WO2016080515A1 - 導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体 - Google Patents

導電性粒子、導電性粒子の製造方法、導電材料及び接続構造体 Download PDF

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Publication number
WO2016080515A1
WO2016080515A1 PCT/JP2015/082686 JP2015082686W WO2016080515A1 WO 2016080515 A1 WO2016080515 A1 WO 2016080515A1 JP 2015082686 W JP2015082686 W JP 2015082686W WO 2016080515 A1 WO2016080515 A1 WO 2016080515A1
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group
conductive
solder
particles
conductive particles
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PCT/JP2015/082686
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English (en)
French (fr)
Japanese (ja)
Inventor
石澤　英亮
伸也 上野山
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積水化学工業株式会社
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Priority to JP2015558281A priority Critical patent/JP5946978B1/ja
Priority to CN201580048612.0A priority patent/CN106688051B/zh
Priority to KR1020167029707A priority patent/KR20170090353A/ko
Publication of WO2016080515A1 publication Critical patent/WO2016080515A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth

Definitions

  • the present invention relates to conductive particles having solder on the surface of a conductive portion and a method for producing conductive particles. Moreover, this invention relates to the manufacturing method of the electrically-conductive material and connection structure using the said electroconductive particle.
  • 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 resin.
  • 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.
  • Patent Documents 1 and 2 include anisotropic conductive materials including a thermosetting binder, solder particles having a melting point of 180 ° C. or lower or 160 ° C. or lower, and a flux component.
  • a material is disclosed.
  • the flux component a compound represented by the following formula (101) or (102) is used.
  • the anisotropic electrically-conductive material of patent document 1 contains an epoxy resin and a cationic curing initiator essential as the said thermosetting binder. Patent Documents 1 and 2 describe that the flux component and the solder particles are coordinated by chelate.
  • R 1 to R 4 represent a hydrogen atom, an alkyl group, or a hydroxyl group
  • X has a lone electron pair or a double bond ⁇ electron that can be coordinated with a metal.
  • Y represents an atom or atomic group forming a main chain skeleton.
  • Y in the above formula (101) and the above formula (102) is an alkyl group.
  • Patent Document 3 discloses a solder ball having a surface coated with at least two kinds of organic acids having 10 to 25 carbon atoms and having a carboxyl group.
  • the carboxyl group of the organic acid is chelated with the surface of the solder ball.
  • Patent Document 4 discloses a solder powder in which at least one of a fatty acid and a dicarboxylic acid is chemically bonded to the surface and coated.
  • Patent Document 4 discloses a conductive adhesive (anisotropic conductive material) containing the solder powder, a resin, and a curing agent.
  • Patent Document 5 discloses conductive particles having a solder on the surface of a conductive portion and a group containing a carboxyl group covalently bonded to the surface of the solder.
  • Patent Documents 1 and 2 a compound represented by the above formula (101) or the above formula (102) is used as a component having a flux action. However, in Patent Documents 1 and 2, apart from the solder particles, only the compound represented by the above formula (101) or the above formula (102) is used.
  • connection structure is obtained using conventional anisotropic conductive materials as described in Patent Documents 1 and 2, voids are formed in the cured product of the anisotropic conductive material in the obtained connection structure. May occur. For this reason, there exists a problem that the connection reliability in a connection structure becomes low, or the connection resistance between electrodes becomes high.
  • Patent Documents 1 and 2 describe that the flux component and the solder particles are chelate coordinated.
  • the flux component tends to be detached from the surface of the solder particles only by coordinating and bonding the flux component and the solder particles so as to chelate.
  • the connection resistance between the electrodes may be increased or the generation of voids may not be sufficiently suppressed only by coordinating the flux component and the solder particles.
  • the organic acid may be easily removed from the surface of the solder ball, the connection resistance between the electrodes may increase, or the generation of voids may not be sufficiently suppressed. is there.
  • Patent Document 4 at least one of fatty acid and dicarboxylic acid is chemically bonded to the surface.
  • the reaction is performed at 40 to 60 ° C. without using a catalyst in order to obtain solder powder. Therefore, fatty acids and dicarboxylic acids are not covalently bonded to the surface of the solder powder. Even if such a solder powder described in Patent Document 4 is used, fatty acid or dicarboxylic acid can be easily removed from the surface of the solder powder, the connection resistance between the electrodes becomes high, or the generation of voids cannot be sufficiently suppressed. There are things to do.
  • connection resistance between the electrodes can be lowered to some extent.
  • a carboxyl group can be introduced into the surface of the solder by a method different from the method described in Patent Document 5, new conductive particles can be obtained.
  • conductive particles having solder on the surface of a conductive portion there are conductive particles having solder on the surface of a conductive portion, and a carboxyl group is formed on the surface of the solder via a group containing a group represented by the following formula (X). Conductive particles having at least one group attached thereto are provided.
  • the carbon atom of the group represented by the formula (X) is directly covalently bonded or bonded through an organic group to the surface of the solder. .
  • the carbon atom of the group represented by the formula (X) is directly covalently bonded to the surface of the solder.
  • the nitrogen atom of the group represented by the formula (X) is directly covalently bonded to the group having at least one carboxyl group or an organic group. Are connected through.
  • the nitrogen atom of the group represented by the formula (X) is directly covalently bonded to the group having at least one carboxyl group or an organic group. Are connected through.
  • the group having at least one carboxyl group has a silicon atom
  • the silicon atom of the group having at least one carboxyl group is represented by the formula (X)
  • the nitrogen atom of the represented group is directly covalently bonded or bonded through an organic group.
