 The solid salt is preferably a solid, and is preferably a neutralized reaction product of the first compound and the second compound. The solid salt is preferably a salt generated by a neutralization reaction. The neutralization reaction is preferably performed at a heating temperature of 25 ° C. to 60 ° C. and a heating time of 5 minutes to 30 minutes.
　上記液体化合物は、液体であることが好ましく、上記第３の化合物と上記第４の化合物との反応物であることが好ましい。上記液体化合物は、上記固体塩とは異なる。上記液体化合物は、反応（脱水反応）により生じた化合物であることが好ましく、アミド結合を有することが好ましい。上記反応（脱水反応）の条件としては、１００℃～２００℃の加熱温度及び５分間～５時間の加熱時間の条件であることが好ましい。 The liquid compound is preferably a liquid, and is preferably a reaction product of the third compound and the fourth compound. The liquid compound is different from the solid salt. The liquid compound is preferably a compound generated by a reaction (dehydration reaction), and preferably has an amide bond. The reaction (dehydration reaction) is preferably performed at a heating temperature of 100 ° C. to 200 ° C. and a heating time of 5 minutes to 5 hours.
　上記固体塩の含有量の、上記液体化合物の含有量に対する重量比（固体塩の含有量／液体化合物の含有量）は、好ましくは２以上、より好ましくは４以上であり、好ましくは２０以下、より好ましくは１０以下である。上記重量比（固体塩の含有量／液体化合物の含有量）が、上記下限以上及び上記上限以下であると、導電材料の保存安定性をより一層効果的に高めることができ、導電材料中にフラックスをより一層高充填することができ、さらに、導電接続時のはんだの凝集性をより一層効果的に高めることができる。 The weight ratio of the content of the solid salt to the content of the liquid compound (content of the solid salt / content of the liquid compound) is preferably 2 or more, more preferably 4 or more, and preferably 20 or less. More preferably, it is 10 or less. When the weight ratio (content of the solid salt / content of the liquid compound) is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively improved, and The flux can be more highly filled, and the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
　上記第１の化合物及び上記第３の化合物は、カルボキシル基を有する有機化合物であることが好ましい。上記第１の化合物及び上記第３の化合物としては、脂肪族系カルボン酸であるマロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、クエン酸、リンゴ酸、環状脂肪族カルボン酸であるシクロヘキシルカルボン酸、１，４－シクロヘキシルジカルボン酸、芳香族カルボン酸であるイソフタル酸、テレフタル酸、トリメリット酸、及びエチレンジアミン四酢酸等が挙げられる。上記第１の化合物及び上記第３の化合物は、グルタル酸、アゼライン酸、又はリンゴ酸であることが好ましい。上記第１の化合物及び上記第３の化合物が、上記の好ましい態様を満足すると、導電材料の保存安定性をより一層効果的に高めることができ、導電材料中にフラックスをより一層高充填することができ、さらに、導電接続時のはんだの凝集性をより一層効果的に高めることができる。 The first compound and the third compound are preferably organic compounds having a carboxyl group. Examples of the first compound and the third compound include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, and malic acid, which are aliphatic carboxylic acids. And cyclohexylcarboxylic acid, 1,4-cyclohexyldicarboxylic acid, which is a cyclic aliphatic carboxylic acid, isophthalic acid, terephthalic acid, trimellitic acid, and ethylenediaminetetraacetic acid, which are aromatic carboxylic acids. The first compound and the third compound are preferably glutaric acid, azelaic acid, or malic acid. When the first compound and the third compound satisfy the above-described preferred embodiment, the storage stability of the conductive material can be more effectively improved, and the conductive material can be more highly filled with flux. In addition, the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
　上記第１の化合物と上記第３の化合物とは、同一の化合物であってもよく、異なる化合物であってもよい。導電材料の保存安定性をより一層効果的に高める観点、導電材料中にフラックスをより一層高充填する観点、及び導電接続時のはんだの凝集性をより一層効果的に高める観点からは、上記第１の化合物と上記第３の化合物とは、同一の化合物であることが好ましい。 The first compound and the third compound may be the same compound or different compounds. From the viewpoint of more effectively improving the storage stability of the conductive material, the viewpoint of further filling the conductive material with flux, and the viewpoint of more effectively increasing the cohesiveness of the solder during the conductive connection, It is preferable that the first compound and the third compound are the same compound.
　上記第２の化合物及び上記第４の化合物は、アミノ基を有する有機化合物であることが好ましい。上記第２の化合物及び上記第４の化合物としては、ジエタノールアミン、トリエタノールアミン、メチルジエタノールアミン、エチルジエタノールアミン、シクロヘキシルアミン、ジシクロヘキシルアミン、ベンジルアミン、ベンズヒドリルアミン、２－メチルベンジルアミン、３－メチルベンジルアミン、４－ｔｅｒｔ－ブチルベンジルアミン、Ｎ－メチルベンジルアミン、Ｎ－エチルベンジルアミン、Ｎ－フェニルベンジルアミン、Ｎ－ｔｅｒｔ－ブチルベンジルアミン、Ｎ－イソプロピルベンジルアミン、Ｎ，Ｎ－ジメチルベンジルアミン、イミダゾール化合物、及びトリアゾール化合物が挙げられる。上記第２の化合物及び上記第４の化合物は、ベンジルアミン、２－メチルベンジルアミン、又は３－メチルベンジルアミンであることが好ましい。上記第２の化合物及び上記第４の化合物が、上記の好ましい態様を満足すると、導電材料の保存安定性をより一層効果的に高めることができ、導電材料中にフラックスをより一層高充填することができ、さらに、導電接続時のはんだの凝集性をより一層効果的に高めることができる。 The second compound and the fourth compound are preferably organic compounds having an amino group. Examples of the second compound and the fourth compound include diethanolamine, triethanolamine, methyldiethanolamine, ethyldiethanolamine, cyclohexylamine, dicyclohexylamine, benzylamine, benzhydrylamine, 2-methylbenzylamine, and 3-methylbenzylamine. , 4-tert-butylbenzylamine, N-methylbenzylamine, N-ethylbenzylamine, N-phenylbenzylamine, N-tert-butylbenzylamine, N-isopropylbenzylamine, N, N-dimethylbenzylamine, imidazole And triazole compounds. The second compound and the fourth compound are preferably benzylamine, 2-methylbenzylamine, or 3-methylbenzylamine. When the second compound and the fourth compound satisfy the above-described preferred embodiment, the storage stability of the conductive material can be more effectively improved, and the conductive material can be charged with a higher flux. In addition, the cohesiveness of the solder at the time of conductive connection can be more effectively increased.
　上記第２の化合物と上記第４の化合物とは、同一の化合物であってもよく、異なる化合物であってもよい。導電材料の保存安定性をより一層効果的に高める観点、導電材料中にフラックスをより一層高充填する観点、及び導電接続時のはんだの凝集性をより一層効果的に高める観点からは、上記第２の化合物と上記第４の化合物とは、同一の化合物であることが好ましい。 The second compound and the fourth compound may be the same compound or different compounds. From the viewpoint of more effectively improving the storage stability of the conductive material, the viewpoint of further filling the conductive material with flux, and the viewpoint of more effectively increasing the cohesiveness of the solder during the conductive connection, Preferably, the second compound and the fourth compound are the same compound.
　上記フラックスは、導電材料中に分散されていてもよく、導電性粒子の表面上に付着していてもよい。フラックス効果をより一層効果的に高める観点からは、上記フラックスは、導電性粒子の表面上に付着していることが好ましい。 The flux may be dispersed in a conductive material or may adhere to the surface of the conductive particles. From the viewpoint of more effectively increasing the flux effect, it is preferable that the flux adheres to the surface of the conductive particles.
　上記固体塩の平均粒子径は、好ましくは０．０１μｍ以上、より好ましくは０．０５μｍ以上であり、好ましくは１０μｍ以下、より好ましくは１μｍ以下である。上記固体塩の平均粒子径が、上記下限以上及び上記上限以下であると、導電材料の保存安定性をより一層効果的に高めることができる。 The average particle size of the solid salt is preferably 0.01 μm or more, more preferably 0.05 μm or more, preferably 10 μm or less, more preferably 1 μm or less. When the average particle size of the solid salt is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively enhanced.
　また、上記固体塩の平均粒子径の、上記導電性粒子の平均粒子径に対する比（固体塩の平均粒子径／導電性粒子の平均粒子径）は、好ましくは０．１以上、より好ましくは０．２以上であり、好ましくは１以下、より好ましくは０．５以下である。上記比（固体塩の平均粒子径／導電性粒子の平均粒子径）が、上記下限以上及び上記上限以下であると、固体塩を導電性粒子に対してより一層効果的に接触させることができ、加熱時のフラックス性能をより一層高めることができる。 The ratio of the average particle diameter of the solid salt to the average particle diameter of the conductive particles (the average particle diameter of the solid salt / the average particle diameter of the conductive particles) is preferably 0.1 or more, and more preferably 0 or more. .2 or more, preferably 1 or less, more preferably 0.5 or less. When the ratio (average particle diameter of solid salt / average particle diameter of conductive particles) is not less than the lower limit and not more than the upper limit, the solid salt can be more effectively brought into contact with the conductive particles. In addition, the flux performance during heating can be further improved.
　上記固体塩の平均粒子径は、数平均粒子径を示す。上記固体塩の平均粒子径は、任意の固体塩５０個を電子顕微鏡にて観察し、各固体塩の粒子径の平均値を算出することにより求めることができる。 平均 The average particle size of the solid salt indicates a number average particle size. The average particle size of the solid salt can be determined by observing 50 arbitrary solid salts with an electron microscope and calculating the average value of the particle size of each solid salt.
