WO2017010445A1 - Conductive material and connection structure - Google Patents

Conductive material and connection structure Download PDF

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Publication number
WO2017010445A1
WO2017010445A1 PCT/JP2016/070386 JP2016070386W WO2017010445A1 WO 2017010445 A1 WO2017010445 A1 WO 2017010445A1 JP 2016070386 W JP2016070386 W JP 2016070386W WO 2017010445 A1 WO2017010445 A1 WO 2017010445A1
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WO
WIPO (PCT)
Prior art keywords
solder
conductive
electrode
particles
conductive particles
Prior art date
Application number
PCT/JP2016/070386
Other languages
French (fr)
Japanese (ja)
Inventor
石澤　英亮
敬三 西岡
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 JP2016546857A priority Critical patent/JP6166849B2/en
Priority to KR1020177016241A priority patent/KR20180029945A/en
Priority to CN201680003614.2A priority patent/CN107077915A/en
Publication of WO2017010445A1 publication Critical patent/WO2017010445A1/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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/83886—Involving a self-assembly process, e.g. self-agglomeration of a material dispersed in a fluid

Definitions

  • the present invention relates to a conductive material including conductive particles having solder.
  • the present invention also 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 may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
  • FOG Glass
  • COF Chip on Film
  • an anisotropic conductive material containing conductive particles is disposed on the glass epoxy substrate. To do.
  • a flexible printed circuit board is laminated, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
  • the following Patent Document 1 describes an anisotropic conductive material including conductive particles and a resin component that cannot be cured at the melting point of the conductive particles.
  • the conductive particles include tin (Sn), indium (In), bismuth (Bi), silver (Ag), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd ), Gallium (Ga), silver (Ag), thallium (Tl), and the like, and alloys of these metals.
  • Patent Document 1 a resin heating step for heating the anisotropic conductive resin to a temperature higher than the melting point of the conductive particles and at which the curing of the resin component is not completed, and a resin component curing step for curing the resin component The electrical connection between the electrodes is described.
  • Patent Document 1 describes that mounting is performed with the temperature profile shown in FIG. In Patent Document 1, the conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive resin is heated.
  • Patent Document 2 discloses an adhesive tape that includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent are present in the resin layer. Yes.
  • This adhesive tape is in the form of a film, not a paste.
  • Patent Document 2 discloses a bonding method using the above adhesive tape. Specifically, a first substrate, an adhesive tape, a second substrate, an adhesive tape, and a third substrate are laminated in this order from the bottom to obtain a laminate. At this time, the first electrode provided on the surface of the first substrate is opposed to the second electrode provided on the surface of the second substrate. Moreover, the 2nd electrode provided in the surface of the 2nd board
  • a semiconductor chip having a plurality of connection terminals is disposed so as to face a wiring board having a plurality of electrode terminals, and the electrode terminals of the wiring board and the above-mentioned semiconductor chip
  • a flip chip mounting method for electrically connecting a connection terminal includes (1) a step of supplying a resin containing solder powder and a convection additive onto the surface of the wiring board having the electrode terminals, and (2) the semiconductor chip on the resin surface. (3) a step of heating the wiring substrate to a temperature at which the solder powder melts, and (4) a step of curing the resin after the heating step.
  • a connection body for electrically connecting the electrode terminal and the connection terminal is formed, and in the resin curing step (4), the semiconductor chip is connected to the wiring board. Secure to.
  • solder powder or conductive particles may not be efficiently disposed on the electrodes (lines).
  • the moving speed of the solder powder or conductive particles onto the electrode may be slow.
  • Patent Document 2 there is no specific description of the conductive particles used for the anisotropic conductive material.
  • the copper layer is formed on the surface of the resin particle, and the electroconductive particle in which the solder layer is formed on the surface of this copper layer is used.
  • the central part of the conductive particles is composed of resin particles.
  • the anisotropic conductive material described in Patent Documents 2 and 3 is used, the conductive particles are difficult to be efficiently arranged on the electrodes (lines), and positional displacement between the upper and lower electrodes to be connected may occur. There are things to do.
  • the dispersibility of the conductive particles may be low. For this reason, when the anisotropic conductive material is used after being stored, the conductive particles may be more difficult to be disposed on the electrode (line).
  • the conductive particles include a plurality of conductive particles, a thermosetting compound, and a thermosetting agent, and the conductive particles have solder on an outer surface portion of a conductive portion, and the conductive The conductive particles are provided with a conductive material having an O—Si bond on the outer surface of the solder of the conductive portion.
  • the conductive particles have a Sn—O—Si bond on the outer surface of the solder of the conductive portion.
  • the conductive material is a surface-treated product with a silane coupling agent.
  • the conductive particles have an amino group on the outer surface of the solder of the conductive portion.
  • the conductive particles have a carboxyl group-containing group on the outer surface of the solder of the conductive portion via a Sn—O—Si bond.
  • the conductive particles are solder particles.
  • the conductive particles have an average particle diameter of 1 ⁇ m or more and 60 ⁇ m or less.
  • the content of the conductive particles is 10% by weight to 80% by weight in 100% by weight of the conductive material.
  • 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 and the A connection part connecting the second connection target member
  • the material of the connection part is the conductive material described above
  • the first electrode and the second electrode are in the conductive particles
  • a connection structure is provided that is electrically connected by solder.
  • the conductive material according to the present invention includes a plurality of conductive particles, a thermosetting compound, and a thermosetting agent, and the conductive particles have solder on the outer surface portion of the conductive portion, and the conductive Since the particles have an O—Si bond on the outer surface of the solder in the conductive part, the dispersibility of the conductive particles in the conductive material is high, and the solder in the conductive particles is efficiently arranged on the electrode. And the reliability of conduction between the electrodes can be improved.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
  • 2A to 2C are cross-sectional views for explaining each step 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 as a conductive material.
  • FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used for the conductive material.
  • FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used for the conductive material.
  • the conductive material according to the present invention includes a plurality of conductive particles, a thermosetting compound, and a thermosetting agent.
  • the conductive particles have a conductive part.
  • the conductive particles have solder on the outer surface portion of the conductive portion. Solder is contained in the conductive part and is a part or all of the conductive part.
  • the conductive particles have an O—Si bond on the outer surface of the solder of the conductive portion.
  • the corrosion of the solder is considerably suppressed.
  • the solder in the conductive particles easily collects between the upper and lower electrodes, and the solder in the conductive particles is removed from the electrode ( Line).
  • a part of the solder in the conductive particles is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be considerably reduced.
  • the electroconductive particle which is not located between the opposing electrodes can be efficiently moved between the opposing electrodes. Therefore, the conduction reliability between the electrodes can be improved.
  • the dispersibility of the conductive particles in the conductive material is high, and the storage stability of the conductive material is excellent.
  • the corrosion of the solder in the conductive particles hardly progresses. For this reason, it is possible to efficiently arrange the solder in the conductive particles on the electrodes regardless of whether the conductive material is stored before or after storage, and the conduction reliability between the electrodes can be improved.
  • the present invention it is possible to prevent displacement between the electrodes.
  • the electrode of the first connection target member and the electrode of the second connection target member Even when the first connection target member and the second connection target member are overlapped in a state where the alignment of the first connection target member and the second connection target member are overlaid, the shift is corrected and the first connection target member electrode and the second connection target are corrected.
  • the electrode of the member can be connected (self-alignment effect).
  • the conductive particles preferably have a Sn—O—Si bond on the outer surface of the solder of the conductive portion.
  • the conductive particles are preferably obtained by surface treatment using a silane coupling agent, and the conductive particles are surface-treated by a silane coupling agent. Preferably it has been treated. That is, the conductive particles are preferably a surface-treated product with a silane coupling agent.
  • the conductive particles may be solder particles.
  • the solder particles are formed of solder.
  • the solder particles have solder on the outer surface portion of the conductive portion.
  • the solder particles are particles in which both the central portion and the outer surface portion of the conductive portion are formed of solder, and both the central portion and the outer surface portion of the conductive portion are solder.
  • the said electroconductive particle may have a base material particle and the electroconductive part arrange
  • the conductive particles including the solder particles are used, the case where the conductive particles including the base particles not formed by the solder and the solder portion arranged on the surface of the base particles are used.
  • the conductive particles are less likely to collect on the electrodes, and the conductive particles that have moved onto the electrodes tend to move out of the electrodes because of the low solderability between the conductive particles. There is a tendency that the effect of suppressing misalignment also becomes low. Therefore, the conductive particles are preferably solder particles formed by solder.
  • the viscosity ( ⁇ 25) at 25 ° C. of the conductive material is preferably 10 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, and further preferably 100 Pa ⁇ s or more. Yes, preferably 800 Pa ⁇ s or less, more preferably 600 Pa ⁇ s or less, and even more preferably 500 Pa ⁇ s or less.
  • the viscosity ( ⁇ 25) can be adjusted as appropriate to the type and amount of the compounding ingredients. Further, the use of a filler can make the viscosity relatively high.
  • the viscosity ( ⁇ 25) can be measured using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) and the like at 25 ° C. and 5 rpm.
  • E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) and the like 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. From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrode, the conductive material is preferably an anisotropic conductive paste.
  • the conductive material is preferably used for electrical connection of electrodes.
  • the conductive material is preferably a circuit connection material.
  • the conductive particles electrically connect the electrodes of the connection target member.
  • the conductive particles have solder on the outer surface portion of the conductive portion.
  • the conductive particles have an O—Si bond on the outer surface of the solder of the conductive portion.
  • a solder component atom constituting the solder
  • the conductive particles have, for example, (solder component) -O-Si bond ((atom constituting the solder) -O-Si bond) on the outer surface of the solder of the conductive portion.
  • the conductive particles are disposed on the outside of the solder of the conductive portion.
  • the surface preferably has a Sn—O—Si bond.
  • a silane coupling agent can be reacted with the hydroxyl group on the solder surface.
  • An O—Si bond can be formed by reacting a hydroxyl group on the surface of the solder with a silane coupling agent.
  • the conductive material is subjected to surface treatment using a silane coupling agent to obtain conductive particles having Sn—O—Si bonds on the outer surface of the solder of the conductive portion, and then thermally cured with the conductive particles. It is preferable that it is obtained by mixing a functional compound and a thermosetting agent.
  • the conductive particles are disposed on the outside of the solder of the conductive portion. It is preferable to have an amino group on the surface.
  • the conductive particles are disposed on the outside of the solder of the conductive portion.
  • the surface has a carboxyl group-containing group via an O—Si bond
  • the outer surface of the solder of the conductive portion has a carboxyl group-containing group via a Sn—O—Si bond. More preferred.
  • the solder aggregating performance is considerably increased.
  • the conductive particles are formed on the surface using a silane coupling agent.
  • a silane coupling agent After the treatment, it is preferably obtained by introducing a carboxyl group-containing group.
  • a carboxyl group-containing group can be introduced into the residue of the silane coupling agent.
  • the conductive particles preferably have a group derived from a silane coupling agent and a carboxyl-containing group, and the solder and the carboxyl group-containing group are bonded via a group derived from the silane coupling agent. Is preferred.
  • the silane coupling agent preferably has an organic functional group and an alkoxy group in one molecule, and the organic functional group is preferably capable of reacting with a compound having a carboxyl group-containing group.
  • the alkoxy group include a methoxy group and an ethoxy group.
  • the silane coupling agent include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, and a silane coupling agent having an isocyanate group.
  • the silane coupling agent is preferably a silane coupling agent having an amino group.
  • the said silane coupling agent only 1 type may be used and 2 or more types may be used together.
  • this amino group may not be an amino group derived from the silane coupling agent which has an amino group.
  • silane coupling agent having an epoxy group examples include KBM-303, KBM-402, KBM-403, KBE-402 and KBE-403 manufactured by Shin-Etsu Silicone.
  • examples of the silane coupling agent having an amino group examples include KBM-602, KBM-603, KBM-903, and the like.
  • examples of the silane coupling agent having an isocyanate group include KBE-9007.
  • Examples of the compound for introducing the carboxyl group-containing group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4 -Aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid Hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, nonadecanoic acid, arachi
  • the conductive particles and the silane coupling agent are placed in a low-polarity solvent such as toluene to cause a dealcoholization reaction. Methods and the like.
  • FIG. 4 is a cross-sectional view showing a first example of conductive particles that can be used as 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 base particles in the core, and are not core-shell particles.
  • both the center part and the outer surface part of an electroconductive part are formed with the solder.
  • FIG. 5 is a cross-sectional view showing a second example of conductive particles that can be used as a conductive material.
  • the electroconductive particle 31 shown in FIG. 5 is equipped with the base material particle 32 and the electroconductive part 33 arrange
  • the conductive portion 33 covers the surface of the base particle 32.
  • the conductive particles 31 are coated particles in which the surface of the base particle 32 is covered with the conductive portion 33.
  • the conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion).
  • the conductive particle 31 includes a second conductive portion 33A between the base particle 32 and the solder portion 33B. Therefore, the conductive particles 31 are composed of the base particle 32, the second conductive portion 33A disposed on the surface of the base particle 32, and the solder portion 33B disposed on the outer surface of the second conductive portion 33A.
  • FIG. 6 is a cross-sectional view showing a third example of conductive particles that can be used as a conductive material.
  • the conductive portion 33 in the conductive particle 31 has a two-layer structure.
  • the conductive particle 41 shown in FIG. 6 has a solder part 42 as a single-layer conductive part.
  • the conductive particles 41 include base particles 32 and solder portions 42 disposed on the surfaces of the base particles 32.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the substrate particles are preferably substrate particles excluding metal, and are preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles.
  • the substrate particles may be copper particles.
  • the base particle may have a core and a shell disposed on the surface of the core, or may be a core-shell particle.
  • the core may be an organic core, and the shell may be an inorganic shell.
  • the resin for forming 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; 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, polyethylene terephthalate, polysulfone, polyphenylene oxide , Polyacetal, polyimide, polyamideimide, polyether ether Tons, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer,
  • polyolefin resins such as polyethylene, polypropylene,
  • the divinylbenzene copolymer examples include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
  • the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and And a crosslinkable monomer.
  • non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-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, etc.
  • Oxygen atom-containing (meth) acrylate compounds Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
  • Nitrile-containing monomers such as (meth) acrylonitrile
  • Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether
  • Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stea
  • crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta 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, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
  • examples of inorganic substances for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black.
  • the inorganic substance is preferably not a metal.
  • the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
  • examples of the organic / inorganic hybrid particles include 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 preferably an organic core.
  • the shell is preferably an inorganic shell.
  • the base material 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 for forming the organic core include the resin for forming the resin particles described above.
  • Examples of the material for forming the inorganic shell include inorganic substances for forming the above-described base material particles.
  • the material for forming the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell by a sol-gel method and then sintering the shell.
  • the metal alkoxide is preferably a silane alkoxide.
  • the inorganic shell is preferably formed of a silane alkoxide.
  • the particle diameter of the core is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 30 ⁇ m or less, particularly preferably 15 ⁇ m or less, and most preferably 10 ⁇ m or less. It is.
  • the particle diameter of the core is not less than the above lower limit and not more than the above upper limit, conductive particles more suitable for electrical connection between electrodes can be obtained, and the base particles can be suitably used for the use of conductive particles. Become.
  • the particle diameter of the core is not less than the lower limit and not more than the upper limit
  • the contact area between the conductive particles and the electrodes is sufficiently large, and Aggregated conductive particles are hardly formed when the conductive layer is formed.
  • the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
  • the particle diameter of the core means a diameter when the core is a true sphere, and means a maximum diameter when the core is a shape other than a true sphere.
  • the particle diameter of a core means the average particle diameter which measured the core with arbitrary particle diameter measuring apparatuses. For example, a particle size distribution measuring machine using principles such as laser light scattering, electrical resistance value change, and image analysis after imaging can be used.
  • the thickness of the shell is preferably 100 nm or more, more preferably 200 nm or more, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the thickness of the shell is an average thickness per base particle. The thickness of the shell can be controlled by controlling the sol-gel method.
  • the substrate particles are metal particles
  • examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
  • the metal particles are preferably copper particles.
  • the substrate particles are preferably not metal particles.
  • the particle diameter of the substrate particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 1.5 ⁇ m or more, particularly preferably 2 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, more More preferably, it is 30 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 10 ⁇ m or less, particularly preferably 5 ⁇ m or less, and most preferably 3 ⁇ m or less.
  • the particle diameter of the base material 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 conduction reliability between the electrodes can be further improved and the connection is made through the conductive particles.
  • connection resistance between the formed electrodes can be further reduced.
  • the particle diameter of the substrate particles is not more than the above upper limit, the conductive particles are sufficiently compressed, the connection resistance between the electrodes can be further reduced, and the distance between the electrodes is further reduced. Can do.
  • the particle diameter of the substrate particles indicates a diameter when the substrate particles are spherical, and indicates a maximum diameter when the substrate particles are not spherical.
  • the particle diameter of the substrate particles is particularly preferably 2 ⁇ m or more and 5 ⁇ m or less.
  • the distance between the electrodes can be further reduced, and even if the thickness of the conductive layer is increased, small conductive particles can be obtained. Can do.
  • the method for forming the conductive part on the surface of the base particle and the method for forming the solder part on the surface of the base particle or the surface of the second conductive part are not particularly limited.
  • Examples of the method for forming the conductive portion and the solder portion include 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 substrate particles with a paste containing metal powder or metal powder and a binder.
  • a method using electroless plating, electroplating, or physical collision is preferable.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kogakusha Co., Ltd.) or the like is used.
  • the melting point of the base material particles is preferably higher than the melting points of the conductive part and the solder part.
  • the melting point of the substrate particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, and particularly preferably higher than 450 ° C.
  • the melting point of the substrate particles may be less than 400 ° C.
  • the melting point of the substrate particles may be 160 ° C. or less.
  • the softening point of the substrate particles is preferably 260 ° C. or higher.
  • the softening point of the substrate 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 parts (solder part, second conductive part). That is, in the conductive particles, two or more conductive portions may be stacked. When the conductive part has two or more layers, the conductive particles preferably have solder on the outer surface portion of the conductive part.
  • the solder is preferably a metal (low melting point metal) having a melting point of 450 ° C. or lower.
  • the solder part is preferably a metal layer (low melting point metal layer) having a melting point of 450 ° C. or lower.
  • the low melting point metal layer is a layer containing a low melting point metal.