  • the group having at least one carboxyl group has a plurality of carboxyl groups.
  • the group having at least one carboxyl group is introduced by a reaction using a silane coupling agent having a carboxyl group, or a silane coupling agent is used. After the reaction used, it is introduced by reacting a compound derived from a silane coupling agent with a compound having at least one carboxyl group.
  • the isocyanate particle is used to react a hydroxyl group on the surface of the solder with the isocyanate compound and then react with a compound having at least one carboxyl group. It is done.
  • the compound having at least one carboxyl group has a plurality of carboxyl groups.
  • the said electroconductive particle is equipped with the base material particle and the solder layer arrange
  • the surface of the conductive portion On the specific situation with the electroconductive particle which concerns on this invention, the said electroconductive particle is equipped with the base material particle and the solder layer arrange
  • the said electroconductive particle is further equipped with the 1st electroconductive layer arrange
  • the solder layer is disposed on the outer surface of the layer.
  • the conductive particles are dispersed in a binder resin and used as a conductive material.
  • a method for producing a conductive particle as described above comprising using a conductive particle having solder on the surface of a conductive portion, and using an isocyanate compound, and a hydroxyl group on the surface of the solder. After reacting the isocyanate compound, the compound having at least one carboxyl group is reacted to have at least one carboxyl group on the surface of the solder via a group represented by the following formula (X).
  • X group represented by the following formula (X).
  • a conductive material including the above-described conductive particles and a binder resin.
  • the content of the conductive particles is 1% by weight or more and 80% by weight or less.
  • 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 portion connecting the second connection target member
  • the material of the connection portion is the above-described conductive particles, or a conductive material containing the conductive particles and a binder resin
  • a connection structure is provided in which the first electrode and the second electrode are electrically connected by the conductive particles.
  • the conductive particles according to the present invention have a solder on the surface of the conductive portion, and a group having at least one carboxyl group on the surface of the solder via a group containing a group represented by the formula (X). Since they are coupled, when the electrodes are electrically connected, the connection resistance between the electrodes can be lowered.
  • FIG. 1 is a cross-sectional view schematically showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing conductive particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing conductive particles according to the third embodiment of the present invention.
  • FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
  • FIG. 5 is a front cross-sectional view schematically showing an enlarged connection portion between conductive particles and electrodes in the connection structure shown in FIG. 4.
  • the conductive particles according to the present invention have solder on the surface (outer surface) of the conductive portion.
  • a group having at least one carboxyl group is bonded to the surface of the solder via a group containing a group represented by the formula (X).
  • the right end and the left end in the following formula (X) represent a binding site.
  • the conductive particles according to the present invention are different from particles obtained by simply coating the conductive particles having solder on the surface of the conductive portion with a compound having a carboxyl group.
  • the conductive particles according to the present invention not only the carboxyl group is present on the surface of the solder, but also at least one carboxyl group is present on the surface of the solder via a group containing a group represented by the formula (X). Are attached to each other.
  • the conductive particles according to the present invention are also different from the conductive particles in which the compound having a carboxyl group has a chelate coordination (coordination bond) on the surface of the solder.
  • the conductive particles according to the present invention have a solder on the surface of a conductive portion, and a group having at least one carboxyl group on the surface of the solder via a group containing a group represented by the formula (X). Therefore, when the connection structure is obtained by electrically connecting the electrodes using the conductive particles according to the present invention, the connection resistance between the electrodes can be lowered.
  • a group having at least one carboxyl group is bonded via a group having a solder on the surface of the conductive portion and a group including a group represented by the formula (X).
  • connection structure when the connection structure is obtained by electrically connecting the electrodes using the conductive particles according to the present invention, generation of voids in the obtained connection structure can be suppressed. As a result of suppressing the generation of voids, connection reliability in the connection structure is increased. Furthermore, it is possible to suppress an increase in connection resistance in the connection structure due to the void. Further, it becomes difficult to form an oxide film on the surface of the solder, and the oxide film on the surface of the electrodes can be effectively eliminated when connecting the electrodes.
  • a group having at least one carboxyl group is present on the surface of the solder in the conductive particles via a group including a group represented by the formula (X). Bonding is preferred. Conductive particles in which a group having at least one carboxyl group is bonded to the surface of the solder via a group containing a group represented by the formula (X) are dispersed in a binder resin to obtain a conductive material. It is preferable. Before dispersing the conductive particles in the binder resin, a group having at least one carboxyl group is bonded to the surface of the solder in the conductive particles via a group containing a group represented by the formula (X).
  • the oxide film on the surface of the solder and the surface of the electrode can be effectively eliminated even if the flux is not added to the conductive material or the amount of the flux added to the conductive material is small.
  • production of the void in a connection structure can be suppressed further by not mix
  • bonded with the surface containing solder via the group containing group represented by Formula (X) is thickened. be able to. As a result, the conductive particles and the oxide film on the surface of the electrode can be effectively eliminated, and the connection resistance between the electrodes can be lowered.
  • the conductive particles according to the present invention are dispersed in a binder resin and are suitably used as a conductive material.
  • the conductive material may be a conductive material that can be cured by both light irradiation and heating.
  • the conductive material can be semi-cured (B-staged) by light irradiation to reduce the fluidity of the conductive material, and then the conductive material can be cured by heating.
  • the conductive particles may not be efficiently collected between the upper and lower electrodes.
  • the conductive particles easily gather efficiently between the upper and lower electrodes.
  • the solder in electroconductive particle can be selectively arrange
  • the solder in the conductive particles can be more selectively disposed on the electrode.
  • 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 solder that 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 conductive particles have solder on the surface of the conductive portion.