　上記固体塩の粒子径は、固体塩が真球状である場合には、直径を示し、固体塩が真球状ではない場合には、最大径を示す。 粒子 The particle size of the solid salt indicates the diameter when the solid salt is spherical, and indicates the maximum particle size when the solid salt is not spherical.
　上記熱硬化性化合物１００重量部に対して、上記フラックスの含有量は、好ましくは１重量部以上、より好ましくは１０重量部以上であり、好ましくは５０重量部以下、より好ましくは４０重量部以下である。上記フラックスの含有量が、上記下限以上及び上記上限以下であると、導電材料の保存安定性をより一層効果的に高めることができ、導電接続時のはんだの凝集性をより一層効果的に高めることができる。本発明に係る導電材料では、上述した好ましい態様を満足しているので、５０重量部以上のフラックスを高充填することができる。 The content of the flux is preferably at least 1 part by weight, more preferably at least 10 parts by weight, preferably at most 50 parts by weight, more preferably at most 40 parts by weight, based on 100 parts by weight of the thermosetting compound. It is. When the content of the flux is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively increased, and the cohesiveness of the solder at the time of conductive connection is more effectively increased. be able to. Since the conductive material according to the present invention satisfies the above-described preferred embodiments, it is possible to highly fill a flux of 50 parts by weight or more.
　導電材料１００重量％中、上記フラックスの含有量は、好ましくは０．０５重量％以上、より好ましくは５重量％以上であり、好ましくは２０重量％以下、より好ましくは１０重量％以下である。上記フラックスの含有量が、上記下限以上及び上記上限以下であると、導電材料の保存安定性をより一層効果的に高めることができ、導電接続時のはんだの凝集性をより一層効果的に高めることができる。また、上記フラックスの含有量が、上記下限以上及び上記上限以下であると、導電性粒子におけるはんだ及び電極の表面に酸化被膜がより一層形成され難くなり、さらに、導電性粒子におけるはんだ及び電極の表面に形成された酸化被膜をより一層効果的に除去できる。本発明に係る導電材料では、上述した好ましい態様を満足しているので、２０重量％以上のフラックスを高充填することができる。 (4) The content of the flux in 100% by weight of the conductive material is preferably 0.05% by weight or more, more preferably 5% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less. When the content of the flux is not less than the lower limit and not more than the upper limit, the storage stability of the conductive material can be more effectively increased, and the cohesiveness of the solder at the time of conductive connection is more effectively increased. be able to. Further, when the content of the flux is not less than the lower limit and not more than the upper limit, an oxide film is more difficult to be formed on the surfaces of the solder and the electrode in the conductive particles, and further, the solder and the electrode in the conductive particles The oxide film formed on the surface can be more effectively removed. Since the conductive material according to the present invention satisfies the above-described preferred embodiment, it can be highly filled with a flux of 20% by weight or more.
　（フィラー）
　上記導電材料は、フィラーを含んでいてもよい。上記フィラーは、有機フィラーであってもよく、無機フィラーであってもよい。フィラーの添加により、基板の全電極上に対して、導電性粒子を均一に凝集させることができる。 (Filler)
The conductive material may include a filler. The filler may be an organic filler or an inorganic filler. By adding the filler, the conductive particles can be uniformly aggregated on all the electrodes of the substrate.
　上記導電材料は、上記フィラーを含まないか、又は上記フィラーを５重量％以下で含むことが好ましい。上記熱硬化性化合物を用いている場合には、フィラーの含有量が少ないほど、電極上に導電性粒子が移動しやすくなる。 The conductive material preferably does not contain the filler or contains the filler at 5% by weight or less. When the thermosetting compound is used, the smaller the filler content, the more easily the conductive particles move on the electrode.
　上記導電材料１００重量％中、上記フィラーの含有量は、好ましくは０重量％（未含有）以上であり、好ましくは５重量％以下、より好ましくは２重量％以下、さらに好ましくは１重量％以下である。上記フィラーの含有量が、上記下限以上及び上記上限以下であると、導電性粒子が電極上により一層効率的に配置される。 In 100% by weight of the conductive material, the content of the filler is preferably 0% by weight (not included) or more, preferably 5% by weight or less, more preferably 2% by weight or less, and further more preferably 1% by weight or less. It is. When the content of the filler is equal to or more than the lower limit and equal to or less than the upper limit, the conductive particles are more efficiently arranged on the electrode.
　（他の成分）
　上記導電材料は、必要に応じて、例えば、充填剤、増量剤、軟化剤、可塑剤、増粘剤、チキソ剤、レベリング剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。 (Other ingredients)
The conductive material may be, if necessary, for example, a filler, a bulking agent, a softener, a plasticizer, a thickener, a thixo agent, a leveling agent, a polymerization catalyst, a curing catalyst, a coloring agent, an antioxidant, and a heat stabilizer. And various additives such as light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and flame retardants.
　（接続構造体）
　本発明に係る接続構造体は、第１の電極を表面に有する第１の接続対象部材と、第２の電極を表面に有する第２の接続対象部材と、上記第１の接続対象部材と、上記第２の接続対象部材とを接続している接続部とを備える。本発明に係る接続構造体では、上記接続部の材料が、上述した導電材料である。本発明に係る接続構造体では、上記接続部が、上述した導電材料の硬化物である。本発明に係る接続構造体では、上記第１の電極と上記第２の電極とが、上記導電性粒子により電気的に接続されている。 (Connection structure)
The connection structure according to the present invention includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, A connection portion connecting the second connection target member. In the connection structure according to the present invention, the material of the connection portion is the above-described conductive material. In the connection structure according to the present invention, the connection portion is a cured product of the above-described conductive material. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by the conductive particles.
　本発明に係る接続構造体では、特定の導電材料を用いているので、導電性粒子におけるはんだが第１の電極と第２の電極との間に集まりやすく、はんだを電極（ライン）上に効率的に配置することができる。また、はんだの一部が、電極が形成されていない領域（スペース）に配置され難く、電極が形成されていない領域に配置されるはんだの量をかなり少なくすることができる。従って、第１の電極と第２の電極との間の導通信頼性を高めることができる。しかも、接続されてはならない横方向に隣接する電極間の電気的な接続を防ぐことができ、絶縁信頼性を高めることができる。 In the connection structure according to the present invention, since the specific conductive material is used, the solder in the conductive particles easily collects between the first electrode and the second electrode, and the solder is efficiently placed on the electrodes (lines). It can be arranged in a way. Further, it is difficult for a part of the solder to be arranged in the region (space) where the electrode is not formed, and the amount of the solder arranged in the region where the electrode is not formed can be considerably reduced. Therefore, conduction reliability between the first electrode and the second electrode can be improved. In addition, electrical connection between horizontally adjacent electrodes that should not be connected can be prevented, and insulation reliability can be improved.
　また、導電性粒子におけるはんだを電極上に効率的に配置し、かつ電極が形成されていない領域に配置されるはんだの量をかなり少なくするためには、上記導電材料は、導電フィルムではなく、導電ペーストを用いることが好ましい。 Further, in order to efficiently arrange the solder in the conductive particles on the electrodes, and to considerably reduce the amount of solder arranged in the region where the electrodes are not formed, the conductive material is not a conductive film, but a conductive film. It is preferable to use a conductive paste.
　電極間でのはんだ部の厚みは、好ましくは１０μｍ以上、より好ましくは２０μｍ以上であり、好ましくは１００μｍ以下、より好ましくは８０μｍ以下である。電極の表面上のはんだ濡れ面積（電極の露出した面積１００％中のはんだが接している面積）は、好ましくは５０％以上、より好ましくは６０％以上、さらに好ましくは７０％以上であり、好ましくは１００％以下である。 は ん だ The thickness of the solder portion between the electrodes is preferably 10 μm or more, more preferably 20 μm or more, preferably 100 μm or less, more preferably 80 μm or less. The solder wet area on the surface of the electrode (the area where the solder is in contact with 100% of the exposed area of the electrode) is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more, and preferably 70% or more. Is 100% or less.
　以下、図面を参照しつつ、本発明の具体的な実施形態を説明する。 Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
　図１は、本発明の一実施形態に係る導電材料を用いて得られる接続構造体を模式的に示す断面図である。 FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to one embodiment of the present invention.
　図１に示す接続構造体１は、第１の接続対象部材２と、第２の接続対象部材３と、第１の接続対象部材２と第２の接続対象部材３とを接続している接続部４とを備える。接続部４は、上述した導電材料により形成されている。本実施形態では、上記導電材料は、導電性粒子と、熱硬化性成分と、フラックスとを含む。上記導電性粒子は、はんだ粒子である。上記熱硬化性成分として、熱硬化性化合物と熱硬化剤とを含む。本実施形態では、導電材料として、導電ペーストが用いられている。 The connection structure 1 shown in FIG. 1 includes a first connection target member 2, a second connection target member 3, and a connection connecting the first connection target member 2 and the second connection target member 3. Unit 4. The connection part 4 is formed of the above-described conductive material. In the present embodiment, the conductive material includes conductive particles, a thermosetting component, and a flux. The conductive particles are solder particles. The thermosetting component contains a thermosetting compound and a thermosetting agent. In the present embodiment, a conductive paste is used as the conductive material.