  • the solder in the conductive particles is preferably metal particles having a melting point of 450 ° C. or lower (low melting point metal particles).
  • the low melting point metal particles are particles containing a low melting point metal.
  • the low melting point metal is a metal having a melting point of 450 ° C. or lower.
  • the melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
  • 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. It is 70% by weight or more, particularly preferably 90% by weight or more.
  • the tin content is determined using a high-frequency inductively coupled plasma emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It can be measured.
  • ICP-AES high-frequency inductively coupled plasma emission spectrometer
  • EDX-800HS fluorescent X-ray 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 not in point contact but in surface contact, the connection resistance is lowered.
  • 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, and as a result, the solder and the electrode are more unlikely to peel off, and the conduction reliability is effective. To be high.
  • the low melting point metal constituting the solder part and the solder particles is not particularly limited.
  • the low melting point metal is preferably tin or an alloy containing tin.
  • 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 with respect to the electrode. More preferred are a tin-bismuth alloy and a tin-indium alloy.
  • the material constituting the solder is preferably a filler material having a liquidus of 450 ° C. or lower based on JIS Z3001: Welding terms.
  • the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like. Of these, a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which is low-melting and lead-free is preferable. 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.
  • the solder in the conductive particles is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese. Further, it may contain a metal such as chromium, molybdenum and palladium. Moreover, from the viewpoint of further increasing the bonding strength between the solder and the electrode, 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 preferably higher than the melting point of the solder part.
  • the melting point of the second conductive part is preferably more than 160 ° C, more preferably more than 300 ° C, still more preferably more than 400 ° C, still more preferably more than 450 ° C, particularly preferably more than 500 ° C, most preferably Preferably it exceeds 600 degreeC. Since the solder part has a low melting point, it melts during conductive connection. It is preferable that the second conductive portion does not melt during conductive connection.
  • the conductive particles are preferably used by melting solder, preferably used by melting the solder part, and used without melting the solder part and melting the second conductive part. It is preferred that Since the melting point of the second conductive part is higher than the melting point of the solder part, it is possible to melt only the solder part without melting the second conductive part during 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, particularly preferably Is 50 ° C. or higher, most preferably 100 ° C. or higher.
  • the second conductive part preferably contains a metal.
  • the metal which comprises the said 2nd electroconductive part is not specifically limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.
  • the second conductive part is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and even more 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 or a gold layer, and still more 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 part is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. .
  • the average particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less, and much more. It is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 20 ⁇ m or less, particularly preferably 15 ⁇ m or less, and most preferably 10 ⁇ m or less.
  • the average particle diameter of the conductive particles is particularly preferably 3 ⁇ m or more and 30 ⁇ m or less.
  • the “average particle size” of the conductive particles indicates a number average particle size.
  • the average particle diameter of the conductive particles is obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing laser diffraction particle size distribution measurement.
  • the coefficient of variation of the particle diameter of the conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less.
  • the variation coefficient of the particle diameter is not less than the above lower limit and not more than the above upper limit, the solder can be more efficiently disposed on the electrode.
  • the coefficient of variation of the particle diameter of the conductive particles may be less than 5%.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the conductive particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 10% by weight or more, particularly preferably 20% by weight or more, most preferably. It is 30% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less.
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be arranged more efficiently on the electrodes, and it is easy to arrange many conductive particles between the electrodes. Therefore, the conduction reliability is further enhanced. From the viewpoint of further improving the conduction reliability, the content of the conductive particles is preferably large.
  • thermosetting compound thermosetting component
  • the thermosetting compound is a compound that can be cured by heating.
  • the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
  • an epoxy compound is preferable from the viewpoint of further improving the curability and viscosity of the conductive material and further improving the connection reliability.
  • the said thermosetting compound only 1 type may be used and 2 or more types may be used together.
  • the above-mentioned epoxy compound includes an aromatic epoxy compound. Crystalline epoxy compounds such as resorcinol-type epoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, and benzophenone-type epoxy compounds are preferred.
  • An epoxy compound that is solid at normal temperature (23 ° C.) and has a melting temperature equal to or lower than the melting point of the solder is preferable. The melting temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and preferably 40 ° C. or higher.
  • the content of the thermosetting compound in 100% by weight of the conductive material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and preferably 99% by weight or less. More preferably, it is 98 weight% or less, More preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting compound is large.
  • thermosetting agent thermosetting component
  • the thermosetting agent thermosets the thermosetting compound.
  • examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and other thiol curing agents, acid anhydrides, thermal cation initiators (thermal cation curing agents), and thermal radical generators. It is done. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.
  • An imidazole curing agent, a thiol curing agent, or an amine curing agent is preferable because the conductive material can be cured more rapidly at a low temperature. Moreover, since a storage stability becomes high when a thermosetting compound and the said thermosetting agent are mixed, a latent hardening agent is preferable.
  • the latent curing agent is preferably a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent.
  • the said thermosetting agent may be coat
  • the imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.
  • the thiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .
  • the amine curing agent is not particularly limited, and hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5].
  • examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.
  • thermal cation initiator examples include iodonium cation curing agents, oxonium cation curing agents, and sulfonium cation curing agents.
  • examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate.
  • examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate.
  • the sulfonium-based cationic curing agent examples include tri-p-tolylsulfonium hexafluorophosphate.
  • the thermal radical generator is not particularly limited, and examples thereof include azo compounds and organic peroxides.
  • 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, still more preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. Hereinafter, it is particularly preferably 140 ° C. or lower.
  • the reaction start temperature of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the solder is more efficiently arranged on the electrode.
  • the reaction initiation temperature of the thermosetting agent is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder, more preferably 5 ° C or higher, more preferably 10 ° C or higher. More preferably.
  • the reaction start temperature of the thermosetting agent means the temperature at which the exothermic peak of DSC starts to rise.
  • the content of the thermosetting agent is not particularly limited.
  • the content of the thermosetting agent with respect to 100 parts by weight of the thermosetting compound is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less, more preferably 75 parts by weight or less.
  • the content of the thermosetting agent is not less than the above lower limit, it is easy to sufficiently cure the conductive material.
  • the content of the thermosetting agent is not more than the above upper limit, it is difficult for an excess thermosetting agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further enhanced.
  • the conductive material preferably contains a flux.
  • flux By using flux, the solder can be more effectively placed on the electrode. Moreover, the connection resistance between electrodes becomes still lower by the expression of the flux effect.
  • the flux is not particularly limited.
  • a flux generally used for soldering or the like can be used. Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an organic acid, and pine resin. Etc.
  • the said flux only 1 type may be used and 2 or more types may be used together.
  • Examples of the molten salt include ammonium chloride.
  • Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid, and glutaric acid.
  • Examples of the pine resin include activated pine resin and non-activated pine resin.
  • the flux is preferably an organic acid having two or more carboxyl groups, pine resin.
  • the flux may be an organic acid having two or more carboxyl groups, or pine resin.
  • the above rosins are rosins whose main component is abietic acid.
  • the flux is preferably rosins, and more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further enhanced.
  • the active temperature (melting point) of the flux is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 200 ° C. or lower, more preferably 190 ° C. or lower, even more preferably 160. ° C or lower, more preferably 150 ° C or lower, still more preferably 140 ° C or lower.
  • the active temperature (melting point) of the flux is preferably 80 ° C. or higher and 190 ° C. or lower.
  • the activation temperature (melting point) of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • the flux having an active temperature (melting point) of 80 ° C. or higher and 190 ° C. or lower includes succinic acid (melting point 186 ° C.), glutaric acid (melting point 96 ° C.), adipic acid (melting point 152 ° C.), pimelic acid (melting point) 104 ° C.), dicarboxylic acids such as suberic acid (melting point 142 ° C.), benzoic acid (melting point 122 ° C.), malic acid (melting point 130 ° C.) and the like.
  • the boiling point of the flux is preferably 200 ° C. or lower.
  • the melting point of the flux is preferably higher than the melting point of the solder, more preferably 5 ° C or higher, and even more preferably 10 ° C or higher. .
  • the melting point of the flux is preferably higher than the reaction start temperature of the thermosetting agent, more preferably 5 ° C or higher, more preferably 10 ° C or higher. More preferably.
  • the flux may be dispersed in the conductive material or may be adhered on the surface of the conductive particles.
  • the flux is preferably a flux that releases cations by heating.
  • a flux that releases cations upon heating the solder can be placed more efficiently on the electrode.
  • thermal cation initiator thermal cation curing agent
  • the content of the flux is preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
  • the conductive material may not contain flux.
  • the flux content is not less than the above lower limit and not more than the above upper limit, it becomes more difficult to form an oxide film on the surface of the solder and the electrode, and the oxide film formed on the surface of the solder and the electrode is more effective. Can be removed.
  • a filler may be added to the conductive material.
  • the filler may be an organic filler or an inorganic filler. By adding the filler, the distance at which the solder aggregates can be suppressed, and the conductive particles can be uniformly aggregated over all the electrodes of the substrate.
  • the filler content is preferably 0% by weight (not contained) or more, preferably 5% by weight or less, more preferably 2% by weight or less, and still more preferably 1% by weight or less. is there.
  • the content of the filler is not less than the above lower limit and not more than the above upper limit, the solder is more efficiently arranged on the electrode.
  • the conductive material may be, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a lubricant as necessary.
  • various additives such as an antistatic agent and a flame retardant may be included.
  • a connection structure according to the present invention includes a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection object member and the connection part which has connected the said 2nd connection object member are provided.
  • the material of the connection portion is the conductive material described above, and the connection portion is formed of the conductive material described above.
  • the first electrode and the second electrode are electrically connected by solder in the conductive particles.
  • the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
  • the manufacturing method of the connection structure according to the present invention includes the step of disposing the conductive material on the surface of the first connection target member having at least one first electrode on the surface, using the conductive material described above.
  • the second connection object member having at least one second electrode on the surface opposite to the first connection object member side of the conductive material, the first electrode and the second electrode
  • the first connection target member and the second connection target member are connected by heating the conductive material to a temperature equal to or higher than the melting point of the solder in the conductive particles, and the step of arranging the electrodes to face each other.
  • the conductive material is heated above the curing temperature of the thermosetting compound.
  • connection structure according to the present invention since the specific conductive material is used, the solder in the conductive particles gathers between the first electrode and the second electrode. It is easy and the solder can be efficiently arranged on the electrode (line). In addition, a part of the solder is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be considerably reduced. Therefore, the conduction reliability between the first electrode and the second electrode can be improved. In addition, it is possible to prevent electrical connection between laterally adjacent electrodes that should not be connected, and to improve insulation reliability.
  • the conductive material is not a conductive film, A conductive paste is preferred.
  • the thickness of the solder part 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 wetted area on the surface of the electrode is preferably 50% or more, more preferably 70% or more, and preferably 100% or less.
  • the second connection target member in the step of arranging the second connection target member and the step of forming the connection portion, no pressure is applied, and the second connection is applied to the conductive material.
  • the weight of the target member is preferably added, and in the step of arranging the second connection target member and the step of forming the connection portion, the conductive material exceeds the weight force of the second connection target member. It is preferable that no pressure is applied.
  • the uniformity of the amount of solder can be further enhanced in the plurality of solder portions.
  • the thickness of the solder portion can be increased more effectively, so that a large amount of solder is easily collected between the electrodes, and the solder can be arranged more efficiently on the electrodes (lines).
  • solder is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be further reduced. Therefore, the conduction reliability between the electrodes can be further enhanced. In addition, the electrical connection between the laterally adjacent electrodes that should not be connected can be further prevented, and the insulation reliability can be further improved.
  • a conductive paste is used instead of a conductive film, it becomes easy to adjust the thicknesses of the connection part and the solder part depending on the amount of the conductive paste applied.
  • the conductive film in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film having a different thickness or to prepare a conductive film having a predetermined thickness. There is.
  • the conductive film in the conductive film, it tends to be difficult to sufficiently lower the melt viscosity of the conductive film at the melting temperature of the solder, and there is a problem that the aggregation of the solder is easily inhibited.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
  • connection structure 1 shown in FIG. 1 is a connection that connects a first connection target member 2, a second connection target member 3, and the first connection target member 2 and the second connection target member 3.
  • Part 4 is formed of the conductive material described above.
  • the conductive material includes a plurality of conductive particles, a thermosetting compound, and a thermosetting agent.
  • the thermosetting compound and the thermosetting agent are thermosetting components.
  • the connecting portion 4 includes a solder portion 4A in which a plurality of conductive particles gather and are joined to each other, and a cured product portion 4B in which a thermosetting component is thermally cured.
  • the first connection object 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 portion 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 product portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a.
  • connection structure 1 after a plurality of conductive particles gather between the first electrode 2a and the second electrode 3a and the plurality of conductive particles melt, the conductive particles The melted material solidifies after the surface of the electrode wets and spreads to form the solder portion 4A. For this reason, the connection area of 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts, and the 2nd electrode 3a becomes large. That is, by using the conductive particles, the solder portion 4A, the first electrode 2a, and the solder are compared with the case where the conductive outer surface is made 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, the conduction
  • the conductive material may contain a flux. When the flux is used, the flux is generally deactivated gradually by heating.
  • connection structure 1 shown in FIG. 1 all of the solder portions 4A are located in the facing region between the first and second electrodes 2a and 3a.
  • the connection structure 1X of the modification shown in FIG. 3 is different from the connection structure 1 shown in FIG. 1 only in the connection portion 4X.
  • the connection part 4X has the solder part 4XA and the hardened
  • most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a are opposed to each other, and a part of the solder portion 4XA is first and second. You may protrude to the side from the area
  • the solder part 4XA protruding laterally from the region where the first and second electrodes 2a and 3a are opposed is a part of the solder part 4XA and is not a solder separated from the solder part 4XA.
  • the amount of solder away from the solder portion can be reduced, but the solder away from the solder portion may exist in the cured product portion.
  • connection structure 1X If the use amount of the conductive particles is reduced, it becomes easy to obtain the connection structure 1. If the usage-amount of electroconductive particle is increased, it will become easy to obtain the connection structure 1X.
  • the first electrode 2a and the second electrode 2a are arranged in the stacking direction of the first electrode 2a, the connection portions 4 and 4X, and the second electrode 3a.
  • the solder portion in the connection portions 4 and 4X is at least 50% of the area of 100% of the portion facing the first electrode 2a and the second electrode 3a.
  • 4A and 4XA are preferably arranged.
  • the 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 seen.
  • the solder portion in the connection portion is preferably disposed.
  • the first electrode and the second electrode are opposed to each other in a direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode.
  • the portion where the first electrode and the second electrode face each other is 70% or more (more preferably 80% or more, more preferably 90%) of the solder portion in the connection portion. In particular, it is preferable that 95% or more, most preferably 99% or more) is disposed.
  • connection structure 1 using the conductive material Next, an example of a method for manufacturing the connection structure 1 using the conductive material according to the embodiment of the present invention will be described.
  • 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 conductive particles 11A is disposed on the surface of the first connection target member 2 (first Process).
  • the conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided.
  • the conductive particles 11A are arranged both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
  • the arrangement method of the conductive material 11 is not particularly limited, and examples thereof include application by a dispenser, screen printing, and discharge by an inkjet device.
  • the 2nd connection object member 3 which has the 2nd electrode 3a on the surface (lower surface) is prepared.
  • the 2nd connection object member 3 is arrange
  • the second connection target member 3 is disposed from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.
  • the conductive material 11 is heated above the melting point of the conductive particles 11A (third step).
  • the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (binder).
  • the conductive particles 11A that existed in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect).
  • the conductive material 11A since the conductive material is used instead of the conductive film, the conductive material 11A has a specific composition, so that the conductive particles 11A are formed between the first electrode 2a and the second electrode 3a. Gather effectively in between.
  • the conductive particles 11A are melted and joined to each other.
  • the thermosetting component 11B is thermoset.
  • connection portion 4 that connects the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11.
  • the connection part 4 is formed of the conductive material 11
  • the solder part 4A is formed by joining the plurality of conductive particles 11A
  • the cured part 4B is formed by thermosetting the thermosetting component 11B. If the conductive particles 11A are sufficiently moved, the first electrode 2a and the second electrode 2a are moved after the movement of the conductive particles 11A that are not positioned between the first electrode 2a and the second electrode 3a starts. The temperature does not have to be kept constant until the movement of the conductive particles 11A between the electrodes 3a is completed.
  • pressurization may be performed as long as the interval between the first electrode and the second electrode can be secured.
  • a spacer corresponding to the desired gap between the electrodes may be added so that at least one, preferably three or more spacers are arranged between the electrodes.
  • the spacer include inorganic particles and organic particles.
  • the spacer is preferably an insulating particle.
  • the electrode of the first connection target member Even when the first connection target member and the second connection target member are overlapped in a state where the alignment of the electrodes of the second connection target member is shifted, the shift is corrected and the first connection target member is corrected. And the electrode of the second connection target member can be connected (self-alignment effect). This is because the molten solder self-aggregated between the electrode of the first connection target member and the electrode of the second connection target member is the electrode of the first connection target member and the electrode of the second connection target member.
  • connection structure with alignment As the area where the solder and the other components of the conductive material are in contact with each other is minimized, the energy becomes more stable. Therefore, the force that makes the connection structure with alignment, which is the connection structure with the smallest area, works. Because. At this time, it is desirable that the conductive material is not cured, and that the viscosity of components other than the conductive particles of the conductive material is sufficiently low at that temperature and time.
  • connection structure 1 shown in FIG. 1 is obtained.
  • the second step and the third step may be performed continuously.
  • the laminated body of the 1st connection object member 2, the electrically-conductive material 11, and the 2nd connection object member 3 which are obtained is moved to a heating part, and the said 3rd connection object is carried out.
  • You may perform a process.
  • the laminate In order to perform the heating, the laminate may be disposed on a heating member, or the laminate may be disposed 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 still more preferably 200 ° C. or lower.
  • a 1st connection object member or a 2nd connection object member can be peeled from a connection part for the purpose of correction of a position, or re-production.
  • the heating temperature for performing this peeling is preferably not lower than the melting point of the conductive particles, more preferably not lower than the melting point (° C.) of the conductive particles + 10 ° C.
  • the heating temperature for performing this peeling may be the melting point (° C.) of the conductive particles + 100 ° C. or less.
  • the heating method in the third step a method of heating the entire connection structure using a reflow furnace or an oven above the melting point of the conductive particles and the curing temperature of the thermosetting component, The method of heating only the connection part of a structure locally is mentioned.