  • a group having at least one carboxyl group is bonded to the surface of the solder via a group including a group represented by the formula (X).
  • the carbon atom of the group represented by the above formula (X) is directly covalently bonded to the surface of the solder. Or bonded via an organic group, and the carbon atom of the group represented by the above formula (X) is preferably directly covalently bonded to the surface of the solder.
  • the group having at least one carboxyl group, the nitrogen atom of the group represented by the above formula (X) are preferably directly covalently bonded or bonded via an organic group, and the nitrogen atom of the group represented by the above formula (X) is directly covalently bonded to the group having at least one carboxyl group. More preferably, they are bonded.
  • the carbon atom of the group represented by the above formula (X) is directly covalently bonded to the surface of the solder.
  • the nitrogen atom of the group represented by the formula (X) is preferably directly covalently bonded or bonded via an organic group to the group having at least one carboxyl group.
  • the group having at least one carboxyl group has a silicon atom and has at least one carboxyl group. It is preferable that the nitrogen atom of the group represented by the above formula (X) is directly covalently bonded to the silicon atom of the group or via an organic group.
  • the group having at least one carboxyl group preferably has a plurality of carboxyl groups.
  • the present inventor noticed that a hydroxyl group exists on the surface of the solder, and by bonding this hydroxyl group and an isocyanate compound, the bond is stronger than when bonding by other coordination bond (chelate coordination) or the like. It was found that conductive particles capable of reducing the connection resistance between the electrodes and suppressing the generation of voids can be obtained.
  • a carboxyl group can be easily introduced into a group derived from an isocyanate compound by utilizing its reactivity. By introducing a carboxyl group into a group derived from an isocyanate compound, the above conductive particles Obtainable.
  • the reaction between hydroxyl groups and carboxyl groups on the solder surface is relatively slow.
  • the reaction between the hydroxyl group on the solder surface and the isocyanate compound is relatively fast.
  • the conductive particles can be obtained efficiently, and a group having at least one carboxyl group is bonded to the surface of the solder via a group containing a group represented by the formula (X).
  • the thickness of the covering portion can be increased efficiently.
  • the bonding form between the surface of the solder and the group having at least one carboxyl group may not include a coordination bond, and does not include a bond due to a chelate coordination. May be.
  • the conductive particles react with the hydroxyl group on the surface of the solder using an isocyanate compound. It is preferable to be obtained through a process. In the above reaction, a covalent bond is formed.
  • the hydroxyl group on the surface of the solder with the isocyanate compound, it is possible to easily obtain conductive particles in which the nitrogen atom of the group derived from the above-mentioned isocyanate group is covalently bonded to the surface of the solder.
  • a group derived from the isocyanate group can be chemically bonded to the surface of the solder in the form of a covalent bond.
  • a silane coupling agent can be easily reacted with a group derived from an isocyanate group. Since the conductive particles can be easily obtained, the group having at least one carboxyl group is introduced by a reaction using a silane coupling agent having a carboxyl group, or a silane coupling agent is used. After the reaction, it is preferably introduced by reacting a group derived from the silane coupling agent with a compound having at least one carboxyl group.
  • the conductive particles are preferably obtained by reacting the isocyanate compound with a hydroxyl group on the surface of the solder using the isocyanate compound and then reacting a compound having at least one carboxyl group.
  • the compound having at least one carboxyl group preferably has a plurality of carboxyl groups.
  • isocyanate compound examples include diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI). Isocyanate compounds other than these may be used. After reacting this compound on the surface of the solder, the residual isocyanate group, and a compound having reactivity with the residual isocyanate group and having a carboxyl group are reacted, and expressed on the solder surface by the formula (X). A carboxyl group can be introduced through a group containing a group.
  • MDI diphenylmethane-4,4'-diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • the isocyanate compound a compound having an unsaturated double bond and having an isocyanate group may be used. Examples include 2-acryloyloxyethyl isocyanate and 2-isocyanatoethyl methacrylate. After reacting the isocyanate group of this compound on the surface of the solder, the surface of the solder is reacted with a compound having a functional group having reactivity with the remaining unsaturated double bond and having a carboxyl group.
  • a carboxyl group can be introduced through a group containing a group represented by the formula (X).
  • silane coupling agent examples include 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-isocyanatepropyltrimethoxysilane (“Y-5187” manufactured by MOMENTIVE). .
  • KBE-9007 3-isocyanatopropyltriethoxysilane
  • Y-5187 manufactured by MOMENTIVE
  • the silane coupling agent only 1 type may be used and 2 or more types may be used together.
  • Examples of the compound having at least one carboxyl group include levulinic acid, glutaric 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, de
  • the compound having at least one carboxyl group is a compound represented by the following formula (1): Is preferred.
  • the compound represented by the following formula (1) has a flux action.
  • the compound represented by following formula (1) has a flux effect
  • X represents a functional group capable of reacting with a hydroxyl group
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • the organic group may contain a carbon atom, a hydrogen atom, and an oxygen atom.
  • the organic group may be a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • the main chain of the organic group is preferably a divalent hydrocarbon group.
  • a carboxyl group or a hydroxyl group may be bonded to a divalent hydrocarbon group.
  • Examples of the compound represented by the above formula (1) include citric acid.
  • the compound having at least one carboxyl group is preferably a compound represented by the following formula (1A) or the following formula (1B).
  • the compound having at least one carboxyl group is preferably a compound represented by the following formula (1A), and preferably a compound represented by the following formula (1B).
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (1A) is the same as R in the above formula (1).
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (1B) is the same as R in the above formula (1).