　接続部４は、複数のはんだ粒子が集まり互いに接合したはんだ部４Ａと、熱硬化性成分が熱硬化された硬化物部４Ｂとを有する。 The connection portion 4 has a solder portion 4A in which a plurality of solder particles are gathered and joined to each other, and a cured product portion 4B in which a thermosetting component is thermoset.
　第１の接続対象部材２は表面（上面）に、複数の第１の電極２ａを有する。第２の接続対象部材３は表面（下面）に、複数の第２の電極３ａを有する。第１の電極２ａと第２の電極３ａとが、はんだ部４Ａにより電気的に接続されている。従って、第１の接続対象部材２と第２の接続対象部材３とが、はんだ部４Ａにより電気的に接続されている。なお、接続部４において、第１の電極２ａと第２の電極３ａとの間に集まったはんだ部４Ａとは異なる領域（硬化物部４Ｂ部分）では、はんだは存在しない。はんだ部４Ａとは異なる領域（硬化物部４Ｂ部分）では、はんだ部４Ａと離れたはんだは存在しない。なお、少量であれば、第１の電極２ａと第２の電極３ａとの間に集まったはんだ部４Ａとは異なる領域（硬化物部４Ｂ部分）に、はんだが存在していてもよい。 The first connection target member 2 has a plurality of first electrodes 2a on the surface (upper surface). The second connection target member 3 has a plurality of second electrodes 3a on the surface (lower surface). The first electrode 2a and the second electrode 3a are electrically connected by the solder 4A. Therefore, the first connection target member 2 and the second connection target member 3 are electrically connected by the solder portion 4A. In the connection portion 4, no solder exists in a region (cured material portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a. In a region different from the solder portion 4A (cured material portion 4B portion), there is no solder separated from the solder portion 4A. If the amount is small, the solder may be present in a region (cured material portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a.
　図１に示すように、接続構造体１では、第１の電極２ａと第２の電極３ａとの間に、複数のはんだ粒子が集まり、複数のはんだ粒子が溶融した後、はんだ粒子の溶融物が電極の表面を濡れ拡がった後に固化して、はんだ部４Ａが形成されている。このため、はんだ部４Ａと第１の電極２ａ、並びにはんだ部４Ａと第２の電極３ａとの接続面積が大きくなる。すなわち、はんだ粒子を用いることにより、導電部の外表面部分がニッケル、金又は銅等の金属である導電性粒子を用いた場合と比較して、はんだ部４Ａと第１の電極２ａ、並びにはんだ部４Ａと第２の電極３ａとの接触面積が大きくなる。このため、接続構造体１における導通信頼性及び接続信頼性が高くなる。なお、導電材料に含まれるフラックスは、一般に、加熱により次第に失活する。 As shown in FIG. 1, in the connection structure 1, a plurality of solder particles gather between the first electrode 2a and the second electrode 3a, and after the plurality of solder particles have melted, Solidifies after the electrode surface wets and spreads to form the solder portion 4A. Therefore, the connection area between the solder portion 4A and the first electrode 2a and the connection area between the solder portion 4A and the second electrode 3a are increased. That is, by using the solder particles, the solder portion 4A, the first electrode 2a, and the solder are compared with the case where the outer surface portion of the conductive portion is made of conductive particles of a metal such as nickel, gold, or copper. The contact area between the portion 4A and the second electrode 3a increases. For this reason, conduction reliability and connection reliability in the connection structure 1 are improved. Note that, generally, the flux contained in the conductive material is gradually deactivated by heating.
　なお、図１に示す接続構造体１では、はんだ部４Ａの全てが、第１，第２の電極２ａ，３ａ間の対向している領域に位置している。図３に示す変形例の接続構造体１Ｘは、接続部４Ｘのみが、図１に示す接続構造体１と異なる。接続部４Ｘは、はんだ部４ＸＡと硬化物部４ＸＢとを有する。接続構造体１Ｘのように、はんだ部４ＸＡの多くが、第１，第２の電極２ａ，３ａの対向している領域に位置しており、はんだ部４ＸＡの一部が第１，第２の電極２ａ，３ａの対向している領域から側方にはみ出していてもよい。第１，第２の電極２ａ，３ａの対向している領域から側方にはみ出しているはんだ部４ＸＡは、はんだ部４ＸＡの一部であり、はんだ部４ＸＡから離れたはんだではない。なお、本実施形態では、はんだ部から離れたはんだの量を少なくすることができるが、はんだ部から離れたはんだが硬化物部中に存在していてもよい。 In the connection structure 1 shown in FIG. 1, all of the solder portions 4A are located in opposing regions between the first and second electrodes 2a and 3a. The connection structure 1X of the modification shown in FIG. 3 differs from the connection structure 1 shown in FIG. 1 only in the connection portion 4X. The connection part 4X has a solder part 4XA and a cured material part 4XB. Like the connection structure 1X, most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a face each other, and a part of the solder portion 4XA is formed in the first and second electrodes. The electrodes 2a and 3a may protrude laterally from the facing regions. The solder portion 4XA protruding laterally from the region where the first and second electrodes 2a and 3a face each other is a part of the solder portion 4XA and is not a solder separated from the solder portion 4XA. In the present embodiment, the amount of the solder separated from the solder portion can be reduced, but the solder separated from the solder portion may be present in the cured product portion.
　はんだ粒子の使用量を少なくすれば、接続構造体１を得ることが容易になる。はんだ粒子の使用量を多くすれば、接続構造体１Ｘを得ることが容易になる。 接 続 If the amount of the solder particles used is reduced, it becomes easier to obtain the connection structure 1. Increasing the amount of the solder particles facilitates obtaining the connection structure 1X.
　接続構造体１，１Ｘでは、第１の電極２ａと接続部４，４Ｘと第２の電極３ａとの積層方向に第１の電極２ａと第２の電極３ａとの対向し合う部分をみたときに、第１の電極２ａと第２の電極３ａとの対向し合う部分の面積１００％中の５０％以上に、接続部４，４Ｘ中のはんだ部４Ａ，４ＸＡが配置されていることが好ましい。接続部４，４Ｘ中のはんだ部４Ａ，４ＸＡが、上記の好ましい態様を満足することで、導通信頼性をより一層高めることができる。 In the connection structures 1 and 1X, when the opposing portions of the first electrode 2a and the second electrode 3a are viewed in the stacking direction of the first electrode 2a, the connection portions 4 and 4X, and the second electrode 3a. In addition, it is preferable that the solder portions 4A and 4XA in the connection portions 4 and 4X are arranged at 50% or more of the area of 100% of the area where the first electrode 2a and the second electrode 3a face each other. . When the solder portions 4A and 4XA in the connection portions 4 and 4X satisfy the above-described preferred embodiment, conduction reliability can be further improved.
　上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の５０％以上に、上記接続部中のはんだ部が配置されていることが好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の６０％以上に、上記接続部中のはんだ部が配置されていることがより好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の７０％以上に、上記接続部中のはんだ部が配置されていることがさらに好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の８０％以上に、上記接続部中のはんだ部が配置されていることが特に好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の９０％以上に、上記接続部中のはんだ部が配置されていることが最も好ましい。上記接続部中のはんだ部が、上記の好ましい態様を満足することで、導通信頼性をより一層高めることができる。 When a portion where the first electrode and the second electrode face each other is viewed in the laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode and the second electrode It is preferable that the solder portion in the connection portion is arranged in 50% or more of 100% of the area of the portion facing the second electrode. When a portion where the first electrode and the second electrode face each other is viewed in the laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode and the second electrode It is more preferable that the solder part in the connection part is arranged in 60% or more of the area of 100% of the part facing the second electrode. When a portion where the first electrode and the second electrode face each other is viewed in the laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode and the second electrode It is further preferable that the solder portion in the connection portion is arranged in 70% or more of 100% of the area of the portion facing the second electrode. When a portion where the first electrode and the second electrode face each other is viewed in the laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode and the second electrode It is particularly preferable that the solder portion in the connection portion is arranged at 80% or more of the area of 100% of the portion facing the second electrode. When a portion where the first electrode and the second electrode face each other is viewed in the laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode and the second electrode Most preferably, the solder part in the connection part is arranged in 90% or more of the area 100% of the part facing the second electrode. When the solder portion in the connection portion satisfies the above-described preferred embodiment, conduction reliability can be further improved.
　上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の６０％以上が配置されていることが好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の７０％以上が配置されていることがより好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の９０％以上が配置されていることがさらに好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の９５％以上が配置されていることが特に好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の９９％以上が配置されていることが最も好ましい。上記接続部中のはんだ部が、上記の好ましい態様を満足することで、導通信頼性をより一層高めることができる。 When the opposing portion of the first electrode and the second electrode is viewed in a direction orthogonal to the laminating direction of the first electrode, the connecting portion, and the second electrode, the first electrode It is preferable that 60% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other. When the opposing portion of the first electrode and the second electrode is viewed in a direction orthogonal to the laminating direction of the first electrode, the connecting portion, and the second electrode, the first electrode It is more preferable that 70% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other. When the opposing portion of the first electrode and the second electrode is viewed in a direction orthogonal to the laminating direction of the first electrode, the connecting portion, and the second electrode, the first electrode It is further preferable that 90% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other. When the opposing portion of the first electrode and the second electrode is viewed in a direction orthogonal to the laminating direction of the first electrode, the connecting portion, and the second electrode, the first electrode It is particularly preferable that 95% or more of the solder portion in the connection portion is arranged in a portion where the electrode and the second electrode face each other. When a portion where the first electrode and the second electrode face each other is viewed in a direction orthogonal to a laminating direction of the first electrode, the connection portion, and the second electrode, the first electrode Most preferably, 99% or more of the solder part in the connection part is arranged in a part where the electrode and the second electrode face each other. When the solder portion in the connection portion satisfies the above preferred embodiment, conduction reliability can be further improved.