  • instruments used in the method of locally heating include a hot plate, a heat gun that applies hot air, a soldering iron, and an infrared heater.
  • the metal directly under the connection is made of a metal with high thermal conductivity, and other places where heating is not preferred are made of a material with low thermal conductivity such as a fluororesin.
  • the upper surface of the hot plate is preferably formed.
  • the first and second connection target members are not particularly limited. Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor chip, a semiconductor package, LED chip, LED package, a capacitor
  • the first and second connection target members are preferably 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.
  • the second connection target member is preferably a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. Resin films, flexible printed boards, flexible flat cables, and rigid flexible boards have the property of being highly flexible and relatively lightweight. When a conductive film is used for connection of such a connection object member, there exists a tendency for electroconductive particle to collect on an electrode easily.
  • the electrode provided on the connection target member examples 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 formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for 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.
  • Thermosetting compound 1 2,4-bis (glycidyloxy) benzophenone (crystalline thermosetting compound, melting point: 94 ° C., molecular weight 362)
  • MEK methyl ethyl ketone
  • n-butanol 3: 1 (weight ratio)
  • DSC -Differential scanning calorimetry
  • Thermosetting compound 2 4,4'-bis (glycidyloxy) benzophenone (crystalline thermosetting compound, melting point: 132 ° C, molecular weight 362)
  • MEK methyl ethyl ketone
  • n-butanol 3: 1 (weight ratio)
  • Obtained epoxy compound melting point by DSC is 132 ° C., epoxy equivalent is 176 g / eq. According to the mass spectrum, the molecular weight was 362, and the melt viscosity at 150 ° C. was 12 mPa ⁇ s.
  • Thermosetting compound 3 Epoxy group-containing acrylic polymer, “MARPROOF G-0150M” manufactured by NOF Corporation
  • Thermosetting agent 1 Pentaerythritol tetrakis (3-mercaptobutyrate), “Karenz MT PE1” manufactured by Showa Denko KK
  • Latent epoxy thermosetting agent 1 T & K TOKA's “Fujicure 7000”
  • Flux 1 glutaric acid, manufactured by Wako Pure Chemical Industries, Ltd., melting point (active temperature) 152 ° C.
  • solder particles 1 In a three-necked flask, SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 12 ⁇ m) 200 g, silane coupling agent (“KBM-903” manufactured by Shin-Etsu Silicone Co., Ltd.), 3-aminopropyl 10 g of trimethoxysilane), 120 g of toluene, and 1 g of water were added and reacted at 80 ° C. for 3 hours under a nitrogen atmosphere using a Dean-Stark apparatus to obtain a silanol group derived from the methoxy group of 3-aminopropyltrimethoxylane. And Sn—OH on the surface of the solder particles were dehydrated and condensed.
  • SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 12 ⁇ m) 200 g
  • silane coupling agent KBM
  • solder particles were collected with a 10 ⁇ m CMF filter and thoroughly washed with acetone.
  • solder particles were transferred to a three-necked flask, and 200 g of acetone and 40 g of glutaric anhydride were added and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere using a Dean-Stark apparatus, thereby producing 3-aminopropyltrimethoxylane.
  • the amino group was reacted with one carboxyl group derived from glutaric anhydride.
  • the solder particles were collected with a 10 ⁇ m CMF filter and sufficiently washed with acetone.
  • top cut removal of coarse particles
  • the average particle diameter is 12 ⁇ m
  • the CV value is 20%
  • Solder particles 2 The same procedure except that 3-aminopropyltrimethoxylane was changed to a silane coupling agent (“KBM-603” manufactured by Shin-Etsu Silicone Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane). Solder particles 2 were obtained. The average particle size was 12 ⁇ m, and the CV value was 20%.
  • KBM-603 silane coupling agent manufactured by Shin-Etsu Silicone Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane.
  • Solder particles A SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 ⁇ m)
  • CV value of solder particles The CV value was measured with a laser diffraction particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.).
  • Example 1 (Examples 1 to 6 and Comparative Example 1) The components shown in Table 1 below were blended in the blending amounts shown in Table 1 below to obtain anisotropic conductive paste.
  • the first, second, and third connection structures were produced as follows using the anisotropic conductive paste immediately after the production.
  • the anisotropic conductive paste immediately after fabrication is applied to the upper surface of the glass epoxy substrate by screen printing using a metal mask so that the thickness becomes 100 ⁇ m on the electrode of the glass epoxy substrate, After forming the conductive conductive paste layer, it was allowed to stand at 23 ° C. and 50% RH for 10 hours in an air atmosphere, and then a flexible printed circuit board was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other.
  • the other conditions were the same as those in Condition A.
  • the viscosity was measured by collecting the paste after being left standing (anisotropic conductive paste layer).
  • connection structure 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. Moreover, the flexible printed circuit board (2nd connection object member) which has a copper electrode pattern (thickness of a copper electrode 12 micrometers) of L / S 50 micrometers / 50 micrometers and electrode length 3mm on the lower surface was prepared.
  • the overlapping area of the glass epoxy substrate and the flexible printed circuit board was 1.5 cm ⁇ 3 mm, and the number of connected electrodes was 75 pairs.
  • the anisotropic conductive paste immediately after production is applied by screen printing using a metal mask so that the thickness is 100 ⁇ m on the electrode of the glass epoxy substrate, and anisotropic conductive A paste layer was formed.
  • the flexible printed circuit board was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. At this time, no pressure was applied. The weight of the flexible printed board is added to the anisotropic conductive paste layer. Thereafter, while heating the anisotropic conductive paste layer to 190 ° C., the solder is melted and the anisotropic conductive paste layer is cured at 190 ° C. for 10 seconds to obtain a first connection structure. It was.
  • a flexible printed circuit board (second connection target member) having a L / S of 75 ⁇ m / 75 ⁇ m and an electrode length of 3 mm on the lower surface of a copper electrode pattern (copper electrode thickness 12 ⁇ m) was prepared.
  • 2nd connection structure was obtained like manufacture of the 1st connection structure except having used the above-mentioned glass epoxy board and flexible printed circuit board from which L / S differs.
  • Glass epoxy substrate having a copper electrode pattern (copper electrode thickness 12 ⁇ m) with L / S of 100 ⁇ m / 100 ⁇ m and electrode length of 3 mm on the upper surface (FR-4 substrate) (first connection target member) was prepared.
  • the flexible printed circuit board (2nd connection object member) which has a copper electrode pattern (thickness of copper electrode 12 micrometers) of L / S of 100 micrometers / 100 micrometers and electrode length 3mm on the lower surface was prepared.
  • 3rd connection structure was obtained like manufacture of the 1st connection structure except having used the above-mentioned glass epoxy board and flexible printed circuit board from which L / S differs.
  • Viscosity The viscosity ( ⁇ 25) at 25 ° C. of the anisotropic conductive paste was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
  • solder placement accuracy on electrode 1 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 provided. When viewed, the ratio X of the area where the solder portion in the connection portion is arranged in the area of 100% of the portion where the first electrode and the second electrode face each other was evaluated.
  • the solder placement accuracy 1 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%
  • solder placement accuracy on electrode 2 In the obtained first, second, and third connection structures, the first electrode and the second electrode are opposed to each other in a direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode.
  • the ratio Y of the solder part in the connecting part arranged in the part where the first electrode and the second electrode face each other in 100% of the solder part in the connecting part was evaluated. .
  • the solder placement accuracy 2 on the electrode was determined according to the following criteria.
  • Ratio Y is 99% or more ⁇ : Ratio Y is 90% or more and less than 99% ⁇ : Ratio Y is 70% or more and less than 90% X: Ratio Y is less than 70%
  • ⁇ Average value of connection resistance is 10 7 ⁇ or more ⁇ : Average value of connection resistance is 10 6 ⁇ or more, less than 10 7 ⁇ ⁇ : Average value of connection resistance is 10 5 ⁇ or more, less than 10 6 ⁇ ⁇ : Connection The average resistance is less than 10 5 ⁇
  • first electrode and the second electrode are stacked in the stacking direction of the first electrode, the connection portion, and the second electrode. Whether the center line of the first electrode and the center line of the second electrode were aligned when the portion facing the two electrodes was viewed, and the distance of the positional deviation were evaluated.
  • the positional deviation between the upper and lower electrodes was determined according to the following criteria.
  • Misalignment is less than 15 ⁇ m ⁇ : Misalignment is 15 ⁇ m or more and less than 25 ⁇ m ⁇ : Misalignment is 25 ⁇ m or more and less than 40 ⁇ m ⁇ : Misalignment is 40 ⁇ m or more

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Abstract

Provided is a conductive material in which the dispersibility of conductive particles in the conductive material is high and the solder in the conductive particles can be efficiently disposed on electrodes, thereby making it possible to improve the reliability of conduction between electrodes. This conductive material includes a plurality of conductive particles, a heat curable compound, and a heat curing agent. The conductive particles each have solder on an outer surface portion of a conductive section and have an O-Si bond on the outer surface of the solder of the conductive section.

Description

導電材料及び接続構造体Conductive material and connection structure
　本発明は、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 including conductive particles having solder. The present invention also 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。 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、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））等に使用されている。 In order to obtain various connection structures, for example, the anisotropic conductive material may be connected between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), or connected between a semiconductor chip and a flexible printed circuit board (COF ( (Chip on Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
　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。 For example, when electrically connecting the electrode of the flexible printed circuit board and the electrode of the glass epoxy substrate by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is disposed on the glass epoxy substrate. To do. Next, a flexible printed circuit board is laminated, and heated and pressurized. As a result, 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、導電性粒子と、該導電性粒子の融点で硬化が完了しない樹脂成分とを含む異方性導電材料が記載されている。上記導電性粒子としては、具体的には、錫（Ｓｎ）、インジウム（Ｉｎ）、ビスマス（Ｂｉ）、銀（Ａｇ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、鉛（Ｐｂ）、カドミウム（Ｃｄ）、ガリウム（Ｇａ）、銀（Ａｇ）及びタリウム（Ｔｌ）等の金属や、これらの金属の合金が挙げられている。 As an example of the anisotropic conductive material, the following Patent Document 1 describes an anisotropic conductive material including conductive particles and a resin component that cannot be cured at the melting point of the conductive particles. Specifically, the conductive particles include tin (Sn), indium (In), bismuth (Bi), silver (Ag), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd ), Gallium (Ga), silver (Ag), thallium (Tl), and the like, and alloys of these metals.
　特許文献１では、上記導電性粒子の融点よりも高く、かつ上記樹脂成分の硬化が完了しない温度に、異方性導電樹脂を加熱する樹脂加熱ステップと、上記樹脂成分を硬化させる樹脂成分硬化ステップとを経て、電極間を電気的に接続することが記載されている。また、特許文献１には、特許文献１の図８に示された温度プロファイルで実装を行うことが記載されている。特許文献１では、異方性導電樹脂が加熱される温度にて硬化が完了しない樹脂成分内で、導電性粒子が溶融する。 In Patent Document 1, a resin heating step for heating the anisotropic conductive resin to a temperature higher than the melting point of the conductive particles and at which the curing of the resin component is not completed, and a resin component curing step for curing the resin component The electrical connection between the electrodes is described. Patent Document 1 describes that mounting is performed with the temperature profile shown in FIG. In Patent Document 1, the conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive resin is heated.
　下記の特許文献２には、熱硬化性樹脂を含む樹脂層と、はんだ粉と、硬化剤とを含み、上記はんだ粉と上記硬化剤とが上記樹脂層中に存在する接着テープが開示されている。この接着テープは、フィルム状であり、ペースト状ではない。 Patent Document 2 below discloses an adhesive tape that includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent are present in the resin layer. Yes. This adhesive tape is in the form of a film, not a paste.
　また、特許文献２では、上記接着テープを用いた接着方法が開示されている。具体的には、第一基板、接着テープ、第二基板、接着テープ、及び第三基板を下からこの順に積層して、積層体を得る。このとき、第一基板の表面に設けられた第一電極と、第二基板の表面に設けられた第二電極とを対向させる。また、第二基板の表面に設けられた第二電極と第三基板の表面に設けられた第三電極とを対向させる。そして、積層体を所定の温度で加熱して接着する。これにより、接続構造体を得る。 Further, Patent Document 2 discloses a bonding method using the above adhesive tape. Specifically, a first substrate, an adhesive tape, a second substrate, an adhesive tape, and a third substrate are laminated in this order from the bottom to obtain a laminate. At this time, the first electrode provided on the surface of the first substrate is opposed to the second electrode provided on the surface of the second substrate. Moreover, the 2nd electrode provided in the surface of the 2nd board | substrate and the 3rd electrode provided in the surface of the 3rd board | substrate are made to oppose. Then, the laminate is heated and bonded at a predetermined temperature. Thereby, a connection structure is obtained.
　また、下記の特許文献３には、複数の電極端子を有する配線基板と対向させて、複数の接続端子を有する半導体チップを配設し、上記配線基板の上記電極端子と、上記半導体チップの上記接続端子とを電気的に接続するフリップチップ実装方法が開示されている。このフリップチップ実装方法は、（１）上記配線基板の上記電極端子を有する表面上に、はんだ粉及び対流添加剤を含有する樹脂を供給する工程と、（２）上記樹脂表面に、上記半導体チップを当接させる工程と、（３）上記配線基板を、上記はんだ粉が溶融する温度に加熱する工程と、（４）上記加熱工程後、上記樹脂を硬化させる工程とを含む。上記配線基板の加熱工程（３）において、上記電極端子と上記接続端子とを電気的に接続する接続体を形成し、また、上記樹脂の硬化工程（４）において、上記半導体チップを上記配線基板に固定する。 Further, in Patent Document 3 below, a semiconductor chip having a plurality of connection terminals is disposed so as to face a wiring board having a plurality of electrode terminals, and the electrode terminals of the wiring board and the above-mentioned semiconductor chip A flip chip mounting method for electrically connecting a connection terminal is disclosed. The flip chip mounting method includes (1) a step of supplying a resin containing solder powder and a convection additive onto the surface of the wiring board having the electrode terminals, and (2) the semiconductor chip on the resin surface. (3) a step of heating the wiring substrate to a temperature at which the solder powder melts, and (4) a step of curing the resin after the heating step. In the heating step (3) of the wiring board, a connection body for electrically connecting the electrode terminal and the connection terminal is formed, and in the resin curing step (4), the semiconductor chip is connected to the wiring board. Secure to.
特開２００４－２６０１３１号公報JP 2004-260131 A ＷＯ２００８／０２３４５２Ａ１WO2008 / 023452A1 特開２００６－１１４８６５号公報JP 2006-1114865 A
　従来のはんだ粉や、はんだ層を表面に有する導電性粒子を含む異方性導電ペーストでは、はんだ粉又は導電性粒子が電極（ライン）上に効率的に配置されないことがある。従来のはんだ粉又は導電性粒子では、はんだ粉又は導電性粒子の電極上への移動速度が遅いことがある。 In the case of conventional anisotropic conductive paste containing solder powder or conductive particles having a solder layer on the surface, the solder powder or conductive particles may not be efficiently disposed on the electrodes (lines). In the conventional solder powder or conductive particles, the moving speed of the solder powder or conductive particles onto the electrode may be slow.
　また、特許文献１に記載の異方性導電材料を用いて、特許文献１に記載の方法で電極間を電気的に接続すると、はんだを含む導電性粒子が電極（ライン）上に効率的に配置されないことがある。また、特許文献１の実施例では、はんだの融点以上の温度で、はんだを十分に移動させるために、一定温度に保持しており、接続構造体の製造効率が低くなる。特許文献１の図８に示された温度プロファイルで実装を行うと、接続構造体の製造効率が低くなる。 Further, when the electrodes are electrically connected by the method described in Patent Document 1 using the anisotropic conductive material described in Patent Document 1, conductive particles including solder are efficiently formed on the electrodes (lines). May not be placed. Moreover, in the Example of patent document 1, in order to move a solder fully at the temperature more than melting | fusing point of solder, it is hold | maintained at fixed temperature, and the manufacturing efficiency of a connection structure becomes low. When mounting is performed with the temperature profile shown in FIG. 8 of Patent Document 1, the manufacturing efficiency of the connection structure is lowered.
　特許文献２では、異方性導電材料に用いる導電性粒子については、具体的な記載がない。特許文献３の実施例では、樹脂粒子の表面上に銅層が形成されており、該銅層の表面にはんだ層が形成されている導電性粒子が用いられている。この導電性粒子の中心部分は、樹脂粒子により構成されている。また、特許文献２，３に記載の異方性導電材料を用いると、導電性粒子が電極（ライン）上に効率的に配置されにくく、接続されるべき上下の電極間の位置ずれが生じたりすることがある。 In Patent Document 2, there is no specific description of the conductive particles used for the anisotropic conductive material. In the Example of patent document 3, the copper layer is formed on the surface of the resin particle, and the electroconductive particle in which the solder layer is formed on the surface of this copper layer is used. The central part of the conductive particles is composed of resin particles. In addition, when the anisotropic conductive material described in Patent Documents 2 and 3 is used, the conductive particles are difficult to be efficiently arranged on the electrodes (lines), and positional displacement between the upper and lower electrodes to be connected may occur. There are things to do.
　また、従来の異方性導電材料では、導電性粒子の分散性が低いことがある。このため、異方性導電材料が保管した後に使用されると、導電性粒子が電極（ライン）上により一層配置されにくくなることがある。 Further, in the conventional anisotropic conductive material, the dispersibility of the conductive particles may be low. For this reason, when the anisotropic conductive material is used after being stored, the conductive particles may be more difficult to be disposed on the electrode (line).
　本発明の目的は、導電材料中での導電性粒子の分散性が高く、導電性粒子におけるはんだを電極上に効率的に配置することができ、電極間の導通信頼性を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 provide a conductive material that has high dispersibility of conductive particles in a conductive material, can efficiently dispose solder in the conductive particles on the electrodes, and can improve conduction reliability between the electrodes. Is to provide materials. Another object of the present invention is to provide a connection structure using the conductive material.
　本発明の広い局面によれば、複数の導電性粒子と、熱硬化性化合物と、熱硬化剤とを含み、前記導電性粒子は、導電部の外表面部分に、はんだを有し、前記導電性粒子は、前記導電部の前記はんだの外表面に、Ｏ－Ｓｉ結合を有する、導電材料が提供される。 According to a wide aspect of the present invention, the conductive particles include a plurality of conductive particles, a thermosetting compound, and a thermosetting agent, and the conductive particles have solder on an outer surface portion of a conductive portion, and the conductive The conductive particles are provided with a conductive material having an O—Si bond on the outer surface of the solder of the conductive portion.