  • a group represented by the following formula (2A) or the following formula (2B) is bonded to the surface of the solder.
  • a group represented by the following formula (2A) is preferably bonded to the surface of the solder, and more preferably a group represented by the following formula (2B) is bonded.
  • the left end in the following formula (2A) represents a binding site.
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (2A) is the same as R in the above formula (1).
  • the left end in the following formula (2B) represents a binding site.
  • R represents a divalent organic group having 1 to 5 carbon atoms.
  • R in the above formula (2B) is the same as R in the above formula (1).
  • the molecular weight of the compound having at least one carboxyl group is preferably 10,000 or less, more preferably 1000 or less, and even more preferably 500 or less.
  • the molecular weight means a molecular weight that can be calculated from the structural formula when the compound having at least one carboxyl group is not a polymer and when the structural formula of the compound having at least one carboxyl group can be specified. Further, when the compound having at least one carboxyl group is a polymer, it means a weight average molecular weight.
  • the isocyanate compound is reacted with the hydroxyl group on the surface of the solder using the conductive particle having the solder on the surface of the conductive portion and using the isocyanate compound. Thereafter, a compound having at least one carboxyl group is reacted, and a group having at least one carboxyl group is bonded to the surface of the solder via a group containing a group represented by the above formula (X). Conductive particles are obtained.
  • transduced on the surface of solder by said process can be obtained easily.
  • the following method can be given as a specific method for producing the conductive particles.
  • Conductive particles are dispersed in an organic solvent, and a silane coupling agent having an isocyanate group is added. Thereafter, a silane coupling agent is covalently bonded to the solder surface using a reaction catalyst of hydroxyl groups and isocyanate groups on the solder surface of the conductive particles.
  • a hydroxyl group is generated by hydrolyzing the alkoxy group bonded to the silicon atom of the silane coupling agent. The produced hydroxyl group is reacted with a carboxyl group of a compound having at least one carboxyl group.
  • the following method is mentioned as a concrete manufacturing method of the said electroconductive particle.
  • Conductive particles are dispersed in an organic solvent, and a compound having an isocyanate group and an unsaturated double bond is added. Then, a covalent bond is formed using the reaction catalyst of the hydroxyl group and isocyanate group of the solder surface of electroconductive particle. Thereafter, the unsaturated double bond introduced is reacted with a compound having an unsaturated double bond and a carboxyl group.
  • a reaction catalyst for the hydroxyl group and isocyanate group on the solder surface of the conductive particles As a reaction catalyst for the hydroxyl group and isocyanate group on the solder surface of the conductive particles, a tin catalyst (dibutyltin dilaurate, etc.), an amine catalyst (triethylenediamine, etc.), a carboxylate catalyst (lead naphthenate, potassium acetate, etc.), And a trialkylphosphine catalyst (such as triethylphosphine).
  • the conductive particles may be solder particles, or may be conductive particles including base material particles and a solder layer disposed on the surface of the base material particles.
  • the solder particles do not have base particles in the core and are not core-shell particles.
  • both a center part and an outer surface are formed with the solder.
  • the solder particles are particles in which both the central portion and the conductive outer surface are solder.
  • the conductive particles preferably include base material particles and a solder layer disposed on the surface of the base material particles.
  • the conductive particles may include a conductive layer (first conductive layer) other than the solder layer between the base material particle and the solder layer.
  • the solder layer may be disposed on the surface of the substrate particle via a conductive layer other than the solder layer.
  • the solder layer may be disposed on the surface of the conductive layer other than the solder layer.
  • the substrate particles are preferably resin particles.
  • the substrate particles are preferably metal particles having a melting point of 400 ° C. or higher or resin particles having a softening point of 260 ° C. or higher.
  • the softening point of the resin particles is preferably higher than the softening point of the solder layer, and more preferably higher by 10 ° C. than the softening point of the solder layer.
  • the substrate particles include resin particles, inorganic particles excluding metal particles, organic-inorganic hybrid particles, and metal particles.
  • the substrate particles are preferably not metal particles, more preferably resin particles or organic-inorganic hybrid particles, and even more preferably resin particles.
  • the resin particles are made of resin.
  • the base material particles may be metal particles having a melting point of less than 400 ° C, may be metal particles having a melting point of 400 ° C or higher, or may be resin particles having a softening point of less than 260 ° C. It may be resin particles having a softening point of 260 ° C. or higher.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the conductive particles 1 has resin particles 2 (base particles) and a conductive layer 3 disposed on the surface 2a of the resin particles 2.
  • the conductive layer 3 covers the surface 2 a of the resin particle 2.
  • the conductive particle 1 is a coated particle in which the surface 2 a of the resin particle 2 is coated with the conductive layer 3. Accordingly, the conductive particles 1 have the conductive layer 3 on the surface 1a.
  • metal particles or the like may be used.
  • the conductive layer 3 includes a first conductive layer 4 disposed on the surface 2 a of the resin particle 2 and a solder layer 5 (second conductive layer) disposed on the outer surface 4 a of the first conductive layer 4. And have.
  • the first conductive layer 4 is disposed between the resin particle 2 (base material particle) and the solder layer 5.
  • the outer surface layer of the conductive layer 3 is a solder layer 5.
  • the conductive particles 1 have solder on the surface of the conductive layer 3 by the solder layer 5. Therefore, the conductive particle 1 has the solder layer 5 as a part of the conductive layer 3, and is further separated between the resin particle 2 and the solder layer 5 as a part of the conductive layer 3 in addition to the solder layer 5.
  • the conductive layer 4 is provided.
  • the conductive layer 3 may have a multilayer structure, or may have a laminated structure of two or more layers.
  • FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • the conductive layer 3 has a two-layer structure.
  • the conductive particles 11 may have a solder layer 12 as a single conductive layer. It suffices that at least the surface (outer surface layer) of the conductive portion (conductive layer) in the conductive particles is solder (solder layer).
  • the conductive particles 1 are preferable among the conductive particles 1 and the conductive particles 11 because the conductive particles can be easily produced.
  • FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
  • conductive particles 16 that are solder particles that do not have base particles in the core and are not core-shell particles may be used.
  • Conductive particles 1, 11, and 16 are conductive particles according to the present invention, and can be used as a conductive material. Of the conductive particles 1, 11, 16, the conductive particles 1, 11 are preferable, and the conductive particles 1 are more preferable.
  • Examples of the resin for forming the resin particles include polyolefin resin, acrylic resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, and polyphenylene.
  • Examples thereof include oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyethersulfone, divinylbenzene polymer, and divinylbenzene copolymer.
  • Examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylic acid ester copolymer.
  • 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 method for forming a conductive layer on the surface of the resin particles and the method for forming a solder layer on the surface of the resin particles or the surface of the first conductive layer are not particularly limited.
  • a method of forming the conductive layer and the solder layer for example, a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption,
  • a method of coating the surface of the resin particles with metal powder or a paste containing metal powder and a binder may be used. 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.
  • the method of forming the solder layer is preferably a method by physical collision.
  • the solder layer is preferably disposed on the surface of the substrate particle by physical impact.
  • 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 content of tin is preferably less than 90% by weight, more preferably 85% by weight or less. Further, the content of tin in 100% by weight of the solder is appropriately determined in consideration of the melting point of the solder and the like. The content of tin in 100% by weight of the solder is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 20% by weight or more.
  • the thickness of the first conductive layer and the solder layer is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 2 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 6 ⁇ m or less. It is.
  • the conductivity is sufficiently high.
  • the thickness of the first conductive layer and the solder layer is not more than the above upper limit, the difference in coefficient of thermal expansion between the base particles and the first conductive layer and the solder layer is reduced, and the first conductive layer and the solder layer Peeling is less likely to occur.
  • the average particle diameter of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less, particularly preferably 50 ⁇ m or less, and most preferably 40 ⁇ m. It is as follows. 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 contact area between the conductive particles and the electrode is sufficiently large, and aggregated conductive particles are formed when the conductive layer is formed. It becomes difficult. 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.
  • the average particle diameter of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 100 ⁇ m or less, still more preferably. Is 50 ⁇ 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 by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, and calculating an average value or performing a laser diffraction particle size distribution measurement.
  • 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 resin particles in the conductive particles can be properly used depending on the electrode size or land diameter of the substrate to be mounted.
  • the ratio of the average particle diameter C of the conductive particles to the average particle diameter A of the resin particles ( C / A) is more than 1.0, preferably 3.0 or less.
  • the ratio of the average particle diameter B of the conductive particle portion excluding the solder layer to the average particle diameter A of the resin particles (B / A) is greater than 1.0, preferably 2.0 or less.
  • the average particle diameter B of the conductive particle portion excluding the solder layer having the average particle diameter C of the conductive particles including the solder layer is more than 1.0, preferably 2.5 or less.
  • Anisotropic conductive materials for FOB and FOF applications The said electroconductive particle is used suitably for the connection (FOB (Film on Board)) of a flexible printed circuit board and a glass epoxy board, or the connection (FOF (Film on Film)) of a flexible printed circuit board and a flexible printed circuit board.
  • the L & S which is the size of the part with the electrode (line) and the part without the electrode (space), is generally 100 to 500 ⁇ m.
  • the average particle diameter of resin particles used for FOB and FOF applications is preferably 3 to 100 ⁇ m. When the average particle diameter of the resin particles is 3 ⁇ m or more, the thickness of the anisotropic conductive material disposed between the electrodes and the connection portion is sufficiently increased, and the adhesive force is further increased. When the average particle diameter of the resin particles is 100 ⁇ m or less, a short circuit is more unlikely to occur between adjacent electrodes.
  • Anisotropic conductive materials for flip chip applications The conductive particles are suitably used for flip chip applications.
  • the land diameter is generally 15 to 80 ⁇ m.
  • the average particle diameter of the resin particles used for flip chip applications is preferably 1 to 15 ⁇ m.
  • the average particle diameter of the resin particles is 1 ⁇ m or more, the thickness of the solder layer disposed on the surface of the resin particles can be sufficiently increased, and the electrodes can be more reliably electrically connected. it can.
  • the average particle diameter of the resin particles is 15 ⁇ m or less, a short circuit is more unlikely to occur between adjacent electrodes.
  • Anisotropic conductive materials for COB and COF The said electroconductive particle is used suitably for the connection (COB (Chip on Board)) of a semiconductor chip and a glass epoxy board
  • the L & S which is the size of the part with the electrode (line) and the part without the electrode (space), is generally 10 to 50 ⁇ m.
  • the average particle diameter of resin particles used for COB and COF applications is preferably 1 to 10 ⁇ m.
  • the average particle diameter of the resin particles is 1 ⁇ m or more, the thickness of the solder layer disposed on the surface of the resin particles can be sufficiently increased, and the electrodes can be more reliably electrically connected. it can.
  • the average particle diameter of the resin particles is 10 ⁇ m or less, a short circuit is more unlikely to occur between adjacent electrodes.
  • the surface of the conductive particles may be insulated with an insulating material, insulating particles, flux, or the like. It is preferable that the insulating material, the insulating particles, the flux, and the like are eliminated at the surface of the conductive portion and the connection portion by being softened and flowed by heat at the time of connection. Thereby, the short circuit between electrodes is suppressed.