　次に、図２では、本発明の一実施形態に係る導電材料を用いて、接続構造体１を製造する方法の一例を説明する。 Next, FIG. 2 illustrates an example of a method for manufacturing the connection structure 1 using the conductive material according to one embodiment of the present invention.
　先ず、第１の電極２ａを表面（上面）に有する第１の接続対象部材２を用意する。次に、図２（ａ）に示すように、第１の接続対象部材２の表面上に、熱硬化性成分１１Ｂと、複数のはんだ粒子１１Ａとを含む導電材料１１を配置する（第１の工程）。導電材料１１は、熱硬化性成分１１Ｂとして、熱硬化性化合物と熱硬化剤とフラックスとを含む。 First, the first connection target member 2 having the first electrode 2a on the surface (upper surface) is prepared. Next, as shown in FIG. 2A, a conductive material 11 including a thermosetting component 11B and a plurality of solder particles 11A is disposed on the surface of the first connection target member 2 (first). Process). The conductive material 11 includes a thermosetting compound, a thermosetting agent, and a flux as the thermosetting component 11B.
　第１の接続対象部材２の第１の電極２ａが設けられた表面上に、導電材料１１を配置する。導電材料１１の配置の後に、はんだ粒子１１Ａは、第１の電極２ａ（ライン）上と、第１の電極２ａが形成されていない領域（スペース）上との双方に配置されている。なお、上記導電材料は、上記第１の電極の表面上にのみ配置されてもよい。 (4) The conductive material 11 is arranged on the surface of the first connection target member 2 on which the first electrode 2a is provided. After disposing the conductive material 11, the solder particles 11A are disposed both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed. Note that the conductive material may be disposed only on the surface of the first electrode.
　導電材料１１の配置方法としては、特に限定されないが、ディスペンサーによる塗布、スクリーン印刷、及びインクジェット装置による吐出等が挙げられる。 (4) The method for arranging the conductive material 11 is not particularly limited, and examples thereof include application using a dispenser, screen printing, and ejection using an inkjet device.
　また、第２の電極３ａを表面（下面）に有する第２の接続対象部材３を用意する。次に、図２（ｂ）に示すように、第１の接続対象部材２の表面上の導電材料１１において、導電材料１１の第１の接続対象部材２側とは反対側の表面上に、第２の接続対象部材３を配置する（第２の工程）。導電材料１１の表面上に、第２の電極３ａ側から、第２の接続対象部材３を配置する。このとき、第１の電極２ａと第２の電極３ａとを対向させる。 Also, a second connection target member 3 having the second electrode 3a on the surface (lower surface) is prepared. Next, as shown in FIG. 2B, in the conductive material 11 on the surface of the first connection target member 2, on the surface of the conductive material 11 opposite to the first connection target member 2 side, The second connection target member 3 is arranged (second step). The second connection target member 3 is arranged on the surface of the conductive material 11 from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a face each other.
　次に、はんだ粒子１１Ａの融点以上に導電材料１１を加熱する（第３の工程）。好ましくは、熱硬化性成分１１Ｂ（熱硬化性化合物）の硬化温度以上に導電材料１１を加熱する。この加熱時には、電極が形成されていない領域に存在していたはんだ粒子１１Ａは、第１の電極２ａと第２の電極３ａとの間に集まる（自己凝集効果）。導電フィルムではなく、導電ペーストを用いた場合には、はんだ粒子１１Ａが、第１の電極２ａと第２の電極３ａとの間により一層効果的に集まる。また、はんだ粒子１１Ａは溶融し、互いに接合する。また、熱硬化性成分１１Ｂは熱硬化する。この結果、図２（ｃ）に示すように、第１の接続対象部材２と第２の接続対象部材３とを接続している接続部４が、導電材料１１により形成される。導電材料１１により接続部４が形成され、複数のはんだ粒子１１Ａが接合することによってはんだ部４Ａが形成され、熱硬化性成分１１Ｂが熱硬化することによって硬化物部４Ｂが形成される。はんだ粒子１１Ａが十分に移動すれば、第１の電極２ａと第２の電極３ａとの間に位置していないはんだ粒子１１Ａの移動が開始してから、第１の電極２ａと第２の電極３ａとの間にはんだ粒子１１Ａの移動が完了するまでに、温度を一定に保持しなくてもよい。 Next, the conductive material 11 is heated above 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 (thermosetting compound). At the time of this heating, the solder particles 11A existing in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect). When the conductive paste is used instead of the conductive film, the solder particles 11A more effectively gather between the first electrode 2a and the second electrode 3a. Further, the solder particles 11A are melted and joined to each other. The thermosetting component 11B is thermoset. As a result, as shown in FIG. 2C, the connection portion 4 connecting the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11. The connection portion 4 is formed by the conductive material 11, the solder portion 4A is formed by joining the plurality of solder particles 11A, and the cured product portion 4B is formed by thermosetting the thermosetting component 11B. If the solder particles 11A move sufficiently, the movement of the solder particles 11A not located between the first electrode 2a and the second electrode 3a starts, and then the first electrode 2a and the second electrode 2a move. The temperature does not need to be kept constant until the movement of the solder particles 11A between the solder particles 3a and 3a is completed.
　本実施形態では、上記第２の工程及び上記第３の工程において、加圧を行わない方が好ましい。この場合には、導電材料１１には、第２の接続対象部材３の重量が加わる。このため、接続部４の形成時に、はんだ粒子１１Ａが、第１の電極２ａと第２の電極３ａとの間により一層効果的に集まる。なお、上記第２の工程及び上記第３の工程の内の少なくとも一方において、加圧を行えば、はんだ粒子１１Ａが第１の電極２ａと第２の電極３ａとの間に集まろうとする作用が阻害される傾向が高くなる。 で は In the present embodiment, it is preferable not to apply pressure in the second step and the third step. In this case, the weight of the second connection target member 3 is added to the conductive material 11. For this reason, when the connection part 4 is formed, the solder particles 11A gather more effectively between the first electrode 2a and the second electrode 3a. If pressure is applied in at least one of the second step and the third step, the action of the solder particles 11A trying to gather between the first electrode 2a and the second electrode 3a. Tend to be inhibited.
　導電材料を塗布した第１の接続対象部材に、第２の接続対象部材を重ね合わせた際に、第１の接続対象部材の電極と第２の接続対象部材の電極とのアライメントがずれた状態で、第１の接続対象部材と第２の接続対象部材とが重ね合わされる場合がある。本実施形態では、加圧を行っていないため、そのずれを補正して、第１の接続対象部材の電極と第２の接続対象部材との電極を接続させることができる（セルフアライメント効果）。これは、第１の接続対象部材の電極と第２の接続対象部材の電極との間に自己凝集している溶融したはんだが、第１の接続対象部材の電極と第２の接続対象部材の電極との間のはんだと導電材料のその他の成分とが接する面積が最小となる方がエネルギー的に安定になるためである。そして、その最小の面積となる接続構造であるアライメントのあった接続構造にする力が働くためである。この際、導電材料が硬化していないこと、及び、その温度、時間にて、導電材料の導電性粒子以外の成分の粘度が十分低いことが望ましい。 When the second connection target member is superimposed on the first connection target member coated with the conductive material, the alignment between the electrode of the first connection target member and the electrode of the second connection target member is shifted. Thus, the first connection target member and the second connection target member may be overlapped. In the present embodiment, since no pressure is applied, the deviation can be corrected and the electrode of the first connection target member and the electrode of the second connection target member can be connected (self-alignment effect). This is because the molten solder that has self-agglomerated between the electrode of the first member to be connected and the electrode of the second member to be connected is formed between the electrode of the first member to be connected and the second member to be connected. This is because the smaller the area where the solder between the electrode and the other components of the conductive material is in contact, the more stable the energy. This is because a force acts on a connection structure having an alignment, which is the connection structure having the minimum area. At this time, it is desirable that the conductive material is not cured and that the viscosity of the components other than the conductive particles of the conductive material is sufficiently low at the temperature and time.
　はんだの融点での導電材料の粘度は、好ましくは５０Ｐａ・ｓ以下、より好ましくは１０Ｐａ・ｓ以下、さらに好ましくは１Ｐａ・ｓ以下であり、好ましくは０．１Ｐａ・ｓ以上、より好ましくは０．２Ｐａ・ｓ以上である。上記粘度が、上記上限以下であれば、導電性粒子におけるはんだを効率的に凝集させることができる。上記粘度が、上記下限以上であれば、接続部でのボイドを抑制し、接続部以外への導電材料のはみだしを抑制することができる。 The viscosity of the conductive material at the melting point of the solder is preferably 50 Pa · s or less, more preferably 10 Pa · s or less, further preferably 1 Pa · s or less, preferably 0.1 Pa · s or more, and more preferably 0.1 Pa · s or more. 2 Pa · s or more. When the viscosity is equal to or less than the upper limit, the solder in the conductive particles can be efficiently aggregated. When the viscosity is equal to or higher than the lower limit, voids at the connection portion can be suppressed, and protrusion of the conductive material to portions other than the connection portion can be suppressed.
　はんだの融点での導電材料の粘度は以下のようにして測定される。 粘度 The viscosity of the conductive material at the melting point of the solder is measured as follows.