　本発明に係る導電材料のある特定の局面では、前記導電性粒子は、前記導電部の前記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を有する。 In a specific aspect of the conductive material according to the present invention, the conductive particles have a Sn—O—Si bond on the outer surface of the solder of the conductive portion.
　本発明に係る導電材料のある特定の局面では、シランカップリング剤による表面処理物である。 In a specific aspect of the conductive material according to the present invention, the conductive material is a surface-treated product with a silane coupling agent.
　本発明に係る導電材料のある特定の局面では、前記導電性粒子は、前記導電部の前記はんだの外表面に、アミノ基を有する。 In a specific aspect of the conductive material according to the present invention, the conductive particles have an amino group on the outer surface of the solder of the conductive portion.
　本発明に係る導電材料のある特定の局面では、前記導電性粒子は、前記導電部の前記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を介して、カルボキシル基含有基を有する。 In a specific aspect of the conductive material according to the present invention, the conductive particles have a carboxyl group-containing group on the outer surface of the solder of the conductive portion via a Sn—O—Si bond.
　本発明に係る導電材料のある特定の局面では、前記導電性粒子は、はんだ粒子である。 In a specific aspect of the conductive material according to the present invention, the conductive particles are solder particles.
　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１μｍ以上、６０μｍ以下である。 In a specific aspect of the conductive material according to the present invention, the conductive particles have an average particle diameter of 1 μm or more and 60 μm 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、前記導電性粒子の含有量が１０重量％以上、８０重量％以下である。 In a specific aspect of the conductive material according to the present invention, the content of the conductive particles is 10% by weight to 80% by weight in 100% by weight of the conductive material.
　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おけるはんだ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 wide aspect of the present invention, 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, and the A connection part connecting the second connection target member, the material of the connection part is the conductive material described above, and the first electrode and the second electrode are in the conductive particles A connection structure is provided that is electrically connected by solder.
　本発明に係る導電材料は、複数の導電性粒子と、熱硬化性化合物と、熱硬化剤とを含み、上記導電性粒子は、導電部の外表面部分に、はんだを有し、上記導電性粒子は、上記導電部の上記はんだの外表面に、Ｏ－Ｓｉ結合を有するので、導電材料中での導電性粒子の分散性が高く、導電性粒子におけるはんだを電極上に効率的に配置することができ、電極間の導通信頼性を高めることができる。 The conductive material according to the present invention includes a plurality of conductive particles, a thermosetting compound, and a thermosetting agent, and the conductive particles have solder on the outer surface portion of the conductive portion, and the conductive Since the particles have an O—Si bond on the outer surface of the solder in the conductive part, the dispersibility of the conductive particles in the conductive material is high, and the solder in the conductive particles is efficiently arranged on the electrode. And the reliability of conduction between the electrodes can be improved.
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 an 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。2A to 2C are cross-sectional views for explaining each step 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 as 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 the 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 the 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、複数の導電性粒子と、熱硬化性化合物と、熱硬化剤とを含む。上記導電性粒子は、導電部を有する。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。はんだは、導電部に含まれ、導電部の一部又は全部である。 (Conductive material)
The conductive material according to the present invention includes a plurality of conductive particles, a thermosetting compound, and a thermosetting agent. The conductive particles have a conductive part. The conductive particles have solder on the outer surface portion of the conductive portion. Solder is contained in the conductive part and is a part or all of the conductive part.
　本発明に係る導電材料では、上記導電性粒子は、上記導電部の上記はんだの外表面に、Ｏ－Ｓｉ結合を有する。 In the conductive material according to the present invention, the conductive particles have an O—Si bond on the outer surface of the solder of the conductive portion.
　本発明では、導電材料中に特定の導電性粒子が含まれているため、はんだの腐食がかなり抑えられる。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、導電性粒子におけるはんだが、上下の対向した電極間に集まりやすく、導電性粒子におけるはんだを電極（ライン）上に効率的に配置することができる。また、導電性粒子におけるはんだの一部が、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。本発明では、対向する電極間に位置していない導電性粒子を、対向する電極間に効率的に移動させることができる。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 specific conductive particles are contained in the conductive material, the corrosion of the solder is considerably suppressed. In the present invention, since the above-described configuration is provided, when the electrodes are electrically connected, the solder in the conductive particles easily collects between the upper and lower electrodes, and the solder in the conductive particles is removed from the electrode ( Line). In addition, a part of the solder in the conductive particles is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be considerably reduced. In this invention, the electroconductive particle which is not located between the opposing electrodes can be efficiently moved between the opposing electrodes. Therefore, the conduction reliability between the electrodes can be improved. In addition, it is possible to prevent electrical connection between laterally adjacent electrodes that should not be connected, and to improve insulation reliability.
　さらに、本発明では、導電材料中での導電性粒子の分散性が高く、導電材料の保存安定性に優れている。また、本発明では、導電性粒子におけるはんだの腐食も進行しにくい。このため、導電材料の保管前及び保管後のいずれの場合であっても、導電性粒子におけるはんだを電極上に効率的に配置することができ、電極間の導通信頼性を高めることができる。 Furthermore, in the present invention, the dispersibility of the conductive particles in the conductive material is high, and the storage stability of the conductive material is excellent. In the present invention, the corrosion of the solder in the conductive particles hardly progresses. For this reason, it is possible to efficiently arrange the solder in the conductive particles on the electrodes regardless of whether the conductive material is stored before or after storage, and the conduction reliability between the electrodes can be improved.
　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た場合でも、そのずれを補正して、第１の接続対象部材の電極と第２の接続対象部材の電極と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 the electrodes. In the present invention, when the second connection target member is superimposed on the first connection target member having the conductive material disposed on the upper surface, the electrode of the first connection target member and the electrode of the second connection target member Even when the first connection target member and the second connection target member are overlapped in a state where the alignment of the first connection target member and the second connection target member are overlaid, the shift is corrected and the first connection target member electrode and the second connection target are corrected. The electrode of the member can be connected (self-alignment effect).
　分散性及びはんだの配置精度を効果的に高める観点からは、上記導電性粒子は、上記導電部の上記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を有することが好ましい。 From the viewpoint of effectively increasing dispersibility and solder placement accuracy, the conductive particles preferably have a Sn—O—Si bond on the outer surface of the solder of the conductive portion.
　分散性及びはんだの配置精度を効果的に高める観点からは、上記導電性粒子は、シランカップリング剤を用いた表面処理により得られることが好ましく、上記導電性粒子は、シランカップリング剤により表面処理されていることが好ましい。即ち、上記導電性粒子は、シランカップリング剤による表面処理物であることが好ましい。 From the viewpoint of effectively increasing dispersibility and solder placement accuracy, the conductive particles are preferably obtained by surface treatment using a silane coupling agent, and the conductive particles are surface-treated by a silane coupling agent. Preferably it has been treated. That is, the conductive particles are preferably a surface-treated product with a silane coupling agent.
　上記導電性粒子は、はんだ粒子であってもよい。上記はんだ粒子は、はんだにより形成されている。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とのいずれもがはんだにより形成されており、中心部分及び導電部の外表面部分と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。 The conductive particles may be solder particles. The solder particles are formed of solder. The solder particles have solder on the outer surface portion of the conductive portion. The solder particles are particles in which both the central portion and the outer surface portion of the conductive portion are formed of solder, and both the central portion and the outer surface portion of the conductive portion are solder. The said electroconductive particle may have a base material particle and the electroconductive part arrange | positioned on the surface of this base material particle. In this case, the conductive particles have solder on the outer surface portion of the conductive portion.
　なお、上記はんだ粒子を備える導電性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にくくなり、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。 Compared to the case where the conductive particles including the solder particles are used, the case where the conductive particles including the base particles not formed by the solder and the solder portion arranged on the surface of the base particles are used. The conductive particles are less likely to collect on the electrodes, and the conductive particles that have moved onto the electrodes tend to move out of the electrodes because of the low solderability between the conductive particles. There is a tendency that the effect of suppressing misalignment also becomes low. Therefore, the conductive particles are preferably solder particles formed by solder.
　はんだを電極上により一層効率的に配置するために、上記導電材料の２５℃での粘度（η２５）は好ましくは１０Ｐａ・ｓ以上、より好ましくは５０Ｐａ・ｓ以上、更に好ましくは１００Ｐａ・ｓ以上であり、好ましくは８００Ｐａ・ｓ以下、より好ましくは６００Ｐａ・ｓ以下、更に好ましくは５００Ｐａ・ｓ以下である。 In order to arrange the solder more efficiently on the electrode, the viscosity (η25) at 25 ° C. of the conductive material is preferably 10 Pa · s or more, more preferably 50 Pa · s or more, and further preferably 100 Pa · s or more. Yes, preferably 800 Pa · s or less, more preferably 600 Pa · s or less, and even more preferably 500 Pa · s or less.
　上記粘度（η２５）は、配合成分の種類及び配合量に適宜調整可能である。また、フィラーの使用により、粘度を比較的高くすることができる。 The viscosity (η25) can be adjusted as appropriate to the type and amount of the compounding ingredients. Further, the use of a filler can make the viscosity relatively high.
　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の条件で測定可能である。 The viscosity (η25) can be measured using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) and the like 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。導電性粒子におけるはんだを電極上により一層効率的に配置する観点からは、上記導電材料は、異方性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. From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrode, the conductive material is preferably an anisotropic conductive paste. The conductive material is preferably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material.
　以下、上記導電材料に含まれる各成分を説明する。 Hereinafter, each component contained in the conductive material will be described.
　（導電性粒子）
　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、上記導電部の上記はんだの外表面に、Ｏ－Ｓｉ結合を有する。上記導電部の上記はんだの外表面に存在するＯ－Ｓｉ結合に関して、例えば、はんだの成分（はんだを構成する原子）が、Ｏ－Ｓｉ結合の酸素原子と結合している。上記導電性粒子は、例えば、上記導電部の上記はんだの外表面に、（はんだの成分）－Ｏ－Ｓｉ結合（（はんだを構成する原子）－Ｏ－Ｓｉ結合）を有する。 (Conductive particles)
The conductive particles electrically connect the electrodes of the connection target member. The conductive particles have solder on the outer surface portion of the conductive portion. The conductive particles have an O—Si bond on the outer surface of the solder of the conductive portion. Regarding the O—Si bond existing on the outer surface of the solder of the conductive portion, for example, a solder component (atom constituting the solder) is bonded to an oxygen atom of the O—Si bond. The conductive particles have, for example, (solder component) -O-Si bond ((atom constituting the solder) -O-Si bond) on the outer surface of the solder of the conductive portion.
　導電性粒子の分散性をより一層高め、はんだを電極上により一層効率的に配置し、電極間の位置ずれをより一層抑える観点からは、上記導電性粒子は、上記導電部の上記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を有することが好ましい。 From the viewpoint of further improving the dispersibility of the conductive particles, more efficiently arranging the solder on the electrodes, and further suppressing the positional deviation between the electrodes, the conductive particles are disposed on the outside of the solder of the conductive portion. The surface preferably has a Sn—O—Si bond.
　はんだの表面の水酸基に、シランカップリング剤を反応させることができる。はんだの表面の水酸基に、シランカップリング剤を反応させることで、Ｏ－Ｓｉ結合を形成することができる。 A silane coupling agent can be reacted with the hydroxyl group on the solder surface. An O—Si bond can be formed by reacting a hydroxyl group on the surface of the solder with a silane coupling agent.
　上記導電材料は、シランカップリング剤を用いて表面処理を行うことで、導電部のはんだの外表面にＳｎ－Ｏ－Ｓｉ結合を有する導電性粒子を得た後に、該導電性粒子と熱硬化性化合物と熱硬化剤とを混合することにより得られることが好ましい。 The conductive material is subjected to surface treatment using a silane coupling agent to obtain conductive particles having Sn—O—Si bonds on the outer surface of the solder of the conductive portion, and then thermally cured with the conductive particles. It is preferable that it is obtained by mixing a functional compound and a thermosetting agent.
　導電性粒子の分散性をより一層高め、はんだを電極上により一層効率的に配置し、電極間の位置ずれをより一層抑える観点からは、上記導電性粒子は、上記導電部の上記はんだの外表面に、アミノ基を有することが好ましい。 From the viewpoint of further improving the dispersibility of the conductive particles, more efficiently arranging the solder on the electrodes, and further suppressing the positional deviation between the electrodes, the conductive particles are disposed on the outside of the solder of the conductive portion. It is preferable to have an amino group on the surface.
　導電性粒子の分散性をより一層高め、はんだを電極上により一層効率的に配置し、電極間の位置ずれをより一層抑える観点からは、上記導電性粒子は、上記導電部の上記はんだの外表面に、Ｏ－Ｓｉ結合を介して、カルボキシル基含有基を有することが好ましく、上記導電部の上記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を介して、カルボキシル基含有基を有することがより好ましい。特に、カルボキシル基含有基の存在により、はんだの凝集性能がかなり高くなる。 From the viewpoint of further improving the dispersibility of the conductive particles, more efficiently arranging the solder on the electrodes, and further suppressing the positional deviation between the electrodes, the conductive particles are disposed on the outside of the solder of the conductive portion. It is preferable that the surface has a carboxyl group-containing group via an O—Si bond, and the outer surface of the solder of the conductive portion has a carboxyl group-containing group via a Sn—O—Si bond. More preferred. In particular, due to the presence of the carboxyl group-containing group, the solder aggregating performance is considerably increased.
　導電性粒子の分散性をより一層高め、はんだを電極上により一層効率的に配置し、電極間の位置ずれをより一層抑える観点からは、上記導電性粒子は、シランカップリング剤を用いて表面処理を行った後、カルボキシル基含有基を導入することにより得られることが好ましい。シランカップリング剤が有する残基に対して、カルボキシル基含有基を導入することができる。上記導電性粒子は、シランカップリング剤に由来する基と、カルボキシル含有基とを有することが好ましく、はんだとカルボキシル基含有基とがシランカップリング剤に由来する基を介して結合していることが好ましい。 From the viewpoint of further improving the dispersibility of the conductive particles, more efficiently arranging the solder on the electrodes, and further suppressing the displacement between the electrodes, the conductive particles are formed on the surface using a silane coupling agent. After the treatment, it is preferably obtained by introducing a carboxyl group-containing group. A carboxyl group-containing group can be introduced into the residue of the silane coupling agent. The conductive particles preferably have a group derived from a silane coupling agent and a carboxyl-containing group, and the solder and the carboxyl group-containing group are bonded via a group derived from the silane coupling agent. Is preferred.
　上記シランカップリング剤は、１分子中に有機官能基とアルコキシ基とを有することが好ましく、該有機官能基は、カルボキシル基含有基を有する化合物と反応可能であることが好ましい。上記アルコキシ基としては、メトキシ基、及びエトキシ基等が挙げられる。上記シランカップリング剤としては、エポキシ基を有するシランカップリング剤、アミノ基を有するシランカップリング剤及びイソシアネート基を有するシランカップリング剤等が挙げられる。導電性粒子におけるはんだを電極上により一層効率的に配置する観点からは、上記シランカップリング剤は、アミノ基を有するシランカップリング剤であることが好ましい。上記シランカップリング剤は、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。なお、上記導電性粒子が、上記導電部の上記はんだの外表面に、アミノ基を有する場合に、該アミノ基は、アミノ基を有するシランカップリング剤に由来するアミノ基でなくてもよい。 The silane coupling agent preferably has an organic functional group and an alkoxy group in one molecule, and the organic functional group is preferably capable of reacting with a compound having a carboxyl group-containing group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the silane coupling agent include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, and a silane coupling agent having an isocyanate group. From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the silane coupling agent is preferably a silane coupling agent having an amino group. As for the said silane coupling agent, only 1 type may be used and 2 or more types may be used together. In addition, when the said electroconductive particle has an amino group in the outer surface of the said solder of the said electroconductive part, this amino group may not be an amino group derived from the silane coupling agent which has an amino group.
　上記エポキシ基を有するシランカップリング剤としては、信越シリコーン社製のＫＢＭ－３０３、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＥ－４０２及びＫＢＥ－４０３等が挙げられる。上記アミノ基を有するシランカップリング剤としては、ＫＢＭ－６０２及びＫＢＭ－６０３、ＫＢＭ－９０３等が挙げられる。上記イソシアネート基を有するシランカップリング剤としては、ＫＢＥ－９００７等が挙げられる。 Examples of the silane coupling agent having an epoxy group include KBM-303, KBM-402, KBM-403, KBE-402 and KBE-403 manufactured by Shin-Etsu Silicone. Examples of the silane coupling agent having an amino group include KBM-602, KBM-603, KBM-903, and the like. Examples of the silane coupling agent having an isocyanate group include KBE-9007.
　上記カルボキシル基含有基を導入するための化合物としては、レブリン酸、グルタル酸、グリコール酸、コハク酸、リンゴ酸、シュウ酸、マロン酸、アジピン酸、５－ケトヘキサン酸、３－ヒドロキシプロピオン酸、４－アミノ酪酸、３－メルカプトプロピオン酸、３－メルカプトイソブチル酸、３－メチルチオプロピオン酸、３－フェニルプロピオン酸、３－フェニルイソブチル酸、４－フェニル酪酸、デカン酸、ドデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、９－ヘキサデセン酸、ヘプタデカン酸、ステアリン酸、オレイン酸、バクセン酸、リノール酸、（９，１２，１５）－リノレン酸、ノナデカン酸、アラキジン酸、デカン二酸及びドデカン二酸等が挙げられる。グルタル酸、アジピン酸又はグリコール酸が好ましい。上記カルボキシル基含有基を導入するための化合物は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。 Examples of the compound for introducing the carboxyl group-containing group include levulinic acid, glutaric acid, glycolic acid, succinic acid, malic acid, oxalic acid, malonic acid, adipic acid, 5-ketohexanoic acid, 3-hydroxypropionic acid, 4 -Aminobutyric acid, 3-mercaptopropionic acid, 3-mercaptoisobutyric acid, 3-methylthiopropionic acid, 3-phenylpropionic acid, 3-phenylisobutyric acid, 4-phenylbutyric acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid Hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, nonadecanoic acid, arachidic acid, decanedioic acid and dodecanedioic acid Can be mentioned. Glutaric acid, adipic acid or glycolic acid is preferred. Only 1 type may be used for the compound for introduce | transducing the said carboxyl group containing group, and 2 or more types may be used together.