  • 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 3% by weight or more, particularly preferably 10% by weight or more, preferably 80%. % By weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, still more preferably 45% by weight or less, particularly preferably less than 45% by weight, particularly preferably 40% by weight or less.
  • a conductive particle can be easily arrange
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 1% by weight or more, more preferably 10% by weight or more, preferably 50% by weight or less, more preferably 45%. % By weight or less.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 1% by weight or more, more preferably 10% by weight or more, preferably 50% by weight or less, more preferably 45%. % By weight or less.
  • the binder resin preferably contains a thermoplastic compound or contains a curable compound that can be cured by heating and a thermosetting agent.
  • the binder resin preferably contains a curable compound that can be cured by heating and a thermosetting agent.
  • thermoplastic compound examples include phenoxy resin, urethane resin, (meth) acrylic resin, polyester resin, polyimide resin, and polyamide resin.
  • the curable compound curable by heating may be a curable compound (thermosetting compound) that is not cured by light irradiation, and is curable by both light irradiation and heating (light and light). Thermosetting compound).
  • the conductive material is a conductive material that can be cured by both light irradiation and heating.
  • a curable compound that can be cured by light irradiation (a photocurable compound, or light and heat curing). It is preferable to further contain a functional compound.
  • the curable compound that can be cured by light irradiation may be a curable compound (photocurable compound) that is not cured by heating, and is a curable compound that can be cured by both light irradiation and heating (light and light).
  • the conductive material preferably contains a photocuring initiator.
  • the conductive material preferably contains a photoradical generator as the photocuring initiator.
  • the conductive material preferably contains a thermosetting compound as the curable compound, and further contains a photocurable compound or light and a thermosetting compound.
  • the conductive material preferably contains a thermosetting compound and a photocurable compound as the curable compound.
  • the conductive material preferably contains two or more thermosetting agents having different reaction start temperatures. Moreover, it is preferable that the thermosetting agent whose reaction start temperature is a low temperature side is a thermal radical generator. It is preferable that the thermosetting agent having a high reaction initiation temperature is a thermal cation generator.
  • the curable compound is not particularly limited, and examples thereof include a curable compound having an unsaturated double bond and a curable compound having an epoxy group or a thiirane group.
  • the curable compound preferably includes a curable compound having an unsaturated double bond, It preferably contains a curable compound having an acryloyl group.
  • the unsaturated double bond is preferably a (meth) acryloyl group.
  • the curable compound having an unsaturated double bond include an curable compound having no epoxy group or thiirane group and having an unsaturated double bond, and having an epoxy group or thiirane group, Examples thereof include curable compounds having a heavy bond.
  • the curable compound having the (meth) acryloyl group an ester compound obtained by reacting a (meth) acrylic acid and a compound having a hydroxyl group, an epoxy obtained by reacting (meth) acrylic acid and an epoxy compound ( A (meth) acrylate, a urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate, or the like is preferably used.
  • the “(meth) acryloyl group” refers to an acryloyl group and a methacryloyl group.
  • the “(meth) acryl” refers to acryl and methacryl.
  • the “(meth) acrylate” refers to acrylate and methacrylate.
  • the ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited.
  • the ester compound any of a monofunctional ester compound, a bifunctional ester compound, and a trifunctional or higher functional ester compound can be used.
  • the conductive material comprises an unsaturated double bond and a thermosetting functional group. It is preferable to contain the curable compound which has both.
  • the thermosetting functional group include an epoxy group, a thiirane group, and an oxetanyl group.
  • the curable compound having both the unsaturated double bond and the thermosetting functional group is preferably a curable compound having an epoxy group or a thiirane group and having an unsaturated double bond, and thermosetting.
  • it is a curable compound which has both a functional functional group and a (meth) acryloyl group, and it is preferable that it is a curable compound which has an epoxy group or a thiirane group, and has a (meth) acryloyl group.
  • the curable compound having an epoxy group or thiirane group and having a (meth) acryloyl group is a part of the epoxy group or part of the curable compound having two or more epoxy groups or two or more thiirane groups.
  • a curable compound obtained by converting a thiirane group into a (meth) acryloyl group is preferred.
  • Such curable compounds are partially (meth) acrylated epoxy compounds or partially (meth) acrylated episulfide compounds.
  • the curable compound is preferably a reaction product of a compound having two or more epoxy groups or two or more thiirane groups and (meth) acrylic acid.
  • This reaction product is obtained by reacting a compound having two or more epoxy groups or two or more thiirane groups with (meth) acrylic acid in the presence of a catalyst such as a basic catalyst according to a conventional method. It is preferable that 20% or more of the epoxy group or thiirane group is converted (converted) to a (meth) acryloyl group.
  • the conversion is more preferably 30% or more, preferably 80% or less, more preferably 70% or less. Most preferably, 40% or more and 60% or less of the epoxy group or thiirane group is converted to a (meth) acryloyl group.
  • Examples of the partially (meth) acrylated epoxy compound include bisphenol type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, carboxylic acid anhydride-modified epoxy (meth) acrylate, and phenol novolac type epoxy (meth) acrylate. Is mentioned.
  • a modified phenoxy resin obtained by converting a part of epoxy groups of a phenoxy resin having two or more epoxy groups or two or more thiirane groups or a part of thiirane groups into a (meth) acryloyl group may be used.
  • a modified phenoxy resin having an epoxy group or thiirane group and a (meth) acryloyl group may be used.