　上記はんだの融点での導電材料の粘度は、ＳＴＲＥＳＳＴＥＣＨ（ＲＥＯＬＯＧＩＣＡ社製）等を用いて、歪制御１ｒａｄ、周波数１Ｈｚ、昇温速度２０℃／分、測定温度範囲２５℃～２００℃（但し、はんだの融点が２００℃を超える場合には温度上限をはんだの融点とする）の条件で測定可能である。測定結果から、はんだの融点（℃）での粘度が評価される。 The viscosity of the conductive material at the melting point of the solder is determined by using a strain control (manufactured by RELOGICA) or the like, with a strain control of 1 rad, a frequency of 1 Hz, a heating rate of 20 ° C./min, and a measurement temperature range of 25 ° C. to 200 ° C. (If the melting point exceeds 200 ° C., the upper limit of the temperature is taken as the melting point of the solder). From the measurement results, the viscosity at the melting point (° C.) of the solder is evaluated.
　このようにして、図１に示す接続構造体１が得られる。なお、上記第２の工程と上記第３の工程とは連続して行われてもよい。また、上記第２の工程を行った後に、得られる第１の接続対象部材２と導電材料１１と第２の接続対象部材３との積層体を、加熱部に移動させて、上記第３の工程を行ってもよい。上記加熱を行うために、加熱部材上に上記積層体を配置してもよく、加熱された空間内に上記積層体を配置してもよい。 よ う Thus, the connection structure 1 shown in FIG. 1 is obtained. Note that the second step and the third step may be performed continuously. After performing the second step, the obtained laminated body of the first connection target member 2, the conductive material 11, and the second connection target member 3 is moved to a heating unit, and the third connection target member 2, the conductive material 11, and the second connection target member 3 are moved to the heating unit. A step may be performed. In order to perform the heating, the laminate may be arranged on a heating member, or the laminate may be arranged in a heated space.
　上記第３の工程における上記加熱温度は、好ましくは１４０℃以上、より好ましくは１６０℃以上であり、好ましくは４５０℃以下、より好ましくは２５０℃以下、さらに好ましくは２００℃以下である。上記第３の工程における上記加熱温度が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができ、接続されるべき上下の電極間の導通信頼性をより一層効果的に高めることができる。 上 記 The heating temperature in the third step is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, preferably 450 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower. When the heating temperature in the third step is equal to or higher than the lower limit and equal to or lower than the upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and the upper and lower electrodes to be connected can be connected. Can be more effectively improved.
　上記第３の工程における加熱方法としては、導電性粒子におけるはんだの融点以上及び熱硬化性成分の硬化温度以上に、接続構造体全体を、リフロー炉を用いて又はオーブンを用いて加熱する方法や、接続構造体の接続部のみを局所的に加熱する方法が挙げられる。 As a heating method in the third step, a method of heating the entire connection structure using a reflow oven or using an oven above the melting point of the solder in the conductive particles and the curing temperature of the thermosetting component, And a method of locally heating only the connection portion of the connection structure.
　局所的に加熱する方法に用いる器具としては、ホットプレート、熱風を付与するヒートガン、はんだゴテ、及び赤外線ヒーター等が挙げられる。 器具 Examples of instruments used for the method of locally heating include a hot plate, a heat gun for applying hot air, a soldering iron, and an infrared heater.
　また、ホットプレートにて局所的に加熱する際、接続部直下は、熱伝導性の高い金属にて、その他の加熱することが好ましくない個所は、フッ素樹脂等の熱伝導性の低い材質にて、ホットプレート上面を形成することが好ましい。 In addition, when heating locally with a hot plate, the metal beneath the connection part is a metal with high thermal conductivity, and other places where heating is not preferable are made of a material with low thermal conductivity such as fluororesin. Preferably, the upper surface of the hot plate is formed.
　上記第１，第２の接続対象部材は、特に限定されない。上記第１，第２の接続対象部材としては、具体的には、半導体チップ、半導体パッケージ、ＬＥＤチップ、ＬＥＤパッケージ、コンデンサ及びダイオード等の電子部品、並びに樹脂フィルム、プリント基板、フレキシブルプリント基板、フレキシブルフラットケーブル、リジッドフレキシブル基板、ガラスエポキシ基板及びガラス基板等の回路基板等の電子部品等が挙げられる。上記第１，第２の接続対象部材は、電子部品であることが好ましい。 The first and second connection target members are not particularly limited. The first and second connection target members specifically include electronic components such as a semiconductor chip, a semiconductor package, an LED chip, an LED package, a capacitor and a diode, a resin film, a printed board, a flexible printed board, and a flexible board. Electronic components such as a flat cable, a rigid flexible substrate, a circuit board such as a glass epoxy substrate and a glass substrate, and the like. Preferably, the first and second connection target members are electronic components.
　上記第１の接続対象部材及び上記第２の接続対象部材の内の少なくとも一方が、樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板であることが好ましい。上記第１の接続対象部材及び上記第２の接続対象部材の内の少なくとも一方が、樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板であることが好ましい。樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル及びリジッドフレキシブル基板は、柔軟性が高く、比較的軽量であるという性質を有する。このような接続対象部材の接続に導電フィルムを用いた場合には、導電性粒子におけるはんだが電極上に集まりにくい傾向がある。これに対して、導電ペーストを用いることで、樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板を用いたとしても、導電性粒子におけるはんだを電極上に効率的に集めることで、電極間の導通信頼性を十分に高めることができる。樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板を用いる場合に、半導体チップ等の他の接続対象部材を用いた場合と比べて、加圧を行わないことによる電極間の導通信頼性の向上効果がより一層効果的に得られる。 It is preferable that at least one of the first connection target member and the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. It is preferable that at least one of the first connection target member and the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. A resin film, a flexible printed board, a flexible flat cable, and a rigid flexible board have properties of high flexibility and relatively light weight. When a conductive film is used for connecting such a connection target member, the solder in the conductive particles tends to hardly collect on the electrodes. On the other hand, by using a conductive paste, even if a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board is used, the solder in the conductive particles is efficiently collected on the electrodes, and thus the distance between the electrodes is increased. Can be sufficiently improved. When using a resin film, a flexible printed board, a flexible flat cable or a rigid flexible board, the reliability of conduction between the electrodes due to the absence of pressure is higher than when using other connection target members such as semiconductor chips. The improvement effect can be obtained even more effectively.
　上記接続対象部材に設けられている電極としては、金電極、ニッケル電極、錫電極、アルミニウム電極、銅電極、モリブデン電極、銀電極、ＳＵＳ電極、及びタングステン電極等の金属電極が挙げられる。上記接続対象部材がフレキシブルプリント基板である場合には、上記電極は金電極、ニッケル電極、錫電極、銀電極又は銅電極であることが好ましい。上記接続対象部材がガラス基板である場合には、上記電極はアルミニウム電極、銅電極、モリブデン電極、銀電極又はタングステン電極であることが好ましい。なお、上記電極がアルミニウム電極である場合には、アルミニウムのみで形成された電極であってもよく、金属酸化物層の表面にアルミニウム層が積層された電極であってもよい。上記金属酸化物層の材料としては、３価の金属元素がドープされた酸化インジウム及び３価の金属元素がドープされた酸化亜鉛等が挙げられる。上記３価の金属元素としては、Ｓｎ、Ａｌ及びＧａ等が挙げられる。 電極 Examples of the electrodes provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode. When the member to be connected is a flexible printed circuit board, the 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. When the electrode is an aluminum electrode, the electrode may be an electrode formed only of aluminum, or may be an electrode in which an aluminum layer is laminated on a surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.
　本発明に係る接続構造体では、上記第１の電極及び上記第２の電極は、エリアアレイ又はペリフェラルにて配置されていることが好ましい。上記第１の電極及び上記第２の電極が、エリアアレイ又はペリフェラルにて配置されている場合において、導電性粒子におけるはんだを電極上により一層効果的に凝集させることができる。上記エリアアレイとは、接続対象部材の電極が配置されている面にて、格子状に電極が配置されている構造のことである。上記ペリフェラルとは、接続対象部材の外周部に電極が配置されている構造のことである。電極が櫛型に並んでいる構造の場合は、櫛に垂直な方向に沿ってはんだが凝集すればよいのに対して、上記エリアアレイ又はペリフェラル構造では電極が配置されている面において、全面にて均一にはんだが凝集する必要がある。そのため、従来の方法では、はんだ量が不均一になりやすいのに対して、本発明の方法では、全面にて均一にはんだを凝集させることができる。 In the connection structure according to the present invention, it is preferable that the first electrode and the second electrode are arranged in an area array or a peripheral. When the first electrode and the second electrode are arranged in an area array or a peripheral, the solder in the conductive particles can be more effectively aggregated on the electrodes. The area array refers to a structure in which electrodes are arranged in a grid on the surface of the connection target member where the electrodes are arranged. The peripheral is a structure in which an electrode is arranged on an outer peripheral portion of a connection target member. In the case of a structure in which the electrodes are arranged in a comb shape, the solder may be aggregated along the direction perpendicular to the comb, whereas in the area array or the peripheral structure, the surface where the electrodes are arranged is entirely covered. It is necessary that the solder coheres uniformly. Therefore, in the conventional method, the amount of solder tends to be non-uniform, whereas in the method of the present invention, the solder can be uniformly agglomerated over the entire surface.
　以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.