　はんだの外表面に、Ｏ－Ｓｉ結合を有する導電性粒子を得る具体的な方法としては、トルエン等の低極性の溶剤中に、導電性粒子とシランカップリング剤とを入れ、脱アルコール反応させる方法等が挙げられる。 As a specific method for obtaining conductive particles having an O—Si bond on the outer surface of the solder, the conductive particles and the silane coupling agent are placed in a low-polarity solvent such as toluene to cause a dealcoholization reaction. Methods and the like.
　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 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 as 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。 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 base particles in the core, and are not core-shell particles. As for the electroconductive particle 21, both the center part and the outer surface part of an electroconductive part are formed with the 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 conductive particles that can be used as a 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。 The electroconductive particle 31 shown in FIG. 5 is equipped with the base material particle 32 and the electroconductive part 33 arrange | positioned on the surface of the base material particle 32. FIG. The conductive portion 33 covers the surface of the base particle 32. The conductive particles 31 are coated particles in which the surface of the base particle 32 is covered with the conductive portion 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。 The conductive portion 33 has a second conductive portion 33A and a solder portion 33B (first conductive portion). The conductive particle 31 includes a second conductive portion 33A between the base particle 32 and the solder portion 33B. Therefore, the conductive particles 31 are composed of the base particle 32, the second conductive portion 33A disposed on the surface of the base particle 32, and the solder portion 33B disposed on the outer surface of the second conductive portion 33A. With.
　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 as a conductive material.
　上記のように、導電性粒子３１における導電部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。 As described above, the conductive portion 33 in the conductive particle 31 has a two-layer structure. The conductive particle 41 shown in FIG. 6 has a solder part 42 as a single-layer conductive part. The conductive particles 41 include base particles 32 and solder portions 42 disposed on the surfaces of the base particles 32.
　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好ましい。上記基材粒子は、銅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有していてもよく、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。 Examples of the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles. The substrate particles are preferably substrate particles excluding metal, and are preferably resin particles, inorganic particles excluding metal particles, or organic-inorganic hybrid particles. The substrate particles may be copper particles. The base particle may have a core and a shell disposed on the surface of the core, or may be a core-shell particle. The core may be an organic core, and the shell may be an inorganic shell.
　上記樹脂粒子を形成するための樹脂として、種々の有機物が好適に用いられる。上記樹脂粒子を形成するための樹脂としては、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及びポリメチルアクリレート等のアクリル樹脂；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、ポリエチレンテレフタレート、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、並びにジビニルベンゼン系共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等としては、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。上記樹脂粒子の硬度を好適な範囲に容易に制御できるので、上記樹脂粒子を形成するための樹脂は、エチレン性不飽和基を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。 Various organic substances are suitably used as the resin for forming the resin particles. Examples of the resin for forming 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; 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, polyethylene terephthalate, polysulfone, polyphenylene oxide , Polyacetal, polyimide, polyamideimide, polyether ether Tons, polyether sulfone, divinyl benzene polymer, and divinylbenzene copolymer, and the like. Examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer. Since the hardness of the resin particles can be easily controlled within a suitable range, the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferably a coalescence.
　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、該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 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；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル等のビニルエーテル化合物；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 monomers such as styrene and α-methylstyrene; carboxyl group-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, etc. Oxygen atom-containing (meth) acrylate compounds; Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; Acids such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate Vinyl ester compounds; unsaturated hydrocarbons such as ethylene, propylene, isoprene, and butadiene; halogen-containing monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, and chlorostyrene Etc.
　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 tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta 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, 1,4-butanediol di (meth) acrylate; triallyl (iso) sia Silane-containing monomers such as rate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane, etc. Can be mentioned.
　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。 The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
　上記基材粒子が金属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 substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal, examples of inorganic substances for forming the substrate particles include silica, alumina, barium titanate, zirconia, and carbon black. The inorganic substance is preferably not a metal. The particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include 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. The core is preferably an organic core. The shell is preferably an inorganic shell. From the viewpoint of effectively reducing the connection resistance between the electrodes, the base material particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
　上記有機コアを形成するための材料としては、上述した樹脂粒子を形成するための樹脂等が挙げられる。 Examples of the material for forming the organic core include the resin for forming the resin particles described above.
　上記無機シェルを形成するための材料としては、上述した基材粒子を形成するための無機物が挙げられる。上記無機シェルを形成するための材料は、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、該シェル状物を焼結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。 Examples of the material for forming the inorganic shell include inorganic substances for forming the above-described base material particles. The material for forming the inorganic shell is preferably silica. The inorganic shell is preferably formed on the surface of the core by forming a metal alkoxide into a shell by a sol-gel method and then sintering the shell. The metal alkoxide is preferably a silane alkoxide. The inorganic shell is preferably formed of a silane alkoxide.
　上記コアの粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上であり、好ましくは１００μｍ以下、より好ましくは６０μｍ以下、更に好ましくは３０μｍ以下、特に好ましくは１５μｍ以下、最も好ましくは１０μｍ以下である。上記コアの粒子径が上記下限以上及び上記上限以下であると、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、基材粒子を導電性粒子の用途に好適に使用可能になる。例えば、上記コアの粒子径が上記下限以上及び上記上限以下であると、上記導電性粒子を用いて電極間を接続した場合に、導電性粒子と電極との接触面積が充分に大きくなり、かつ導電層を形成する際に凝集した導電性粒子が形成されにくくなる。また、導電性粒子を介して接続された電極間の間隔が大きくなりすぎず、かつ導電層が基材粒子の表面から剥離し難くなる。 The particle diameter of the core is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 60 μm or less, still more preferably 30 μm or less, particularly preferably 15 μm or less, and most preferably 10 μm or less. It is. When the particle diameter of the core is not less than the above lower limit and not more than the above upper limit, conductive particles more suitable for electrical connection between electrodes can be obtained, and the base particles can be suitably used for the use of conductive particles. Become. For example, when the particle diameter of the core is not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrodes is sufficiently large, and Aggregated conductive particles are hardly formed when the conductive layer is formed. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
　上記コアの粒子径は、上記コアが真球状である場合には直径を意味し、上記コアが真球状以外の形状である場合には、最大径を意味する。また、コアの粒子径は、コアを任意の粒子径測定装置により測定した平均粒子径を意味する。例えば、レーザー光散乱、電気抵抗値変化、撮像後の画像解析などの原理を用いた粒度分布測定機が利用できる。 The particle diameter of the core means a diameter when the core is a true sphere, and means a maximum diameter when the core is a shape other than a true sphere. Moreover, the particle diameter of a core means the average particle diameter which measured the core with arbitrary particle diameter measuring apparatuses. For example, a particle size distribution measuring machine using principles such as laser light scattering, electrical resistance value change, and image analysis after imaging can be used.
　上記シェルの厚みは、好ましくは１００ｎｍ以上、より好ましくは２００ｎｍ以上であり、好ましくは５μｍ以下、より好ましくは３μｍ以下である。上記シェルの厚みが上記下限以上及び上記上限以下であると、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、基材粒子を導電性粒子の用途に好適に使用可能になる。上記シェルの厚みは、基材粒子１個あたりの平均厚みである。ゾルゲル法の制御によって、上記シェルの厚みを制御可能である。 The thickness of the shell is preferably 100 nm or more, more preferably 200 nm or more, preferably 5 μm or less, more preferably 3 μm or less. When the thickness of the shell is not less than the above lower limit and not more than the above upper limit, conductive particles more suitable for electrical connection between the electrodes can be obtained, and the base particles can be suitably used for the use of conductive particles. . The thickness of the shell is an average thickness per base particle. The thickness of the shell can be controlled by controlling the sol-gel method.
　上記基材粒子が金属粒子である場合に、該金属粒子を形成するための金属としては、銀、銅、ニッケル、ケイ素、金及びチタン等が挙げられる。上記基材粒子が金属粒子である場合に、該金属粒子は銅粒子であることが好ましい。但し、上記基材粒子は金属粒子ではないことが好ましい。 When the substrate particles are metal particles, examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium. When the base material particles are metal particles, the metal particles are preferably copper particles. However, the substrate particles are preferably not metal particles.
　上記基材粒子の粒子径は、好ましくは０．１μｍ以上、より好ましくは１μｍ以上、更に好ましくは１．５μｍ以上、特に好ましくは２μｍ以上であり、好ましくは１００μｍ以下、より好ましくは６０μｍ以下、より一層好ましくは３０μｍ以下、更に好ましくは２０μｍ以下、更に一層好ましくは１０μｍ以下、特に好ましくは５μｍ以下、最も好ましくは３μｍ以下である。上記基材粒子の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をより一層高めることができ、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低くすることができる。上記基材粒子の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、電極間の接続抵抗をより一層低くすることができ、さらに電極間の間隔をより一層小さくすることができる。 The particle diameter of the substrate particles is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 100 μm or less, more preferably 60 μm or less, more More preferably, it is 30 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, particularly preferably 5 μm or less, and most preferably 3 μm or less. When the particle diameter of the base material 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 conduction reliability between the electrodes can be further improved and the connection is made through the conductive particles. The connection resistance between the formed electrodes can be further reduced. When the particle diameter of the substrate particles is not more than the above upper limit, the conductive particles are sufficiently compressed, the connection resistance between the electrodes can be further reduced, and the distance between the electrodes is further reduced. Can do.
　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。 The particle diameter of the substrate particles indicates a diameter when the substrate particles are spherical, and indicates a maximum diameter when the substrate particles are not spherical.
　上記基材粒子の粒子径は、２μｍ以上、５μｍ以下であることが特に好ましい。上記基材粒子の粒子径が２μｍ以上、５μｍ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、かつ導電層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。 The particle diameter of the substrate particles is particularly preferably 2 μm or more and 5 μm or less. When the particle diameter of the substrate particles is in the range of 2 μm or more and 5 μm or less, the distance between the electrodes can be further reduced, and even if the thickness of the conductive layer is increased, small conductive particles can be obtained. Can do.
　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。なかでも、無電解めっき、電気めっき又は物理的な衝突による方法が好適である。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。 The method for forming the conductive part on the surface of the base particle and the method for forming the solder part on the surface of the base particle or the surface of the second conductive part are not particularly limited. Examples of the method for forming the conductive portion and the solder portion include 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 substrate particles with a paste containing metal powder or metal powder and a binder. Among these, a method using electroless plating, electroplating, or physical collision is preferable. Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, in the method based on the physical collision, for example, a sheeter composer (manufactured by Tokuju Kogakusha Co., Ltd.) or the like 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、更に好ましくは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。 The melting point of the base material particles is preferably higher than the melting points of the conductive part and the solder part. The melting point of the substrate particles is preferably higher than 160 ° C, more preferably higher than 300 ° C, still more preferably higher than 400 ° C, and particularly preferably higher than 450 ° C. The melting point of the substrate particles may be less than 400 ° C. The melting point of the substrate particles may be 160 ° C. or less. The softening point of the substrate particles is preferably 260 ° C. or higher. The softening point of the substrate 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 parts (solder part, second conductive part). That is, in the conductive particles, two or more conductive portions may be stacked. When the conductive part has two or more layers, the conductive particles preferably have solder on the outer surface portion of the conductive part.
　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。該低融点金属とは、融点が４５０℃以下の金属を示す。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。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、更に好ましくは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。 The solder is preferably a metal (low melting point metal) having a melting point of 450 ° C. or lower. The solder part is preferably a metal layer (low melting point metal layer) having a melting point of 450 ° C. or lower. The low melting point metal layer is a layer containing a low melting point metal. The solder in the conductive particles is preferably metal particles having a melting point of 450 ° C. or lower (low melting point metal particles). The low melting point metal particles are particles containing a low melting point metal. The low melting point metal is a metal having a melting point of 450 ° C. or lower. The melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower. 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. It is 70% by weight or more, particularly preferably 90% by weight or more. When the content of tin contained in the solder in the conductive particles is not less than the above lower limit, the conduction reliability between the conductive particles and the electrode is further enhanced.
　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」）等を用いて測定可能である。 The tin content is determined using a high-frequency inductively coupled plasma emission spectrometer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-800HS” manufactured by Shimadzu). It 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。 Using the conductive particles having the solder on the outer surface portion 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 not in point contact but in surface contact, the connection resistance is lowered. 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, and as a result, the solder and the electrode are more unlikely to peel off, and the conduction reliability is effective. To be high.
　上記はんだ部及び上記はんだ粒子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。なかでも、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。 The low melting point metal constituting the solder part and the solder particles is not particularly limited. The low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy. Of these, 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 with respect to the electrode. More preferred are a tin-bismuth alloy and 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、インジウムなどを含む金属組成が挙げられる。なかでも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。 The material constituting the solder (solder part) is preferably a filler material having a liquidus of 450 ° C. or lower based on JIS Z3001: Welding terms. Examples of the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like. Of these, a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which is low-melting and lead-free is preferable. 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.
　上記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, the solder in the conductive particles is nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese. Further, it may contain a metal such as chromium, molybdenum and palladium. Moreover, from the viewpoint of further increasing the bonding strength between the solder and the electrode, 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、更に好ましくは４００℃を超え、更に一層好ましくは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。 The melting point of the second conductive part is preferably higher than the melting point of the solder part. The melting point of the second conductive part is preferably more than 160 ° C, more preferably more than 300 ° C, still more preferably more than 400 ° C, still more preferably more than 450 ° C, particularly preferably more than 500 ° C, most preferably Preferably it exceeds 600 degreeC. Since the solder part has a low melting point, it melts during conductive connection. It is preferable that the second conductive portion does not melt during conductive connection. The conductive particles are preferably used by melting solder, preferably used by melting the solder part, and used without melting the solder part and melting the second conductive part. It is preferred that Since the melting point of the second conductive part is higher than the melting point of the solder part, it is possible to melt only the solder part without melting the second conductive part during 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、更に好ましくは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, particularly preferably Is 50 ° C. or higher, most preferably 100 ° C. or higher.
　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 part preferably contains a metal. The metal which comprises the said 2nd electroconductive part is not specifically limited. Examples of the metal include gold, silver, copper, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and alloys thereof. Further, tin-doped indium oxide (ITO) may be used as the metal. As for the said metal, only 1 type may be used and 2 or more types may be used together.
　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、ニッケル層又は金層であることがより好ましく、銅層であることが更に好ましい。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、ニッケル層又は金層を有することがより好ましく、銅層を有することが更に好ましい。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 part is preferably a nickel layer, a palladium layer, a copper layer or a gold layer, more preferably a nickel layer or a gold layer, and even more 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 or a gold layer, and still more preferably have a copper layer. By using the conductive particles having these preferable conductive parts for the connection between the electrodes, the connection resistance between the electrodes is further reduced. Moreover, a solder part can be more easily formed on the surface of these preferable conductive parts.
　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、更に好ましくは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、充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を充分に変形する。 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 part is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. .
　上記導電性粒子の平均粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上、更に好ましくは３μｍ以上、特に好ましくは５μｍ以上であり、好ましくは１００μｍ以下、より好ましくは６０μｍ以下、より一層好ましくは４０μｍ以下、更に好ましくは３０μｍ以下、更に一層好ましくは２０μｍ以下、特に好ましくは１５μｍ以下、最も好ましくは１０μｍ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、導電性粒子を電極上により一層効率的に配置することができる。上記導電性粒子の平均粒子径は、３μｍ以上、３０μｍ以下であることが特に好ましい。 The average particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm or more, particularly preferably 5 μm or more, preferably 100 μm or less, more preferably 60 μm or less, and much more. It is preferably 40 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, particularly preferably 15 μm or less, and most preferably 10 μm or less. When the average particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be more efficiently arranged on the electrode. The average particle diameter of the conductive particles is particularly preferably 3 μm or more and 30 μm or less.
　上記導電性粒子の「平均粒子径」は、数平均粒子径を示す。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。 The “average particle size” of the conductive particles indicates a number average particle size. The average particle diameter of the conductive particles is obtained, for example, by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value, or performing laser diffraction particle size distribution measurement.
　上記導電性粒子の粒子径の変動係数は、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。上記粒子径の変動係数が上記下限以上及び上記上限以下であると、電極上に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変動係数は、５％未満であってもよい。 The coefficient of variation of the particle diameter 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 variation coefficient of the particle diameter is not less than the above lower limit and not more than the above upper limit, the solder can be more efficiently disposed on the electrode. However, the coefficient of variation of the particle diameter of the conductive particles may be less than 5%.
　上記変動係数（ＣＶ値）は下記式で表される。 The above coefficient of variation (CV value) is expressed by the following equation.
　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 particle diameter of conductive particles Dn: Average value of particle diameter of 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、扁平状などの球形状以外の形状であってもよい。 The shape of the conductive particles is not particularly limited. The conductive particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
　上記導電材料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、更に好ましくは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、更に好ましくは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。 The content of the conductive particles in 100% by weight of the conductive material is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 10% by weight or more, particularly preferably 20% by weight or more, most preferably. It is 30% by weight or more, preferably 80% by weight or less, more preferably 60% by weight or less, and still more preferably 50% by weight or less. When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be arranged more efficiently on the electrodes, and it is easy to arrange many conductive particles between the electrodes. Therefore, the conduction reliability is further enhanced. From the viewpoint of further improving the conduction reliability, the content of the conductive particles is preferably large.
　（熱硬化性化合物：熱硬化性成分）
　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。なかでも、導電材料の硬化性及び粘度をより一層良好にし、接続信頼性をより一層高める観点から、エポキシ化合物が好ましい。上記熱硬化性化合物は、１種のみが用いられもよく、２種以上が併用されてもよい。 (Thermosetting compound: thermosetting component)
The thermosetting compound is a compound that can be cured by heating. Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. Among these, an epoxy compound is preferable from the viewpoint of further improving the curability and viscosity of the conductive material and further improving the connection reliability. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.