  • the “phenoxy resin” is generally a resin obtained by reacting, for example, an epihalohydrin and a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound and a divalent phenol compound. is there.
  • the curable compound may be a crosslinkable compound or a non-crosslinkable compound.
  • crosslinkable compound examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (poly ) Ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, tri Examples include methylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, polyester (meth) acrylate, and urethane (meth) acrylate.
  • non-crosslinkable compound examples include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate,
  • examples of the curable 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.
  • the curable compound preferably includes a curable compound having an epoxy group or a thiirane group.
  • the curable compound having an epoxy group is an epoxy compound.
  • the curable compound having a thiirane group is an episulfide compound.
  • the content of the compound having an epoxy group or thiirane group is preferably 10% by weight or more, more preferably 20% by weight or more, 100% by weight in 100% by weight of the curable compound. % Or less.
  • the total amount of the curable compound may be a curable compound having the epoxy group or thiirane group.
  • the compound having the epoxy group or thiirane group is preferably an epoxy compound.
  • the conductive material preferably contains a curable compound having an epoxy group or a thiirane group and a curable compound having an unsaturated double bond.
  • the curable compound having an epoxy group or thiirane group preferably has an aromatic ring.
  • the aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, pentacene ring, picene ring, and perylene ring.
  • the said aromatic ring is a benzene ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a benzene ring or a naphthalene ring.
  • a naphthalene ring is preferred because it has a planar structure and can be cured more rapidly.
  • the conductive material preferably contains the photocurable compound and the thermosetting compound in a weight ratio of 1:99 to 90:10, more preferably 5:95 to 60:40, and more preferably 10:90. More preferably, it is contained at about 40:60.
  • the conductive material includes a thermosetting agent.
  • the thermosetting agent cures the curable compound that can be cured by the heating.
  • a conventionally known thermosetting agent can be used.
  • the said thermosetting agent only 1 type may be used and 2 or more types may be used together.
  • thermosetting agent examples include imidazole curing agents, amine curing agents, phenol curing agents, polythiol curing agents, and other thiol curing agents, thermal cation generators, acid anhydrides, and thermal radical generators.
  • 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.
  • a latent curing agent is preferable since a storage stability becomes high when the curable compound curable by heating and the thermosetting agent are mixed.
  • the latent curing agent is preferably a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent.
  • these thermosetting agents only 1 type may be used and 2 or more types may be used together.
  • 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 generator examples include iodonium-based cation curing agents, oxonium-based cation curing agents, and sulfonium-based 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.
  • thermosetting agent includes a thermal cation generator. It is preferable.
  • the content of the thermosetting agent is not particularly limited.
  • the content of the thermosetting agent is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, based on 100 parts by weight of the curable compound that can be cured by heating.
  • the amount is 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 content of the thermal cation generator is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the curable compound curable by heating. More preferably it is 0.05 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
  • the content of the thermal cation generator is not less than the above lower limit and not more than the above upper limit, the curable composition is sufficiently thermally cured.
  • the conductive material preferably contains a photocuring initiator.
  • the photocuring initiator is not particularly limited. A conventionally known photocuring initiator can be used as the photocuring initiator. From the viewpoint of further enhancing the conduction reliability between the electrodes and the connection reliability of the connection structure, the conductive material preferably contains a photoradical generator. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.
  • the photocuring initiator is not particularly limited, and is not limited to acetophenone photocuring initiator (acetophenone photoradical generator), benzophenone photocuring initiator (benzophenone photoradical generator), thioxanthone, ketal photocuring initiator (ketal photoradical). Generator), halogenated ketones, acyl phosphinoxides, acyl phosphonates, and the like.
  • acetophenone photocuring initiator examples include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone.
  • ketal photocuring initiator examples include benzyldimethyl ketal.
  • the content of the photocuring initiator is not particularly limited.
  • the content of the photocuring initiator (the content of the photoradical generator when the photocuring initiator is a photoradical generator) is: Preferably it is 0.1 weight part or more, More preferably, it is 0.2 weight part or more, Preferably it is 2 weight part or less, More preferably, it is 1 weight part or less.
  • the conductive material can be appropriately photocured. By irradiating the conductive material with light and forming a B-stage, the flow of the conductive material can be suppressed.
  • the conductive material preferably contains a thermal radical generator.
  • the thermal radical generator is not particularly limited.
  • As the thermal radical generator a conventionally known thermal radical generator can be used. By using the thermal radical generator, the conduction reliability between the electrodes and the connection reliability of the connection structure are further enhanced.
  • As for the said thermal radical generator only 1 type may be used and 2 or more types may be used together.
  • 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 content of the thermal radical generator is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, preferably 5 parts by weight or less based on 100 parts by weight of the curable compound curable by heating. More preferably, it is 3 parts by weight or less.
  • the conductive material can be appropriately heat-cured. By making the conductive material B-staged, the flow of the conductive material can be suppressed, and the generation of voids at the time of joining can be further suppressed.
  • the conductive material preferably contains a flux.
  • the use of the flux makes it difficult for an oxide film to be formed on the solder surface, and the oxide film formed on the solder surface or electrode surface can be effectively removed. As a result, the conduction reliability in the connection structure is further increased.
  • the conductive material does not necessarily include a flux.
  • the flux is not particularly limited.
  • the flux it is possible to use a flux generally used for soldering or the like.
  • 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, and glutamic acid.
  • Examples of the pine resin include activated pine resin and non-activated pine resin.
  • the flux is preferably rosin. By using rosin, the connection resistance between the electrodes is further reduced.
  • the above rosins are rosins whose main component is abietic acid.