　熱硬化性成分（熱硬化性化合物）：
　熱硬化性化合物１：ダウ・ケミカル社製「Ｄ．Ｅ．Ｎ－４３１」、エポキシ樹脂
　熱硬化性化合物２：三菱ケミカル社製「ｊＥＲ１５２」、エポキシ樹脂 Thermosetting component (thermosetting compound):
Thermosetting compound 1: "DEN-431" manufactured by Dow Chemical Company, epoxy resin Thermosetting compound 2: "jER152" manufactured by Mitsubishi Chemical Corporation, epoxy resin
　熱硬化性成分（熱硬化剤）：
　熱硬化剤１：東京化成工業社製「ＢＦ３－ＭＥＡ」、三フッ化ホウ素－モノエチルアミン錯体
　熱硬化剤２：四国化成工業社製「２ＰＺ－ＣＮ」、１－シアノエチル－２－フェニルイミダゾール Thermosetting component (thermosetting agent):
Thermosetting agent 1: "BF3-MEA" manufactured by Tokyo Kasei Kogyo Co., Ltd., boron trifluoride-monoethylamine complex Thermosetting agent 2: "2PZ-CN" manufactured by Shikoku Kasei Kogyo Co., 1-cyanoethyl-2-phenylimidazole
　導電性粒子：
　導電性粒子１：はんだ粒子、三井金属鉱業社製「ＳｎＡｇ３Ｃｕ０．５（ＳＴ－２）」（平均粒子径２．２μｍ）
　導電性粒子２：はんだ粒子、三井金属鉱業社製「ＳｎＡｇ３Ｃｕ０．５（ＤＳ－１０）」（平均粒子径１３μｍ） Conductive particles:
Conductive particles 1: Solder particles, “SnAg3Cu0.5 (ST-2)” manufactured by Mitsui Kinzoku Mining (average particle size 2.2 μm)
Conductive particles 2: solder particles, “SnAg3Cu0.5 (DS-10)” manufactured by Mitsui Mining & Smelting Co., Ltd. (average particle diameter 13 μm)
　フラックス：
　フラックス１：グルタル酸とベンジルアミンとの固体塩、平均粒子径１μｍ
　フラックス１の作製方法：
　ガラスビンに、反応溶媒である水２４ｇと、グルタル酸（和光純薬工業社製）１３．２１２ｇとを入れ、室温で均一になるまで溶解させた。その後、ベンジルアミン（和光純薬工業社製）１０．７１５ｇを入れて、約５分間撹拌し、混合液を得た。得られた混合液を５℃～１０℃の冷蔵庫に入れて、一晩放置した。析出した結晶をろ過により分取し、水で洗浄し、真空乾燥した。乾燥した結晶を１４０℃で１５分間加熱して完全に溶融させ、２５℃で３０分間かけて徐々に再析出させることで、フラックス１を得た。 flux:
Flux 1: solid salt of glutaric acid and benzylamine, average particle size 1 μm
Method for preparing flux 1:
24 g of water as a reaction solvent and 13.212 g of glutaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle and dissolved at room temperature until uniform. Thereafter, 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for about 5 minutes to obtain a mixed solution. The obtained mixture was put in a refrigerator at 5 ° C to 10 ° C and left overnight. The precipitated crystals were separated by filtration, washed with water, and dried under vacuum. Flux 1 was obtained by heating the dried crystals at 140 ° C. for 15 minutes to completely melt them and gradually reprecipitating them at 25 ° C. over 30 minutes.
　フラックス２：グルタル酸とベンジルアミンとの反応物である液体化合物
　フラックス２の作製方法：
　３つ口フラスコに、グルタル酸（和光純薬工業社製）１３．２１２ｇと、ベンジルアミン（和光純薬工業社製）１０．７１５ｇとを入れて、１２０℃で３時間加熱して反応させ、フラックス２を得た。 Flux 2: Liquid compound which is a reaction product of glutaric acid and benzylamine Method for preparing flux 2:
13.212 g of glutaric acid (manufactured by Wako Pure Chemical Industries) and 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries) are placed in a three-necked flask, and heated at 120 ° C. for 3 hours to react. Flux 2 was obtained.
　フラックス３：コハク酸とベンジルアミンとの固体塩、平均粒子径１０μｍ
　フラックス３の作製方法：
　ガラスビンに、反応溶媒である水２４ｇと、コハク酸（和光純薬工業社製）１１．８０９ｇとを入れ、室温で均一になるまで溶解させた。その後、ベンジルアミン（和光純薬工業社製）１０．７１５ｇを入れて、約５分間撹拌し、混合液を得た。得られた混合液を５℃～１０℃の冷蔵庫に入れて、一晩放置した。析出した結晶をろ過により分取し、水で洗浄し、真空乾燥した。乾燥した結晶を１９０℃で１０分間加熱して完全に溶融させ、２５℃で３０分間かけて徐々に再析出させることで、フラックス３を得た。 Flux 3: solid salt of succinic acid and benzylamine, average particle diameter 10 μm
Flux 3 production method:
24 g of water as a reaction solvent and 11.809 g of succinic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle and dissolved at room temperature until uniform. Thereafter, 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for about 5 minutes to obtain a mixed solution. The obtained mixture was put in a refrigerator at 5 ° C to 10 ° C and left overnight. The precipitated crystals were separated by filtration, washed with water, and dried under vacuum. The dried crystal was heated at 190 ° C. for 10 minutes to completely melt it, and gradually reprecipitated at 25 ° C. for 30 minutes to obtain flux 3.
　フラックス４：コハク酸とベンジルアミンとの反応物である液体化合物
　フラックス４の作製方法：
　３つ口フラスコに、コハク酸（和光純薬工業社製）１１．８０９ｇと、ベンジルアミン（和光純薬工業社製）１０．７１５ｇとを入れて、２００℃で２時間加熱して反応させ、フラックス４を得た。 Flux 4: Liquid compound which is a reaction product of succinic acid and benzylamine Method for preparing flux 4:
In a three-necked flask, 11.809 g of succinic acid (manufactured by Wako Pure Chemical Industries) and 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries) were added, and heated at 200 ° C. for 2 hours to react. Flux 4 was obtained.
　フラックス５：リンゴ酸とベンジルアミンとの固体塩、平均粒子径５μｍ
　フラックス５の作製方法：
　ガラスビンに、反応溶媒である水２４ｇと、リンゴ酸（和光純薬工業社製）１３．４０９ｇとを入れ、室温で均一になるまで溶解させた。その後、ベンジルアミン（和光純薬工業社製）１０．７１５ｇを入れて、約５分間撹拌し、混合液を得た。得られた混合液を５℃～１０℃の冷蔵庫に入れて、一晩放置した。析出した結晶をろ過により分取し、水で洗浄し、真空乾燥した。乾燥した結晶を１８０℃で１５分間加熱して完全に溶融させ、２５℃で３０分間かけて徐々に再析出させることで、フラックス５を得た。 Flux 5: solid salt of malic acid and benzylamine, average particle size 5 μm
Method for preparing flux 5:
24 g of water as a reaction solvent and 13.409 g of malic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle and dissolved at room temperature until uniform. Thereafter, 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for about 5 minutes to obtain a mixed solution. The obtained mixture was put in a refrigerator at 5 ° C to 10 ° C and left overnight. The precipitated crystals were separated by filtration, washed with water, and dried under vacuum. The dried crystal was heated at 180 ° C. for 15 minutes to completely melt it, and was gradually reprecipitated at 25 ° C. for 30 minutes to obtain flux 5.
　フラックス６：リンゴ酸とベンジルアミンとの反応物である液体化合物
　フラックス６の作製方法：
　３つ口フラスコに、リンゴ酸（和光純薬工業社製）１３．４０９ｇと、ベンジルアミン（和光純薬工業社製）１０．７１５ｇとを入れて、１５０℃で３時間加熱して反応させ、フラックス６を得た。 Flux 6: liquid compound which is a reaction product of malic acid and benzylamine Method for preparing flux 6:
13.409 g of malic acid (manufactured by Wako Pure Chemical Industries) and 10.715 g of benzylamine (manufactured by Wako Pure Chemical Industries) were placed in a three-necked flask, and reacted by heating at 150 ° C. for 3 hours. Flux 6 was obtained.
　（固体塩の平均粒子径）
　固体塩の平均粒子径は、走査型電子顕微鏡（日立製作所社製「Ｓ－４３００ＳＥＮ」）を用いて、任意の固体塩５０個の粒子径を測定し、その平均値から算出した。 (Average particle size of solid salt)
The average particle size of the solid salt was calculated from the average value by measuring the particle size of 50 arbitrary solid salts using a scanning electron microscope (“S-4300SEN” manufactured by Hitachi, Ltd.).
　（実施例１～３及び比較例１～４）
　（１）導電材料（異方性導電ペースト）の作製
　下記の表１，２に示す成分を下記の表１，２に示す配合量で配合して、導電材料（異方性導電ペースト）を得た。 (Examples 1-3 and Comparative Examples 1-4)
(1) Preparation of conductive material (anisotropic conductive paste) The components shown in Tables 1 and 2 below are blended in the amounts shown in Tables 1 and 2 below to obtain a conductive material (anisotropic conductive paste). Was.
　（２）第１の接続構造体（Ｌ／Ｓ＝５０μｍ／５０μｍ）の作製
　作製直後の導電材料（異方性導電ペースト）を用いて、以下のようにして、第１の接続構造体を作製した。 (2) Preparation of First Connection Structure (L / S = 50 μm / 50 μm) Using a conductive material (anisotropic conductive paste) immediately after preparation, a first connection structure is prepared as follows. did.