　上記エポキシ化合物としては、芳香族エポキシ化合物が挙げられる。レゾルシノール型エポキシ化合物、ナフタレン型エポキシ化合物、ビフェニル型エポキシ化合物、ベンゾフェノン型エポキシ化合物等の結晶性エポキシ化合物が好ましい。常温（２３℃）で固体であり、かつ溶融温度がはんだの融点以下であるエポキシ化合物が好ましい。溶融温度は好ましくは１００℃以下、より好ましくは８０℃以下であり、好ましくは４０℃以上である。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、なおかつ、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、はんだ粒子の凝集を効率よく進行させることができる。 The above-mentioned epoxy compound includes an aromatic epoxy compound. Crystalline epoxy compounds such as resorcinol-type epoxy compounds, naphthalene-type epoxy compounds, biphenyl-type epoxy compounds, and benzophenone-type epoxy compounds are preferred. An epoxy compound that is solid at normal temperature (23 ° C.) and has a melting temperature equal to or lower than the melting point of the solder is preferable. The melting temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and preferably 40 ° C. or higher. By using the preferable epoxy compound, the first connection target member and the second connection target are high when the connection target member is bonded to each other when the viscosity is high and acceleration is applied by impact such as conveyance. The positional deviation from the member can be suppressed, and the viscosity of the conductive material can be greatly reduced by the heat at the time of curing, and the aggregation of solder particles can be efficiently advanced.
　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２０重量％以上、より好ましくは４０重量％以上、更に好ましくは５０重量％以上であり、好ましくは９９重量％以下、より好ましくは９８重量％以下、更に好ましくは９０重量％以下、特に好ましくは８０重量％以下である。耐衝撃性をより一層高める観点からは、上記熱硬化性化合物の含有量は多い方が好ましい。 The content of the thermosetting compound in 100% by weight of the conductive material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and preferably 99% by weight or less. More preferably, it is 98 weight% or less, More preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting compound is large.
　（熱硬化剤：熱硬化性成分）
　上記熱硬化剤は、上記熱硬化性化合物を熱硬化させる。上記熱硬化剤としては、イミダゾール硬化剤、アミン硬化剤、フェノール硬化剤、ポリチオール硬化剤等のチオール硬化剤、酸無水物、熱カチオン開始剤（熱カチオン硬化剤）及び熱ラジカル発生剤等が挙げられる。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 agent: thermosetting component)
The thermosetting agent thermosets the thermosetting compound. Examples of the thermosetting agent include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and other thiol curing agents, acid anhydrides, thermal cation initiators (thermal cation curing agents), and thermal radical generators. It is done. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.
　導電材料を低温でより一層速やかに硬化可能であるので、イミダゾール硬化剤、チオール硬化剤又はアミン硬化剤が好ましい。また、熱硬化性化合物と上記熱硬化剤とを混合したときに保存安定性が高くなるので、潜在性の硬化剤が好ましい。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。 An imidazole curing agent, a thiol curing agent, or an amine curing agent is preferable because the conductive material can be cured more rapidly at a low temperature. Moreover, since a storage stability becomes high when a thermosetting compound and the said thermosetting agent are mixed, a latent hardening agent is preferable. The latent curing agent is preferably a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent. In addition, the said thermosetting agent may be coat | covered with polymeric substances, such as a polyurethane resin or a polyester resin.
　上記イミダゾール硬化剤としては、特に限定されず、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等が挙げられる。 The imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.
　上記チオール硬化剤としては、特に限定されず、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, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .
　上記アミン硬化剤としては、特に限定されず、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, and hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]. Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.
　上記熱カチオン開始剤（熱カチオン硬化剤）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。 Examples of the thermal cation initiator (thermal cation curing agent) include iodonium cation curing agents, oxonium cation curing agents, and sulfonium cation curing agents. Examples of the 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としては、特に限定されず、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, and examples thereof include azo compounds and organic peroxides. 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、更に好ましくは８０℃以上であり、好ましくは２５０℃以下、より好ましくは２００℃以下、更に好ましくは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、はんだが電極上により一層効率的に配置される。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, still more preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. Hereinafter, it is particularly preferably 140 ° C. or lower. When the reaction start temperature of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the solder is more efficiently arranged on the electrode. The reaction initiation temperature of the thermosetting agent is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
　はんだを電極上に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℃以上高いことが更に好ましい。 From the viewpoint of more efficiently arranging the solder on the electrode, the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder, more preferably 5 ° C or higher, more preferably 10 ° C or higher. More preferably.
　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。 The reaction start temperature of the thermosetting agent means the temperature at which the exothermic peak of DSC starts to rise.
　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、更に好ましくは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、導電材料を充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。 The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent with respect to 100 parts by weight of the thermosetting compound is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less, more preferably 75 parts by weight or less. When the content of the thermosetting agent is not less than the above lower limit, it is easy to sufficiently cure the conductive material. When the content of the thermosetting agent is not more than the above upper limit, it is difficult for an excess thermosetting agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further enhanced.
　（フラックス）
　上記導電材料は、フラックスを含むことが好ましい。フラックスの使用により、はんだを電極上により一層効果的に配置することができる。また、フラックス効果の発現により、電極間の接続抵抗がより一層低くなる。上記フラックスは特に限定されない。フラックスとして、はんだ接合等に一般的に用いられているフラックスを使用できる。上記フラックスとしては、例えば、塩化亜鉛、塩化亜鉛と無機ハロゲン化物との混合物、塩化亜鉛と無機酸との混合物、溶融塩、リン酸、リン酸の誘導体、有機ハロゲン化物、ヒドラジン、有機酸及び松脂等が挙げられる。上記フラックスは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。 (flux)
The conductive material preferably contains a flux. By using flux, the solder can be more effectively placed on the electrode. Moreover, the connection resistance between electrodes becomes still lower by the expression of the flux effect. The flux is not particularly limited. As the flux, a flux generally used for soldering or the like can be used. Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an organic acid, and pine resin. Etc. As for the said flux, only 1 type may be used and 2 or more types may be used together.
　上記溶融塩としては、塩化アンモニウム等が挙げられる。上記有機酸としては、乳酸、クエン酸、ステアリン酸、グルタミン酸及びグルタル酸等が挙げられる。上記松脂としては、活性化松脂及び非活性化松脂等が挙げられる。上記フラックスは、カルボキシル基を２個以上有する有機酸、松脂であることが好ましい。上記フラックスは、カルボキシル基を２個以上有する有機酸であってもよく、松脂であってもよい。カルボキシル基を２個以上有する有機酸、松脂の使用により、電極間の導通信頼性がより一層高くなる。 Examples of the molten salt include ammonium chloride. Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid, and glutaric acid. Examples of the pine resin include activated pine resin and non-activated pine resin. The flux is preferably an organic acid having two or more carboxyl groups, pine resin. The flux may be an organic acid having two or more carboxyl groups, or pine resin. By using an organic acid having two or more carboxyl groups, pine resin, the conduction reliability between the electrodes is further enhanced.
　上記松脂はアビエチン酸を主成分とするロジン類である。フラックスは、ロジン類であることが好ましく、アビエチン酸であることがより好ましい。この好ましいフラックスの使用により、電極間の導通信頼性がより一層高くなる。 The above rosins are rosins whose main component is abietic acid. The flux is preferably rosins, and more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further enhanced.
　上記フラックスの活性温度（融点）は、好ましくは５０℃以上、より好ましくは７０℃以上、更に好ましくは８０℃以上であり、好ましくは２００℃以下、より好ましくは１９０℃以下、より一層好ましくは１６０℃以下、更に好ましくは１５０℃以下、更に一層好ましくは１４０℃以下である。上記フラックスの活性温度が上記下限以上及び上記上限以下であると、フラックス効果がより一層効果的に発揮され、はんだが電極上により一層効率的に配置される。上記フラックスの活性温度（融点）は８０℃以上、１９０℃以下であることが好ましい。上記フラックスの活性温度（融点）は８０℃以上、１４０℃以下であることが特に好ましい。 The active temperature (melting point) of the flux is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 200 ° C. or lower, more preferably 190 ° C. or lower, even more preferably 160. ° C or lower, more preferably 150 ° C or lower, still more preferably 140 ° C or lower. When the activation temperature of the flux is not less than the above lower limit and not more than the above upper limit, the flux effect is more effectively exhibited and the solder is more efficiently arranged on the electrode. The active temperature (melting point) of the flux is preferably 80 ° C. or higher and 190 ° C. or lower. The activation temperature (melting point) of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
　フラックスの活性温度（融点）が８０℃以上、１９０℃以下である上記フラックスとしては、コハク酸（融点１８６℃）、グルタル酸（融点９６℃）、アジピン酸（融点１５２℃）、ピメリン酸（融点１０４℃）、スベリン酸（融点１４２℃）等のジカルボン酸、安息香酸（融点１２２℃）、リンゴ酸（融点１３０℃）等が挙げられる。 The flux having an active temperature (melting point) of 80 ° C. or higher and 190 ° C. or lower includes succinic acid (melting point 186 ° C.), glutaric acid (melting point 96 ° C.), adipic acid (melting point 152 ° C.), pimelic acid (melting point) 104 ° C.), dicarboxylic acids such as suberic acid (melting point 142 ° C.), benzoic acid (melting point 122 ° C.), malic acid (melting point 130 ° C.) and the like.
　また、上記フラックスの沸点は２００℃以下であることが好ましい。 The boiling point of the flux is preferably 200 ° C. or lower.
　はんだを電極上により一層効率的に配置する観点からは、上記フラックスの融点は、上記はんだの融点よりも、高いことが好ましく、５℃以上高いことがより好ましく、１０℃以上高いことが更に好ましい。 From the viewpoint of more efficiently arranging the solder on the electrode, the melting point of the flux is preferably higher than the melting point of the solder, more preferably 5 ° C or higher, and even more preferably 10 ° C or higher. .
　はんだを電極上により一層効率的に配置する観点からは、上記フラックスの融点は、上記熱硬化剤の反応開始温度よりも、高いことが好ましく、５℃以上高いことがより好ましく、１０℃以上高いことが更に好ましい。 From the viewpoint of more efficiently arranging the solder on the electrode, the melting point of the flux is preferably higher than the reaction start temperature of the thermosetting agent, more preferably 5 ° C or higher, more preferably 10 ° C or higher. More preferably.
　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。 The flux may be dispersed in the conductive material or may be adhered on the surface of the conductive particles.
　上記フラックスは、加熱によりカチオンを放出するフラックスであることが好ましい。加熱によりカチオンを放出するフラックスの使用により、はんだを電極上により一層効率的に配置することができる。 The flux is preferably a flux that releases cations by heating. By using a flux that releases cations upon heating, the solder can be placed more efficiently on the electrode.
　上記加熱によりカチオンを放出するフラックスとしては、上記熱カチオン開始剤（熱カチオン硬化剤）が挙げられる。 The above-mentioned thermal cation initiator (thermal cation curing agent) is exemplified as the flux that releases cations by the heating.
　上記導電材料１００重量％中、上記フラックスの含有量は好ましくは０．５重量％以上であり、好ましくは３０重量％以下、より好ましくは２５重量％以下である。上記導電材料は、フラックスを含んでいなくてもよい。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、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、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。 In 100% by weight of the conductive material, the content of the flux is preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less. The conductive material may not contain flux. When the flux content is not less than the above lower limit and not more than the above upper limit, it becomes more difficult to form an oxide film on the surface of the solder and the electrode, and the oxide film formed on the surface of the solder and the electrode is more effective. Can be removed.
　（フィラー）
　上記導電材料には、フィラーを添加してもよい。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、はんだの凝集する距離を抑制し、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)
A filler may be added to the conductive material. The filler may be an organic filler or an inorganic filler. By adding the filler, the distance at which the solder aggregates can be suppressed, and the conductive particles can be uniformly aggregated over all the electrodes of the substrate.
　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、更に好ましくは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、はんだ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 filler content is preferably 0% by weight (not contained) or more, preferably 5% by weight or less, more preferably 2% by weight or less, and still more preferably 1% by weight or less. is there. When the content of the filler is not less than the above lower limit and not more than the above upper limit, the solder is 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、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, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, and a lubricant as necessary. In addition, various additives such as an antistatic agent and a flame retardant may be included.
　（接続構造体及び接続構造体の製造方法）
　本発明に係る接続構造体は、少なくとも１つの第１の電極を表面に有する第１の接続対象部材と、少なくとも１つの第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り、上記接続部が上述した導電材料により形成されている。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、上記導電性粒子におけるはんだにより電気的に接続されている。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、上記接続部中のはんだ部により電気的に接続されている。 (Connection structure and method of manufacturing connection structure)
A connection structure according to the present invention includes a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection object member and the connection part which has connected the said 2nd connection object member are provided. In the connection structure according to the present invention, the material of the connection portion is the conductive material described above, and the connection portion is formed of the conductive material described above. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by solder in the conductive particles. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
　本発明に係る接続構造体の製造方法は、上述した導電材料を用いて、少なくとも１つの第１の電極を表面に有する第１の接続対象部材の表面上に、上記導電材料を配置する工程と、上記導電材料の上記第１の接続対象部材側とは反対の表面上に、少なくとも１つの第２の電極を表面に有する第２の接続対象部材を、上記第１の電極と上記第２の電極とが対向するように配置する工程と、上記導電性粒子におけるはんだの融点以上に上記導電材料を加熱することで、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を、上記導電材料により形成し、かつ、上記第１の電極と上記第２の電極とを、上記接続部中のはんだ部により電気的に接続する工程とを備える。好ましくは、上記熱硬化性化合物の硬化温度以上に上記導電材料を加熱する。 The manufacturing method of the connection structure according to the present invention includes the step of disposing the conductive material on the surface of the first connection target member having at least one first electrode on the surface, using the conductive material described above. The second connection object member having at least one second electrode on the surface opposite to the first connection object member side of the conductive material, the first electrode and the second electrode The first connection target member and the second connection target member are connected by heating the conductive material to a temperature equal to or higher than the melting point of the solder in the conductive particles, and the step of arranging the electrodes to face each other. Forming a connecting portion made of the conductive material, and electrically connecting the first electrode and the second electrode by a solder portion in the connecting portion. Preferably, the conductive material is heated above the curing temperature of the thermosetting compound.
　本発明に係る接続構造体及び本発明に係る接続構造体の製造方法では、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 and the method for manufacturing the connection structure according to the present invention, since the specific conductive material is used, the solder in the conductive particles gathers between the first electrode and the second electrode. It is easy and the solder can be efficiently arranged on the electrode (line). In addition, a part of the solder is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be considerably reduced. Therefore, the conduction reliability between the first electrode and the second electrode can be improved. In addition, it is possible to prevent electrical connection between laterally adjacent electrodes that should not be connected, and to improve insulation reliability.
　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、導電ペーストであることが好ましい。 Further, in order to efficiently arrange the solder in the conductive particles on the electrode and to considerably reduce the amount of solder arranged in the region where the electrode is not formed, the conductive material is not a conductive film, A conductive paste is preferred.
　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７０％以上であり、好ましくは１００％以下である。 The thickness of the solder part 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 wetted area on the surface of the electrode (area where the solder is in contact with 100% of the exposed area of the electrode) is preferably 50% or more, more preferably 70% or more, and preferably 100% or less.
　本発明に係る接続構造体の製造方法では、上記第２の接続対象部材を配置する工程及び上記接続部を形成する工程において、加圧を行わず、上記導電材料には、上記第２の接続対象部材の重量が加わることが好ましく、上記第２の接続対象部材を配置する工程及び上記接続部を形成する工程において、上記導電材料には、上記第２の接続対象部材の重量の力を超える加圧圧力は加わらないことが好ましい。これらの場合には、複数のはんだ部において、はんだ量の均一性をより一層高めることができる。さらに、はんだ部の厚みをより一層効果的に厚くすることができ、はんだが電極間に多く集まりやすくなり、はんだを電極（ライン）上により一層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より一層少なくすることができる。従って、電極間の導通信頼性をより一層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より一層防ぐことができ、絶縁信頼性をより一層高めることができる。 In the method for manufacturing a connection structure according to the present invention, in the step of arranging the second connection target member and the step of forming the connection portion, no pressure is applied, and the second connection is applied to the conductive material. The weight of the target member is preferably added, and in the step of arranging the second connection target member and the step of forming the connection portion, the conductive material exceeds the weight force of the second connection target member. It is preferable that no pressure is applied. In these cases, the uniformity of the amount of solder can be further enhanced in the plurality of solder portions. Furthermore, the thickness of the solder portion can be increased more effectively, so that a large amount of solder is easily collected between the electrodes, and the solder can be arranged more efficiently on the electrodes (lines). Further, a part of the solder is difficult to be disposed in a region (space) where no electrode is formed, and the amount of solder disposed in a region where no electrode is formed can be further reduced. Therefore, the conduction reliability between the electrodes can be further enhanced. In addition, the electrical connection between the laterally adjacent electrodes that should not be connected can be further prevented, and the insulation reliability can be further improved.
　また、導電フィルムではなく、導電ペーストを用いれば、導電ペーストの塗布量によって、接続部及びはんだ部の厚みを調整することが容易になる。一方で、導電フィルムでは、接続部の厚みを変更したり、調整したりするためには、異なる厚みの導電フィルムを用意したり、所定の厚みの導電フィルムを用意したりしなければならないという問題がある。また、導電フィルムでは、はんだの溶融温度で、導電フィルムの溶融粘度を十分に下げることが困難である傾向があり、はんだの凝集が阻害されやすいという問題がある。 Also, if a conductive paste is used instead of a conductive film, it becomes easy to adjust the thicknesses of the connection part and the solder part depending on the amount of the conductive paste applied. On the other hand, in the conductive film, in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film having a different thickness or to prepare a conductive film having a predetermined thickness. There is. Moreover, in the conductive film, it tends to be difficult to sufficiently lower the melt viscosity of the conductive film at the melting temperature of the solder, and there is a problem that the aggregation of the solder is easily inhibited.
　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 an 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、複数の導電性粒子と、熱硬化性化合物と、熱硬化剤とを含む。上記熱硬化性化合物と上記熱硬化剤とは、熱硬化性成分である。 The connection structure 1 shown in FIG. 1 is a connection that connects a first connection target member 2, a second connection target member 3, and the first connection target member 2 and the second connection target member 3. Part 4. The connection part 4 is formed of the conductive material described above. In the present embodiment, the conductive material includes a plurality of conductive particles, a thermosetting compound, and a thermosetting agent. The thermosetting compound and the thermosetting agent are thermosetting components.
　接続部４は、複数の導電性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 connecting portion 4 includes a solder portion 4A in which a plurality of conductive particles gather and are joined to each other, and a cured product portion 4B in which a thermosetting component is thermally cured.
　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 object 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 portion 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 product portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a. In an area different from the solder part 4A (hardened product part 4B part), there is no solder separated from the solder part 4A. If the amount is small, the solder may be present in a region (cured product 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、複数の導電性粒子が集まり、複数の導電性粒子が溶融した後、導電性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、導電性粒子を用いることにより、導電性の外表面がニッケル、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、導電材料は、フラックスを含んでいてもよい。フラックスを用いた場合には、加熱により、一般にフラックスは次第に失活する。 As shown in FIG. 1, in the connection structure 1, after a plurality of conductive particles gather between the first electrode 2a and the second electrode 3a and the plurality of conductive particles melt, the conductive particles The melted material solidifies after the surface of the electrode wets and spreads to form the solder portion 4A. For this reason, the connection area of 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts, and the 2nd electrode 3a becomes large. That is, by using the conductive particles, the solder portion 4A, the first electrode 2a, and the solder are compared with the case where the conductive outer surface is made 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, the conduction | electrical_connection reliability and connection reliability in the connection structure 1 become high. Note that the conductive material may contain a flux. When the flux is used, the flux is generally deactivated gradually 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 addition, in the connection structure 1 shown in FIG. 1, all of the solder portions 4A are located in the facing region between the first and second electrodes 2a and 3a. The connection structure 1X of the modification shown in FIG. 3 is different from the connection structure 1 shown in FIG. 1 only in the connection portion 4X. The connection part 4X has the solder part 4XA and the hardened | cured material part 4XB. As in the connection structure 1X, most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a are opposed to each other, and a part of the solder portion 4XA is first and second. You may protrude to the side from the area | region which electrode 2a, 3a has opposed. The solder part 4XA protruding laterally from the region where the first and second electrodes 2a and 3a are opposed is a part of the solder part 4XA and is not a solder separated from the solder part 4XA. In the present embodiment, the amount of solder away from the solder portion can be reduced, but the solder away from the solder portion may exist in the cured product portion.
　導電性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。導電性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。 If the use amount of the conductive particles is reduced, it becomes easy to obtain the connection structure 1. If the usage-amount of electroconductive particle is increased, it will become easy to obtain the connection structure 1X.
　導通信頼性をより一層高める観点からは、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。 From the viewpoint of further improving the conduction reliability, in the connection structures 1 and 1X, the first electrode 2a and the second electrode 2a are arranged in the stacking direction of the first electrode 2a, the connection portions 4 and 4X, and the second electrode 3a. When the portion facing the electrode 3a is viewed, the solder portion in the connection portions 4 and 4X is at least 50% of the area of 100% of the portion facing the first electrode 2a and the second electrode 3a. 4A and 4XA are preferably arranged.
　導通信頼性をより一層高める観点からは、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（より好ましくは６０％以上、更に好ましくは７０％以上、特に好ましくは８０％以上、最も好ましくは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好ましい。 From the viewpoint of further improving the conduction reliability, the 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 seen. Sometimes, 50% or more (more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more) out of 100% of the area where the first electrode and the second electrode face each other. , Most preferably 90% or more), the solder portion in the connection portion is preferably disposed.
　導通信頼性をより一層高める観点からは、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（より好ましくは８０％以上、更に好ましくは９０％以上、特に好ましくは９５％以上、最も好ましくは９９％以上）が配置されていることが好ましい。 From the viewpoint of further improving the conduction reliability, the first electrode and the second electrode are opposed to each other in a direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode. When the matching portion is viewed, the portion where the first electrode and the second electrode face each other is 70% or more (more preferably 80% or more, more preferably 90%) of the solder portion in the connection portion. In particular, it is preferable that 95% or more, most preferably 99% or more) is disposed.
　次に、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, an example of a method for manufacturing the connection structure 1 using the conductive material according to the embodiment of the present invention will be described.
　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、複数の導電性粒子１１Ａとを含む導電材料１１を配置する（第１の工程）。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、導電性粒子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。 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 conductive particles 11A is disposed on the surface of the first connection target member 2 (first Process). The conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided. After the arrangement of the conductive material 11, the conductive particles 11A are arranged both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
　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。 The arrangement method of the conductive material 11 is not particularly limited, and examples thereof include application by a dispenser, screen printing, and discharge by 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。 Moreover, the 2nd connection object member 3 which has the 2nd 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 opposite to the first connection target member 2 side of the conductive material 11, The 2nd connection object member 3 is arrange | positioned (2nd process). On the surface of the conductive material 11, the second connection target member 3 is disposed from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.
　次に、導電性粒子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（バインダー）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導電性粒子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）。本実施形態では、導電フィルムではなく、導電材料を用いているために、更に導電材料が特定の組成を有するために、導電性粒子１１Ａが、第１の電極２ａと第２の電極３ａとの間に効果的に集まる。また、導電性粒子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を、導電材料１１により形成する。導電材料１１により接続部４が形成され、複数の導電性粒子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。導電性粒子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導電性粒子１１Ａの移動が開始してから、第１の電極２ａと第２の電極３ａとの間に導電性粒子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 conductive particles 11A (third step). Preferably, the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (binder). At the time of this heating, the conductive particles 11A that existed in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect). In this embodiment, since the conductive material is used instead of the conductive film, the conductive material 11A has a specific composition, so that the conductive particles 11A are formed between the first electrode 2a and the second electrode 3a. Gather effectively in between. In addition, the conductive particles 11A are melted and joined to each other. Further, the thermosetting component 11B is thermoset. As a result, as shown in FIG. 2C, the connection portion 4 that connects the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11. The connection part 4 is formed of the conductive material 11, the solder part 4A is formed by joining the plurality of conductive particles 11A, and the cured part 4B is formed by thermosetting the thermosetting component 11B. If the conductive particles 11A are sufficiently moved, the first electrode 2a and the second electrode 2a are moved after the movement of the conductive particles 11A that are not positioned between the first electrode 2a and the second electrode 3a starts. The temperature does not have to be kept constant until the movement of the conductive particles 11A between the electrodes 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、導電性粒子１１Ａが、第１の電極２ａと第２の電極３ａとの間に効果的に集まる。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、導電性粒子が第１の電極と第２の電極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。 In this embodiment, it is preferable that no pressure is applied 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, the conductive particles 11A are effectively collected between the first electrode 2a and the second electrode 3a when the connection portion 4 is formed. In addition, if pressure is applied in at least one of the second step and the third step, the action of the conductive particles trying to collect between the first electrode and the second electrode is inhibited. The tendency to be higher.
　ただし、第１の電極と第２の電極との間隔を確保できれば、加圧を行ってもよい。電極間の間隔を確保する手段として、例えば、所望の電極間の間隔に相当するスペーサーを添加し、少なくとも１個、好ましくは３個以上のスペーサーが電極間に配置されるようにすればよい。スペーサーとしては、無機粒子、有機粒子が挙げられる。スペーサーは絶縁性粒子であることが好ましい。 However, pressurization may be performed as long as the interval between the first electrode and the second electrode can be secured. As a means for ensuring the gap between the electrodes, for example, a spacer corresponding to the desired gap between the electrodes may be added so that at least one, preferably three or more spacers are arranged between the electrodes. Examples of the spacer include inorganic particles and organic particles. The spacer is preferably an insulating particle.
　また、本実施形態では、加圧を行っていないため、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た場合でも、そのずれを補正して、第１の接続対象部材の電極と第２の接続対象部材の電極と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た溶融したはんだが、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、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。 Moreover, in this embodiment, since pressurization is not performed, when the second connection target member is superimposed on the first connection target member to which the conductive material is applied, the electrode of the first connection target member Even when the first connection target member and the second connection target member are overlapped in a state where the alignment of the electrodes of the second connection target member is shifted, the shift is corrected and the first connection target member is corrected. And the electrode of the second connection target member can be connected (self-alignment effect). This is because the molten solder self-aggregated between the electrode of the first connection target member and the electrode of the second connection target member is the electrode of the first connection target member and the electrode of the second connection target member. As the area where the solder and the other components of the conductive material are in contact with each other is minimized, the energy becomes more stable. Therefore, the force that makes the connection structure with alignment, which is the connection structure with the smallest area, works. Because. At this time, it is desirable that the conductive material is not cured, and that the viscosity of components other than the conductive particles of the conductive material is sufficiently low at that temperature and time.
　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。 In this way, the connection structure 1 shown in FIG. 1 is obtained. The second step and the third step may be performed continuously. Moreover, after performing the said 2nd process, the laminated body of the 1st connection object member 2, the electrically-conductive material 11, and the 2nd connection object member 3 which are obtained is moved to a heating part, and the said 3rd connection object is carried out. You may perform a process. In order to perform the heating, the laminate may be disposed on a heating member, or the laminate may be disposed 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、更に好ましくは２００℃以下である。 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 still more preferably 200 ° C. or lower.
　なお、上記第３の工程の後に、位置の修正や製造のやり直しを目的として、第１の接続対象部材又は第２の接続対象部材を、接続部から剥離することができる。この剥離を行うための加熱温度は、好ましくは導電性粒子の融点以上、より好ましくは導電性粒子の融点（℃）＋１０℃以上である。この剥離を行うための加熱温度は、導電性粒子の融点（℃）＋１００℃以下であってもよい。 In addition, after the said 3rd process, a 1st connection object member or a 2nd connection object member can be peeled from a connection part for the purpose of correction of a position, or re-production. The heating temperature for performing this peeling is preferably not lower than the melting point of the conductive particles, more preferably not lower than the melting point (° C.) of the conductive particles + 10 ° C. The heating temperature for performing this peeling may be the melting point (° C.) of the conductive particles + 100 ° C. or less.
　上記第３の工程における加熱方法としては、導電性粒子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 the heating method in the third step, a method of heating the entire connection structure using a reflow furnace or an oven above the melting point of the conductive particles and the curing temperature of the thermosetting component, The method of heating only the connection part of a structure locally is mentioned.
　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。 Examples of instruments used in the method of locally heating include a hot plate, a heat gun that applies 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 directly under the connection is made of a metal with high thermal conductivity, and other places where heating is not preferred are made of a material with low thermal conductivity such as a fluororesin. The upper surface of the hot plate is preferably 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など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. Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor chip, a semiconductor package, LED chip, LED package, a capacitor | condenser, a diode, and a resin film, a printed circuit board, a flexible printed circuit board, flexible Examples include electronic components such as flat cables, rigid flexible substrates, glass epoxy substrates, and circuit boards such as glass substrates. The first and second connection target members are preferably 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２の接続対象部材が、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充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、半導体チップなど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. The second connection target member is preferably a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. Resin films, flexible printed boards, flexible flat cables, and rigid flexible boards have the property of being highly flexible and relatively lightweight. When a conductive film is used for connection of such a connection object member, there exists a tendency for electroconductive particle to collect on an electrode easily. On the other hand, even if a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible circuit board is used by using a conductive paste, the conductive particles are efficiently collected on the electrode, so that conduction between the electrodes is achieved. Reliability can be sufficiently increased. When using a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible circuit board, the reliability of conduction between electrodes by not applying pressure compared to the case of using other connection target members such as a semiconductor chip. The improvement effect can be obtained 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。 Examples of the electrode 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 connection object member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for 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.
　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.
　熱硬化性化合物１：２，４－ビス（グリシジルオキシ）ベンゾフェノン（結晶性熱硬化性化合物、融点：９４℃、分子量３６２） Thermosetting compound 1: 2,4-bis (glycidyloxy) benzophenone (crystalline thermosetting compound, melting point: 94 ° C., molecular weight 362)
　２，４－ビス（グリシジルオキシ）ベンゾフェノンの合成：
　３つ口フラスコに、２，４－ジヒドロキシベンゾフェノン２７ｇ、エピクロルヒドリン２３０ｇ、ｎ－ブタノール７０ｇ、及びテトラエチルベンジルアンモニウムクロライド１ｇを入れ、室温にて撹拌、溶解させた。その後、窒素雰囲気下、撹拌下にて、７０℃に昇温し、減圧還流下、水酸化ナトリウム水溶液（濃度４８重量％）４５ｇを滴下した。滴下は、４時間かけて行った。その後、７０℃にて、ディーンスターク管を用い、水分を除去しながら２時間反応させた。その後、減圧下で、未反応のエピクロルヒドリンを除去した。 Synthesis of 2,4-bis (glycidyloxy) benzophenone:
In a three-necked flask, 27 g of 2,4-dihydroxybenzophenone, 230 g of epichlorohydrin, 70 g of n-butanol, and 1 g of tetraethylbenzylammonium chloride were stirred and dissolved at room temperature. Thereafter, the temperature was raised to 70 ° C. under stirring in a nitrogen atmosphere, and 45 g of an aqueous sodium hydroxide solution (concentration: 48 wt%) was added dropwise under reduced pressure. The dropping was performed over 4 hours. Then, it was made to react at 70 degreeC for 2 hours, using a Dean-Stark tube, removing a water | moisture content. Thereafter, unreacted epichlorohydrin was removed under reduced pressure.
　得られた反応生成物を、ＭＥＫ（メチルエチルケトン）：ｎ－ブタノール＝３：１（重量比）の混合溶剤４００ｇに溶解し、水酸化ナトリウム水溶液（濃度１０重量％）５ｇを添加し、８０℃で２時間加熱した。 The obtained reaction product was dissolved in 400 g of a mixed solvent of MEK (methyl ethyl ketone): n-butanol = 3: 1 (weight ratio), and 5 g of an aqueous sodium hydroxide solution (concentration: 10 wt%) was added at 80 ° C. Heated for 2 hours.
　その後、室温に冷却し、純水により、洗液が中性になるまで洗浄を行った。有機層をろ過しながら分取し、減圧下にて、残水分及び混合溶媒を除去し、反応生成物を得た。 Then, it was cooled to room temperature and washed with pure water until the washing solution became neutral. The organic layer was collected by filtration, and the remaining water and the mixed solvent were removed under reduced pressure to obtain a reaction product.
　ｎ－ヘキサンを用い、上記反応生成物３４ｇを再結晶により精製し、真空乾燥により残溶剤分を除去した。 Using n-hexane, 34 g of the reaction product was purified by recrystallization, and the residual solvent was removed by vacuum drying.
　得られたエポキシ化合物：ＤＳＣによる融点は９４℃、エポキシ当量は１７６ｇ／ｅｑ．、マススペクトルによる分子量は３６２、１５０℃での溶融粘度は５ｍＰａ・ｓであった。 Obtained epoxy compound: melting point by DSC was 94 ° C., epoxy equivalent was 176 g / eq. According to the mass spectrum, the molecular weight was 362, and the melt viscosity at 150 ° C. was 5 mPa · s.
　・示差走査熱量測定（ＤＳＣ）測定装置及び測定条件
　装置；日立ハイテクサイエンス社製「Ｘ－ＤＳＣ７０００」、サンプル量；３ｍｇ、温度条件；１０℃／ｍｉｎ -Differential scanning calorimetry (DSC) measuring device and measuring conditions Device: "X-DSC7000" manufactured by Hitachi High-Tech Science Co., sample amount: 3 mg, temperature condition: 10 ° C / min
　・１５０℃における溶融粘度：ＡＳＴＭ　Ｄ４２８７に準拠し、エムエスティーエンジニアリング社製のＩＣＩコーンプレート粘度計を用いて測定 · Melt viscosity at 150 ° C: Measured using ICI cone plate viscometer manufactured by MST Engineering in accordance with ASTM D4287
　・エポキシ当量の測定：ＪＩＳ　Ｋ７２３６：２００１に準拠して測定 ・ Measurement of epoxy equivalent: Measured according to JIS K7236: 2001
　・分子量の測定：マススペクトル　ＧＣ－ＭＳ装置（日本電子社製「ＪＭＳ　Ｋ－９」）を用いて測定 ・ Molecular weight measurement: Mass spectrum Measured using GC-MS equipment (“JMS K-9” manufactured by JEOL Ltd.)
　熱硬化性化合物２：４，４’－ビス（グリジジルオキシ）ベンゾフェノン（結晶性熱硬化性化合物、融点：１３２℃、分子量３６２） Thermosetting compound 2: 4,4'-bis (glycidyloxy) benzophenone (crystalline thermosetting compound, melting point: 132 ° C, molecular weight 362)
　４，４’－ビス（グリジジルオキシ）ベンゾフェノンの合成：
　３つ口フラスコに、４，４’－ジヒドロキシベンゾフェノン２７ｇ、エピクロルヒドリン２３０ｇ、ｎ－ブタノール７０ｇ、及びテトラエチルベンジルアンモニウムクロライド１ｇを入れ、室温にて撹拌、溶解させた。その後、窒素雰囲気下、撹拌下にて、７０℃に昇温し、減圧還流下、水酸化ナトリウム水溶液（濃度４８重量％）４５ｇを滴下した。滴下は、４時間かけて行った。その後。７０℃にて、ディーンスターク管を用い、水分を除去しながら２時間反応させた。その後、減圧下で、未反応のエピクロルヒドリンを除去した。 Synthesis of 4,4′-bis (glycidyloxy) benzophenone:
In a three-necked flask, 27 g of 4,4′-dihydroxybenzophenone, 230 g of epichlorohydrin, 70 g of n-butanol, and 1 g of tetraethylbenzylammonium chloride were added and stirred and dissolved at room temperature. Thereafter, the temperature was raised to 70 ° C. under stirring in a nitrogen atmosphere, and 45 g of an aqueous sodium hydroxide solution (concentration: 48 wt%) was added dropwise under reduced pressure. The dropping was performed over 4 hours. afterwards. The reaction was carried out at 70 ° C. for 2 hours using a Dean-Stark tube while removing moisture. Thereafter, unreacted epichlorohydrin was removed under reduced pressure.
　得られた反応生成物を、ＭＥＫ（メチルエチルケトン）：ｎ－ブタノール＝３：１（重量比）の混合溶剤４００ｇに溶解し、水酸化ナトリウム水溶液（濃度１０重量％）５ｇを添加し、８０℃で２時間加熱した。 The obtained reaction product was dissolved in 400 g of a mixed solvent of MEK (methyl ethyl ketone): n-butanol = 3: 1 (weight ratio), and 5 g of an aqueous sodium hydroxide solution (concentration: 10 wt%) was added at 80 ° C. Heated for 2 hours.