　Ｌ／Ｓが５０μｍ／５０μｍ、電極長さ３ｍｍの銅電極パターン（銅電極の厚み１２μｍ）を上面に有するガラスエポキシ基板（ＦＲ－４基板）（第１の接続対象部材）を用意した。また、Ｌ／Ｓが５０μｍ／５０μｍ、電極長さ３ｍｍの銅電極パターン（銅電極の厚み１２μｍ）を下面に有するフレキシブルプリント基板（第２の接続対象部材）を用意した。 ガ ラ ス A glass epoxy substrate (FR-4 substrate) (first connection target member) having a copper electrode pattern (copper electrode thickness: 12 μm) having an L / S of 50 μm / 50 μm and an electrode length of 3 mm on the upper surface was prepared. In addition, a flexible printed circuit board (second connection target member) having a copper electrode pattern (copper electrode thickness: 12 μm) having an L / S of 50 μm / 50 μm and an electrode length of 3 mm on the lower surface was prepared.
　上記ガラスエポキシ基板と上記フレキシブルプリント基板との重ね合わせ面積は、１．５ｃｍ×３ｍｍとし、接続した電極数は７５対とした。 (4) The overlapping area of the glass epoxy substrate and the flexible printed board was 1.5 cm × 3 mm, and the number of connected electrodes was 75 pairs.
　上記ガラスエポキシ基板の上面に、作製直後の導電材料（異方性導電ペースト）を、ガラスエポキシ基板の電極上で厚さ１００μｍとなるように、メタルマスクを用い、スクリーン印刷にて塗工し、導電材料（異方性導電ペースト）層を形成した。次に、導電材料（異方性導電ペースト）層の上面に上記フレキシブルプリント基板を、電極同士が対向するように積層した。このとき、加圧を行わなかった。導電材料（異方性導電ペースト）層には、上記フレキシブルプリント基板の重量は加わる。その状態から、導電材料（異方性導電ペースト）層の温度が、昇温開始から５秒後にはんだの融点となるように加熱した。さらに、昇温開始から１５秒後に、導電材料（異方性導電ペースト）層の温度が２２０℃以上となるように加熱し、導電材料（異方性導電ペースト）層を硬化させ、接続構造体を得た。加熱時には、加圧を行わなかった。 On the upper surface of the glass epoxy substrate, a conductive material (anisotropic conductive paste) immediately after production is applied by screen printing using a metal mask so as to have a thickness of 100 μm on the electrodes of the glass epoxy substrate, A conductive material (anisotropic conductive paste) layer was formed. Next, the flexible printed circuit board was laminated on the upper surface of the conductive material (anisotropic conductive paste) layer so that the electrodes faced each other. At this time, no pressurization was performed. The weight of the flexible printed board is added to the conductive material (anisotropic conductive paste) layer. From this state, heating was performed so that the temperature of the conductive material (anisotropic conductive paste) layer became the melting point of the solder 5 seconds after the start of the temperature rise. Further, 15 seconds after the start of the temperature increase, the conductive material (anisotropic conductive paste) layer is heated so that the temperature of the conductive material (anisotropic conductive paste) layer becomes 220 ° C. or higher, and the conductive material (anisotropic conductive paste) layer is cured. I got No pressure was applied during heating.
　（３）第２の接続構造体（Ｌ／Ｓ＝７５μｍ／７５μｍ）の作製
　Ｌ／Ｓが７５μｍ／７５μｍ、電極長さ３ｍｍの銅電極パターン（銅電極の厚み１２μｍ）を上面に有するガラスエポキシ基板（ＦＲ－４基板）（第１の接続対象部材）を用意した。また、Ｌ／Ｓが７５μｍ／７５μｍ、電極長さ３ｍｍの銅電極パターン（銅電極の厚み１２μｍ）を下面に有するフレキシブルプリント基板（第２の接続対象部材）を用意した。 (3) Production of Second Connection Structure (L / S = 75 μm / 75 μm) Glass epoxy substrate having a copper electrode pattern (copper electrode thickness 12 μm) having an L / S of 75 μm / 75 μm and an electrode length of 3 mm on the upper surface (FR-4 substrate) (first connection target member) was prepared. Also, a flexible printed board (second connection target member) having a copper electrode pattern (copper electrode thickness: 12 μm) with an L / S of 75 μm / 75 μm and an electrode length of 3 mm on the lower surface was prepared.
　Ｌ／Ｓが異なる上記ガラスエポキシ基板及びフレキシブルプリント基板を用いたこと以外は第１の接続構造体の作製と同様にして、第２の接続構造体を得た。 ２A second connection structure was obtained in the same manner as in the production of the first connection structure except that the above-mentioned glass epoxy substrate and flexible printed circuit board having different L / S were used.
　（４）第３の接続構造体（Ｌ／Ｓ＝１００μｍ／１００μｍ）の作製
　Ｌ／Ｓが１００μｍ／１００μｍ、電極長さ３ｍｍの銅電極パターン（銅電極の厚み１２μｍ）を上面に有するガラスエポキシ基板（ＦＲ－４基板）（第１の接続対象部材）を用意した。また、Ｌ／Ｓが１００μｍ／１００μｍ、電極長さ３ｍｍの銅電極パターン（銅電極の厚み１２μｍ）を下面に有するフレキシブルプリント基板（第２の接続対象部材）を用意した。 (4) Preparation of Third Connection Structure (L / S = 100 μm / 100 μm) Glass epoxy substrate having a copper electrode pattern (copper electrode thickness: 12 μm) having an L / S of 100 μm / 100 μm and an electrode length of 3 mm on the upper surface (FR-4 substrate) (first connection target member) was prepared. Further, a flexible printed board (second connection target member) having a copper electrode pattern (thickness of the copper electrode: 12 μm) having an L / S of 100 μm / 100 μm and an electrode length of 3 mm on the lower surface was prepared.
　Ｌ／Ｓが異なる上記ガラスエポキシ基板及びフレキシブルプリント基板を用いたこと以外は第１の接続構造体の作製と同様にして、第３の接続構造体を得た。 ３A third connection structure was obtained in the same manner as in the production of the first connection structure except that the above-mentioned glass epoxy substrate and flexible printed circuit board having different L / S were used.
　（評価）
　（１）フラックスの存在状態
　得られた導電材料中のフラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物を含んでいるか否かを確認した。フラックスの存在状態を以下の基準で判定した。 (Evaluation)
(1) Existence state of flux The flux in the obtained conductive material is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group. It was confirmed whether or not a liquid compound which was a reaction product with the fourth compound having an amino group was contained. The existence state of the flux was determined based on the following criteria.
　［フラックスの存在状態の判定基準］
　○：導電材料中のフラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物の双方を含む
　×：導電材料中のフラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物の内の少なくとも一方を含まない [Judgment criteria for flux existence state]
：: a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a third compound having a carboxyl group and a fourth compound having an amino group, wherein the flux in the conductive material is X: the flux in the conductive material is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a flux having a carboxyl group. Not containing at least one of the liquid compounds which are the reaction product of the compound of No. 3 with the fourth compound having an amino group
　（２）保存安定性
　作製直後の導電材料（異方性導電ペースト）の２５℃での粘度（η１）を測定した。また、作製直後の導電材料（異方性導電ペースト）を常温で２４時間放置し、放置後の導電材料（異方性導電ペースト）の２５℃での粘度（η２）を測定した。上記粘度は、Ｅ型粘度計（東機産業社製「ＴＶＥ２２Ｌ」）を用いて、２５℃及び５ｒｐｍの条件で測定した。粘度の測定値から、粘度上昇率（η２／η１）を算出した。保存安定性を以下の基準で判定した。 (2) Storage stability The viscosity (η1) at 25 ° C. of the conductive material (anisotropic conductive paste) immediately after preparation was measured. Further, the conductive material (anisotropic conductive paste) immediately after the preparation was allowed to stand at room temperature for 24 hours, and the viscosity (η2) at 25 ° C. of the conductive material (anisotropic conductive paste) after standing was measured. The viscosity was measured at 25 ° C. and 5 rpm using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.). The viscosity increase rate (η2 / η1) was calculated from the measured viscosity value. Storage stability was determined based on the following criteria.
　［保存安定性の判定基準］
　○：粘度上昇率（η２／η１）が１．５以下
　△：粘度上昇率（η２／η１）が１．５を超え２．０以下
　×：粘度上昇率（η２／η１）が２．０を超える [Criteria for storage stability]
：: Viscosity increase rate (η2 / η1) is 1.5 or less Δ: Viscosity increase rate (η2 / η1) exceeds 1.5 and 2.0 or less ×: Viscosity increase rate (η2 / η1) is 2.0 Exceed
　（３）電極上のはんだの配置精度（はんだの凝集性）
　得られた第１、第２及び第３の接続構造体において、第１の電極と接続部と第２の電極との積層方向に第１の電極と第２の電極との対向し合う部分をみたときに、第１の電極と第２の電極との対向し合う部分の面積１００％中の、接続部中のはんだ部が配置されている面積の割合Ｘを評価した。電極上のはんだの配置精度（はんだの凝集性）を下記の基準で判定した。 (3) Solder placement accuracy on electrodes (solder cohesion)
In the obtained first, second, and third connection structures, a portion where the first electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode is As a result, the ratio X of the area where the solder portion in the connection portion was arranged in 100% of the area of the portion where the first electrode and the second electrode face each other was evaluated. The placement accuracy (solder cohesion) of the solder on the electrode was determined according to the following criteria.
　［電極上のはんだの配置精度（はんだの凝集性）の判定基準］
　○○：割合Ｘが７０％以上
　○：割合Ｘが６０％以上７０％未満
　△：割合Ｘが５０％以上６０％未満
　×：割合Ｘが５０％未満 [Criteria for determining placement accuracy of solder on electrodes (solder cohesion)]
○: Ratio X is 70% or more ：: Ratio X is 60% or more and less than 70% Δ: Ratio X is 50% or more and less than 60% X: Ratio X is less than 50%
　（４）上下の電極間の導通信頼性
　得られた第１、第２及び第３の接続構造体（ｎ＝１５個）において、上下の電極間の１接続箇所当たりの接続抵抗をそれぞれ、４端子法により、測定した。接続抵抗の平均値を算出した。なお、電圧＝電流×抵抗の関係から、一定の電流を流した時の電圧を測定することにより接続抵抗を求めることができる。導通信頼性を下記の基準で判定した。 (4) Conduction reliability between upper and lower electrodes In the obtained first, second, and third connection structures (n = 15), the connection resistance per connection between the upper and lower electrodes is set to 4 It was measured by the terminal method. The average value of the connection resistance was calculated. The connection resistance can be obtained by measuring the voltage when a constant current flows from the relationship of voltage = current × resistance. The conduction reliability was determined according to the following criteria.
　［導通信頼性の判定基準］
　○○：接続抵抗の平均値が５０ｍΩ以下
　○：接続抵抗の平均値が５０ｍΩを超え７０ｍΩ以下
　△：接続抵抗の平均値が７０ｍΩを超え１００ｍΩ以下
　×：接続抵抗の平均値が１００ｍΩを超える、又は接続不良が生じている [Criteria for continuity reliability]
○: The average value of the connection resistance is 50 mΩ or less ○: The average value of the connection resistance is more than 50 mΩ and 70 mΩ or less △: The average value of the connection resistance is more than 70 mΩ and 100 mΩ or less ×: The average value of the connection resistance exceeds 100 mΩ, or Poor connection
　（５）横方向に隣接する電極間の絶縁信頼性
　得られた第１、第２及び第３の接続構造体（ｎ＝１５個）において、８５℃、湿度８５％の雰囲気中に１００時間放置した後、横方向に隣接する電極間に、５Ｖを印加し、抵抗値を２５箇所で測定した。絶縁信頼性を下記の基準で判定した。 (5) Insulation reliability between laterally adjacent electrodes The obtained first, second, and third connection structures (n = 15) were left in an atmosphere of 85 ° C. and 85% humidity for 100 hours. After that, 5 V was applied between the horizontally adjacent electrodes, and the resistance was measured at 25 points. The insulation reliability was determined based on the following criteria.
　［絶縁信頼性の判定基準］
　○○：接続抵抗の平均値が１０７Ω以上
　○：接続抵抗の平均値が１０６Ω以上１０７Ω未満
　△：接続抵抗の平均値が１０５Ω以上１０６Ω未満
　×：接続抵抗の平均値が１０５Ω未満 [Criteria for insulation reliability]
○: The average value of the connection resistance is 10 7 Ω or more. ○: The average value of the connection resistance is 10 6 Ω or more and less than 10 7 Ω. Δ: The average value of the connection resistance is 10 5 Ω or more and less than 10 6 Ω. Average value is less than 10 5 Ω
　結果を下記の表１，２に示す。 The results are shown in Tables 1 and 2 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　フレキシブルプリント基板に代えて、樹脂フィルム、フレキシブルフラットケーブル及びリジッドフレキシブル基板を用いた場合でも、同様の傾向が見られた。 同 様 The same tendency was observed when a resin film, a flexible flat cable, and a rigid flexible substrate were used instead of the flexible printed substrate.
　１，１Ｘ…接続構造体
　２…第１の接続対象部材
　２ａ…第１の電極
　３…第２の接続対象部材
　３ａ…第２の電極
　４，４Ｘ…接続部
　４Ａ，４ＸＡ…はんだ部
　４Ｂ，４ＸＢ…硬化物部
　１１…導電材料
　１１Ａ…はんだ粒子（導電性粒子）
　１１Ｂ…熱硬化性成分
　２１…導電性粒子（はんだ粒子）
　３１…導電性粒子
　３２…基材粒子
　３３…導電部（はんだを有する導電部）
　３３Ａ…第２の導電部
　３３Ｂ…はんだ部
　４１…導電性粒子
　４２…はんだ部 1, 1X Connection structure 2 First member to be connected 2a First electrode 3 Second member to be connected 3a Second electrode 4, 4X Connection part 4A, 4XA Solder part 4B, 4XB … Curing material part 11… Conductive material 11A… Solder particles (conductive particles)
11B: thermosetting component 21: conductive particles (solder particles)
31 conductive particles 32 base particles 33 conductive part (conductive part having solder)
33A: second conductive portion 33B: solder portion 41: conductive particles 42: solder portion

Claims (10)

  1. 　導電部の外表面部分にはんだを有する複数の導電性粒子と、熱硬化性成分と、フラックスとを含み、
    　前記フラックスが、カルボキシル基を有する第１の化合物とアミノ基を有する第２の化合物との固体塩、及び、カルボキシル基を有する第３の化合物とアミノ基を有する第４の化合物との反応物である液体化合物を含む、導電材料。     Including a plurality of conductive particles having solder on the outer surface portion of the conductive portion, a thermosetting component, and a flux,
    The flux is a solid salt of a first compound having a carboxyl group and a second compound having an amino group, and a reaction product of a third compound having a carboxyl group and a fourth compound having an amino group. A conductive material containing a liquid compound.
  2. 　前記固体塩の含有量の、前記液体化合物の含有量に対する重量比が、２以上２０以下である、請求項１に記載の導電材料。 The conductive material according to claim 1, wherein the weight ratio of the content of the solid salt to the content of the liquid compound is 2 or more and 20 or less.
  3. 　前記第１の化合物と前記第３の化合物とが、同一の化合物である、請求項１又は２に記載の導電材料。 The conductive material according to claim 1 or 2, wherein the first compound and the third compound are the same compound.
  4. 　前記第２の化合物と前記第４の化合物とが、同一の化合物である、請求項１～３のいずれか１項に記載の導電材料。 4. The conductive material according to claim 1, wherein the second compound and the fourth compound are the same compound.
  5. 　前記固体塩の平均粒子径が、０．０１μｍ以上１０μｍ以下である、請求項１～４のいずれか１項に記載の導電材料。 The conductive material according to any one of claims 1 to 4, wherein the solid salt has an average particle size of 0.01 μm or more and 10 μm or less.
  6. 　前記熱硬化性成分が、熱硬化性化合物を含み、
    　前記熱硬化性化合物１００重量部に対して、前記フラックスの含有量が、１重量部以上５０重量部以下である、請求項１～５のいずれか１項に記載の導電材料。     The thermosetting component contains a thermosetting compound,
    The conductive material according to any one of claims 1 to 5, wherein the content of the flux is 1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the thermosetting compound.
  7. 　導電材料１００重量％中、前記フラックスの含有量が、０．０５重量％以上２０重量％以下である、請求項１～６のいずれか１項に記載の導電材料。 (7) The conductive material according to any one of (1) to (6), wherein the content of the flux is from 0.05% by weight to 20% by weight based on 100% by weight of the conductive material.
  8. 　前記導電性粒子の平均粒子径が、０．０１μｍ以上５０μｍ以下である、請求項１～７のいずれか１項に記載の導電材料。 (8) The conductive material according to any one of (1) to (7), wherein the average particle size of the conductive particles is 0.01 μm or more and 50 μm or less.
  9. 　導電ペーストである、請求項１～８のいずれか１項に記載の導電材料。 The conductive material according to any one of claims 1 to 8, which is a conductive paste.
  10. 　第１の電極を表面に有する第１の接続対象部材と、
    　第２の電極を表面に有する第２の接続対象部材と、
    　前記第１の接続対象部材と、前記第２の接続対象部材とを接続している接続部とを備え、
    　前記接続部の材料が、請求項１～９のいずれか１項に記載の導電材料であり、
    　前記第１の電極と前記第２の電極とが、前記導電性粒子により電気的に接続されている、接続構造体。     A first connection target member having a first electrode on its surface;
    A second member to be connected having a second electrode on its surface;
    The first connection target member, and a connection portion that connects the second connection target member,
    The material of the connection portion is the conductive material according to any one of claims 1 to 9,
    A connection structure, wherein the first electrode and the second electrode are electrically connected by the conductive particles.
PCT/JP2019/031425 2018-09-14 2019-08-08 Conductive material and connection structure WO2020054288A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004025305A (en) * 2002-04-16 2004-01-29 Tadatomo Suga Residue-free solder paste
JP2017080797A (en) * 2015-10-30 2017-05-18 パナソニックＩｐマネジメント株式会社 Solder paste, flux for soldering, and mounting structure using the same
JP2018060709A (en) * 2016-10-06 2018-04-12 積水化学工業株式会社 Conductive material, connection structure, and method for producing connection structure

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108028090B (en) 2016-01-25 2020-11-13 积水化学工业株式会社 Conductive material and connection structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004025305A (en) * 2002-04-16 2004-01-29 Tadatomo Suga Residue-free solder paste
JP2017080797A (en) * 2015-10-30 2017-05-18 パナソニックＩｐマネジメント株式会社 Solder paste, flux for soldering, and mounting structure using the same
JP2018060709A (en) * 2016-10-06 2018-04-12 積水化学工業株式会社 Conductive material, connection structure, and method for producing connection structure

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