　その後、室温に冷却し、純水により、洗液が中性になるまで洗浄を行った。有機層をろ過しながら分取し、減圧下にて、残水分及び混合溶媒を除去し、反応生成物を得た。 Then, it was cooled to room temperature and washed with pure water until the washing solution became neutral. The organic layer was collected by filtration, and the remaining water and the mixed solvent were removed under reduced pressure to obtain a reaction product.
　ｎ－ヘキサンを用い、上記反応生成物３４ｇを再結晶により精製し、真空乾燥により残溶剤分を除去した。 Using n-hexane, 34 g of the reaction product was purified by recrystallization, and the residual solvent was removed by vacuum drying.
　得られたエポキシ化合物：ＤＳＣによる融点は１３２℃、エポキシ当量は１７６ｇ／ｅｑ．、マススペクトルによる分子量は３６２、１５０℃での溶融粘度は１２ｍＰａ・ｓであった。 Obtained epoxy compound: melting point by DSC is 132 ° C., epoxy equivalent is 176 g / eq. According to the mass spectrum, the molecular weight was 362, and the melt viscosity at 150 ° C. was 12 mPa · s.
　熱硬化性化合物３：エポキシ基含有アクリルポリマー、日油社製「ＭＡＲＰＲＯＯＦ　Ｇ－０１５０Ｍ」 Thermosetting compound 3: Epoxy group-containing acrylic polymer, “MARPROOF G-0150M” manufactured by NOF Corporation
　熱硬化剤１：ペンタエリスリトールテトラキス（３－メルカプトブチレート）、昭和電工社製「カレンズＭＴ　ＰＥ１」 Thermosetting agent 1: Pentaerythritol tetrakis (3-mercaptobutyrate), “Karenz MT PE1” manufactured by Showa Denko KK
　潜在性エポキシ熱硬化剤１：Ｔ＆Ｋ　ＴＯＫＡ社製「フジキュア７０００」 Latent epoxy thermosetting agent 1: T & K TOKA's “Fujicure 7000”
　フラックス１：グルタル酸、和光純薬工業社製、融点（活性温度）１５２℃ Flux 1: glutaric acid, manufactured by Wako Pure Chemical Industries, Ltd., melting point (active temperature) 152 ° C.
　はんだ粒子１～２の作製方法：
　はんだ粒子１：
　３つ口フラスコに、ＳｎＢｉはんだ粒子（三井金属社製「ＤＳ－１０」、平均粒子径（メディアン径）１２μｍ）２００ｇ、シランカップリング剤（信越シリコーン社製「ＫＢＭ－９０３」、３－アミノプロピルトリメトキシシラン）１０ｇ、トルエン１２０ｇ、及び水１ｇを添加し、８０℃で３時間、窒素雰囲気下、ディーンスターク装置を用い反応させることで、３－アミノプロピルトリメトキシランのメトキシ基由来のシラノール基と、はんだ粒子の表面のＳｎ－ＯＨとを脱水縮合させた。 Method for producing solder particles 1-2:
Solder particles 1:
In a three-necked flask, SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle size (median diameter) 12 μm) 200 g, silane coupling agent (“KBM-903” manufactured by Shin-Etsu Silicone Co., Ltd.), 3-aminopropyl 10 g of trimethoxysilane), 120 g of toluene, and 1 g of water were added and reacted at 80 ° C. for 3 hours under a nitrogen atmosphere using a Dean-Stark apparatus to obtain a silanol group derived from the methoxy group of 3-aminopropyltrimethoxylane. And Sn—OH on the surface of the solder particles were dehydrated and condensed.
　その後、１０μｍＣＭＦフィルターにて、はんだ粒子を回収し、アセトンにて十分洗浄した。 Thereafter, the solder particles were collected with a 10 μm CMF filter and thoroughly washed with acetone.
　このはんだ粒子を３つ口フラスコに移し、アセトン２００ｇ、グルタル酸無水物４０ｇを入れ、６０℃で３時間、窒素雰囲気下、ディーンスターク装置を用い反応させることで、３－アミノプロピルトリメトキシランのアミノ基と、グルタル酸無水物由来の一方のカルボキシル基とを反応させた。その後、１０μｍＣＭＦフィルターにて、はんだ粒子を回収し、アセトンにて十分洗浄した。 The solder particles were transferred to a three-necked flask, and 200 g of acetone and 40 g of glutaric anhydride were added and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere using a Dean-Stark apparatus, thereby producing 3-aminopropyltrimethoxylane. The amino group was reacted with one carboxyl group derived from glutaric anhydride. Thereafter, the solder particles were collected with a 10 μm CMF filter and sufficiently washed with acetone.
　篩にて、トップ２０μｍにてトップカット（粗大粒子の除去）を行い、平均粒子径１２μｍ、ＣＶ値２０％であり、グルタル酸無水物由来のもう一方のカルボキシル基を表面に有するはんだ粒子１を得た。 Using a sieve, top cut (removal of coarse particles) at the top 20 μm, the average particle diameter is 12 μm, the CV value is 20%, and the solder particles 1 having the other carboxyl group derived from glutaric anhydride on the surface Obtained.
　　はんだ粒子２：
　３－アミノプロピルトリメトキシランを、シランカップリング剤（信越シリコーン社製「ＫＢＭ－６０３」、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン）に変更したこと以外は同様にして、はんだ粒子２を得た。平均粒子径１２μｍ、ＣＶ値２０％であった。 Solder particles 2:
The same procedure except that 3-aminopropyltrimethoxylane was changed to a silane coupling agent (“KBM-603” manufactured by Shin-Etsu Silicone Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane). Solder particles 2 were obtained. The average particle size was 12 μm, and the CV value was 20%.
　はんだ粒子Ａ：ＳｎＢｉはんだ粒子（三井金属社製「ＤＳ－１０」、平均粒子径（メディアン径）１２μｍ） Solder particles A: SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 μm)
　（はんだ粒子のＣＶ値）
　ＣＶ値を、レーザー回折式粒度分布測定装置（堀場製作所社製「ＬＡ－９２０」）にて、測定した。 (CV value of solder particles)
The CV value was measured with a laser diffraction particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.).
　（実施例１～６及び比較例１）
　下記の表１に示す成分を下記の表１に示す配合量で配合して、異方性導電ペーストを得た。 (Examples 1 to 6 and Comparative Example 1)
The components shown in Table 1 below were blended in the blending amounts shown in Table 1 below to obtain anisotropic conductive paste.
　（１）第１の接続構造体（Ｌ／Ｓ＝５０μｍ／５０μｍ）の作製
　（条件Ａ）
　作成直後の異方性導電ペーストを用いて、以下のようにして、第１，第２，第３の接続構造体を作製した。 (1) Production of first connection structure (L / S = 50 μm / 50 μm) (Condition A)
Using the anisotropic conductive paste immediately after the production, first, second and third connection structures were produced as follows.
　（条件Ｂ）
　さらに、作成直後の異方性導電ペーストを用いて、以下のようにして、第１，第２，第３の接続構造体を作製した。この際、ガラスエポキシ基板の上面に、作製直後の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、異方性導電ペースト層を形成し後、大気雰囲気下、２３℃、５０％ＲＨで１０時間放置後、異方性導電ペースト層の上面に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。それ以外は、条件Ａと同様とした。粘度は、上記放置後のペースト（異方性導電ペースト層）を回収して測定を行った。 (Condition B)
Furthermore, the first, second, and third connection structures were produced as follows using the anisotropic conductive paste immediately after the production. At this time, the anisotropic conductive paste immediately after fabrication is applied to the upper surface of the glass epoxy substrate by screen printing using a metal mask so that the thickness becomes 100 μm on the electrode of the glass epoxy substrate, After forming the conductive conductive paste layer, it was allowed to stand at 23 ° C. and 50% RH for 10 hours in an air atmosphere, and then a flexible printed circuit board was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. The other conditions were the same as those in Condition A. The viscosity was measured by collecting the paste after being left standing (anisotropic conductive paste layer).
　（接続構造体の具体的な作製方法）
　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。 (Specific manufacturing method of connection structure)
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. Moreover, the flexible printed circuit board (2nd connection object member) which has a copper electrode pattern (thickness of a copper electrode 12 micrometers) of L / S 50 micrometers / 50 micrometers and electrode length 3mm on the lower surface was prepared.
　ガラスエポキシ基板と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。 The overlapping area of the glass epoxy substrate and the flexible printed circuit 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、異方性導電ペースト層を形成した。次に、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。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。その後、異方性導電ペースト層の温度が１９０℃となるように加熱しながら、はんだを溶融させ、かつ異方性導電ペースト層を１９０℃１０秒で硬化させ、第１の接続構造体を得た。 On the upper surface of the glass epoxy substrate, the anisotropic conductive paste immediately after production is applied by screen printing using a metal mask so that the thickness is 100 μm on the electrode of the glass epoxy substrate, and anisotropic conductive A paste layer was formed. Next, the flexible printed circuit board was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. At this time, no pressure was applied. The weight of the flexible printed board is added to the anisotropic conductive paste layer. Thereafter, while heating the anisotropic conductive paste layer to 190 ° C., the solder is melted and the anisotropic conductive paste layer is cured at 190 ° C. for 10 seconds to obtain a first connection structure. It was.
　（２）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。 (2) Production of second connection structure (L / S = 75 μm / 75 μm) Glass epoxy substrate having a L / S of 75 μm / 75 μm and an electrode length of 3 mm on a copper electrode pattern (copper electrode thickness 12 μm) on the upper surface (FR-4 substrate) (first connection target member) was prepared. In addition, a flexible printed circuit board (second connection target member) having a L / S of 75 μm / 75 μm and an electrode length of 3 mm on the lower surface of a copper electrode pattern (copper electrode thickness 12 μm) 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。 2nd connection structure was obtained like manufacture of the 1st connection structure except having used the above-mentioned glass epoxy board and flexible printed circuit board from which L / S differs.
　（３）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。 (3) Production of third connection structure (L / S = 100 μm / 100 μm) Glass epoxy substrate having a copper electrode pattern (copper electrode thickness 12 μm) with L / S of 100 μm / 100 μm and electrode length of 3 mm on the upper surface (FR-4 substrate) (first connection target member) was prepared. Moreover, the flexible printed circuit board (2nd connection object member) which has a copper electrode pattern (thickness of copper electrode 12 micrometers) of L / S of 100 micrometers / 100 micrometers and electrode length 3mm 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。 3rd connection structure was obtained like manufacture of the 1st connection structure except having used the above-mentioned glass epoxy board and flexible printed circuit board from which L / S differs.
　（評価）
　（１）粘度
　異方性導電ペーストの２５℃での粘度（η２５）を、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。 (Evaluation)
(1) Viscosity The viscosity (η25) at 25 ° C. of the anisotropic conductive paste was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 5 rpm.
　（２）はんだ部の厚み
　得られた第１の接続構造体を断面観察することにより、上下の電極が間に位置しているはんだ部の厚みを評価した。 (2) Thickness of solder part By observing a cross section of the obtained first connection structure, the thickness of the solder part between which the upper and lower electrodes are positioned was evaluated.
　（３）電極上のはんだの配置精度１
　得られた第１，第２，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１を下記の基準で判定した。 (3) Solder placement accuracy on electrode 1
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 provided. When viewed, the ratio X of the area where the solder portion in the connection portion is arranged in the area of 100% of the portion where the first electrode and the second electrode face each other was evaluated. The solder placement accuracy 1 on the electrode was determined according to the following criteria.
　［電極上のはんだの配置精度１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 solder placement accuracy 1 on electrode]
○○: 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）電極上のはんだの配置精度２
　得られた第１，第２，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と直交する方向に第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、接続部中のはんだ部１００％中、第１の電極と第２の電極との対向し合う部分に配置されている接続部中のはんだ部の割合Ｙを評価した。電極上のはんだの配置精度２を下記の基準で判定した。 (4) Solder placement accuracy on electrode 2
In the obtained first, second, and third connection structures, the first electrode and the second electrode are opposed to each other in a direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode. When looking at the mating part, the ratio Y of the solder part in the connecting part arranged in the part where the first electrode and the second electrode face each other in 100% of the solder part in the connecting part was evaluated. . The solder placement accuracy 2 on the electrode was determined according to the following criteria.
　［電極上のはんだの配置精度２の判定基準］
　○○：割合Ｙが９９％以上
　○：割合Ｙが９０％以上、９９％未満
　△：割合Ｙが７０％以上、９０％未満
　×：割合Ｙが７０％未満 [Criteria for solder placement accuracy 2 on electrode]
◯: Ratio Y is 99% or more ○: Ratio Y is 90% or more and less than 99% △: Ratio Y is 70% or more and less than 90% X: Ratio Y is less than 70%
　（５）上下の電極間の導通信頼性
　得られた第１，第２，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。 (5) Conduction reliability between upper and lower electrodes In the obtained first, second and third connection structures (n = 15), the connection resistance per connection point between the upper and lower electrodes is 4 respectively. It was measured by the terminal method. The average value of connection resistance was calculated. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed 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 [Judgment criteria for conduction reliability]
◯: Average connection resistance is 50 mΩ or less ○: Average connection resistance exceeds 50 mΩ, 70 mΩ or less △: Average connection resistance exceeds 70 mΩ, 100 mΩ or less ×: Average connection resistance exceeds 100 mΩ Or there is a bad connection
　（６）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，第３の接続構造体（ｎ＝１５個）について、８５℃、湿度８５％の雰囲気中に１００時間放置後、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。 (6) Insulation reliability between electrodes adjacent in the lateral direction The obtained first, second and third connection structures (n = 15) were left in an atmosphere of 85 ° C. and 85% humidity for 100 hours. Then, 5V was applied between the electrodes adjacent to the horizontal direction, and the resistance value was measured at 25 locations. Insulation reliability was judged according to 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]
◯: Average value of connection resistance is 10 7 Ω or more ○: Average value of connection resistance is 10 6 Ω or more, less than 10 7 Ω △: Average value of connection resistance is 10 5 Ω or more, less than 10 6 Ω ×: Connection The average resistance is less than 10 5 Ω
　（７）上下の電極間の位置ずれ
　得られた第１，第２，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の電極の中心線と第２の電極の中心線とが揃っているか否か、並びに位置ずれの距離を評価した。上下の電極間の位置ずれを下記の基準で判定した。 (7) Position shift between upper and lower electrodes In the obtained first, second, and third connection structures, the first electrode and the second electrode are stacked in the stacking direction of the first electrode, the connection portion, and the second electrode. Whether the center line of the first electrode and the center line of the second electrode were aligned when the portion facing the two electrodes was viewed, and the distance of the positional deviation were evaluated. The positional deviation between the upper and lower electrodes was determined according to the following criteria.
　［上下の電極間の位置ずれの判定基準］
　○○：位置ずれが１５μｍ未満
　○：位置ずれが１５μｍ以上、２５μｍ未満
　△：位置ずれが２５μｍ以上、４０μｍ未満
　×：位置ずれが４０μｍ以上 [Criteria for misregistration between upper and lower electrodes]
○: Misalignment is less than 15 μm ○: Misalignment is 15 μm or more and less than 25 μm Δ: Misalignment is 25 μm or more and less than 40 μm ×: Misalignment is 40 μm or more
　結果を下記の表１に示す。 The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　フレキシブルプリント基板にかえて、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。 The same tendency was observed when using a resin film, a flexible flat cable, and a rigid flexible board instead of the flexible printed board.
　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…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 DESCRIPTION OF SYMBOLS 1,1X ... Connection structure 2 ... 1st connection object member 2a ... 1st electrode 3 ... 2nd connection object member 3a ... 2nd electrode 4, 4X ... Connection part 4A, 4XA ... Solder part 4B, 4XB ... Cured part 11 ... Conductive material 11A ... Conductive particles 11B ... Thermosetting component 21 ... Conductive particles (solder particles)
31 ... Conductive particles 32 ... Base particle 33 ... Conductive part (conductive part having solder)
33A ... second conductive part 33B ... solder part 41 ... conductive particles 42 ... solder part

Claims (9)

  1. 　複数の導電性粒子と、熱硬化性化合物と、熱硬化剤とを含み、
    　前記導電性粒子は、導電部の外表面部分に、はんだを有し、
    　前記導電性粒子は、前記導電部の前記はんだの外表面に、Ｏ－Ｓｉ結合を有する、導電材料。     A plurality of conductive particles, a thermosetting compound, and a thermosetting agent;
    The conductive particles have solder on the outer surface portion of the conductive portion,
    The conductive material is a conductive material having an O—Si bond on an outer surface of the solder of the conductive portion.
  2. 　前記導電性粒子は、前記導電部の前記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を有する、請求項１に記載の導電材料。 2. The conductive material according to claim 1, wherein the conductive particles have a Sn—O—Si bond on an outer surface of the solder of the conductive portion.
  3. 　前記導電性粒子は、シランカップリング剤による表面処理物である、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 conductive particles are a surface-treated product with a silane coupling agent.
  4. 　前記導電性粒子は、前記導電部の前記はんだの外表面に、アミノ基を有する、請求項１～３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 3, wherein the conductive particles have an amino group on an outer surface of the solder of the conductive portion.
  5. 　前記導電性粒子は、前記導電部の前記はんだの外表面に、Ｓｎ－Ｏ－Ｓｉ結合を介して、カルボキシル基含有基を有する、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 conductive particles have a carboxyl group-containing group on the outer surface of the solder of the conductive portion via a Sn-O-Si bond.
  6. 　前記導電性粒子は、はんだ粒子である、請求項１～５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 5, wherein the conductive particles are solder particles.
  7. 　前記導電性粒子の平均粒子径が１μｍ以上、６０μｍ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。 The conductive material according to any one of claims 1 to 6, wherein an average particle diameter of the conductive particles is 1 µm or more and 60 µm or less.
  8. 　導電材料１００重量％中、前記導電性粒子の含有量が１０重量％以上、８０重量％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。 The conductive material according to any one of claims 1 to 7, wherein a content of the conductive particles is 10% by weight or more and 80% by weight or less in 100% by weight of the conductive material.
  9. 　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１～８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おけるはんだにより電気的に接続されている、接続構造体。     A first connection object member having a first electrode on its surface;
    A second connection target member having a second electrode on its surface;
    A connection portion connecting the first connection target member and the second connection target member;
    The material of the connection part is the conductive material according to any one of claims 1 to 8,
    A connection structure in which the first electrode and the second electrode are electrically connected by solder in the conductive particles.
PCT/JP2016/070386 2015-07-14 2016-07-11 Conductive material and connection structure WO2017010445A1 (en)

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