  • the flux is preferably a rosin, and more preferably abietic acid. By using this preferable flux, the connection resistance between the electrodes is further reduced.
  • 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 content of the flux is not less than the lower limit and not more than the upper limit, an oxide film is hardly formed on the solder surface, and the oxide film formed on the solder surface or the electrode surface can be more effectively removed.
  • the content of the flux is equal to or more than the lower limit, the effect of adding the flux is more effectively expressed.
  • the content of the flux is not more than the above upper limit, the hygroscopic property of the cured product is further lowered, and the reliability of the connection structure is further enhanced.
  • the conductive material does not contain the flux, or the conductive material contains the flux and the content of the flux in 100% by weight of the conductive material. Is preferably 25% by weight or less. From the viewpoint of further suppressing the generation of voids in the connection structure, the smaller the flux content in the conductive material, the better. From the viewpoint of further suppressing the generation of voids in the connection structure, the content of the flux in the conductive material is more preferably 15% by weight or less, further preferably 10% by weight or less, and particularly preferably 5% by weight or less. Most preferably, it is 1% by weight or less.
  • the conductive material preferably contains a filler.
  • a filler By using the filler, the coefficient of thermal expansion of the cured conductive material is lowered.
  • Specific examples of the filler include silica, aluminum nitride, alumina, glass, boron nitride, silicon nitride, silicone, carbon, graphite, graphene, and talc.
  • a filler only 1 type may be used and 2 or more types may be used together. When a filler having a high thermal conductivity is used, the main curing time is shortened.
  • the conductive material may contain a solvent.
  • the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran and diethyl ether.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably a paste-like or film-like conductive material, and more preferably a paste-like conductive material.
  • the paste-like conductive material is a conductive paste.
  • the film-like conductive material is a conductive film. When the conductive material is a conductive film, a film that does not include conductive particles may be laminated on the conductive film that includes conductive particles.
  • the conductive material is preferably a conductive paste that is applied on the connection target member in a paste state.
  • the conductive material is preferably used for electrical connection between electrodes.
  • the conductive material is preferably a circuit connection material.
  • the viscosity of the conductive paste at 25 ° C. is preferably 3 Pa ⁇ s or more, more preferably 5 Pa ⁇ s or more, preferably 500 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less.
  • the viscosity is equal to or higher than the lower limit, sedimentation of conductive particles in the conductive paste can be suppressed.
  • the viscosity is equal to or lower than the upper limit, the dispersibility of the conductive particles is further increased. If the viscosity of the conductive paste before coating is within the above range, after applying the conductive paste on the first connection target member, the flow of the conductive paste before curing can be further suppressed, and the voids are further reduced. It becomes difficult to occur.
  • the conductive particles are preferably conductive particles used for connecting a connection target member having a copper electrode.
  • the conductive material is preferably a conductive material used for connecting a connection target member having a copper electrode.
  • An oxide film is easily formed on the surface of the copper electrode.
  • a group containing a carboxyl group is covalently bonded to the surface of the solder of the conductive particles, the oxide film on the surface of the copper electrode can be effectively removed, and the conduction reliability in the connection structure is improved. Can be increased.
  • the conductive particles and the conductive material can be used for bonding various connection target members.
  • the conductive material is preferably used for obtaining a connection structure in which the first and second connection target members are electrically connected.
  • FIG. 4 is a cross-sectional view schematically showing an example of a connection structure using conductive particles according to the first embodiment of the present invention.
  • connection structure 21 shown in FIG. 4 includes a first connection target member 22, a second connection target member 23, and a connection portion that electrically connects the first and second connection target members 22 and 23. 24.
  • the material of the connection portion 24 is a conductive material (such as an anisotropic conductive material) including the conductive particles 1.
  • the material of the connection part 24 may be the conductive particles 1.
  • the connection part 24 is formed of a conductive material (such as an anisotropic conductive material) including the conductive particles 1.
  • the connection part 24 may be formed of the conductive particles 1. In this case, the conductive particles 1 themselves become connection portions. Further, instead of the conductive particles 1, conductive particles 11, 16 and the like may be used.
  • the first connection target member 22 has a plurality of first electrodes 22b on the surface 22a.
  • the second connection target member 23 has a plurality of second electrodes 23b on the surface 23a.
  • the first electrode 22 b and the second electrode 23 b are electrically connected by one or a plurality of conductive particles 1. Accordingly, the first and second connection target members 22 and 23 are electrically connected by the conductive particles 1.
  • the manufacturing method of the connection structure is not particularly limited.
  • the conductive material is disposed between the first connection target member and the second connection target member to obtain a multilayer body, and then the multilayer body is heated. And a method of applying pressure.
  • the solder layer 5 of the conductive particles 1 is melted by heating and pressurization, and the electrodes are electrically connected by the conductive particles 1.
  • the binder resin contains a thermosetting compound
  • the binder resin is cured, and the first and second connection target members 22 and 23 are connected by the cured binder resin.
  • the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is about 120 to 220 ° C.
  • FIG. 5 is an enlarged front sectional view showing a connection portion between the conductive particle 1 and the first and second electrodes 22b and 23b in the connection structure 21 shown in FIG.
  • the connection structure 21 after the solder layer 5 of the conductive particles 1 is melted by heating and pressurizing the laminated body, the melted solder layer portion 5a has first and second solder layers. It is in sufficient contact with the electrodes 22b and 23b. That is, by using the conductive particles 1 whose surface layer is the solder layer 5, the conductive particles are compared with the case where the surface layer of the conductive layer is a metal such as nickel, gold or copper. 1 and the contact area between the electrodes 22b and 23b can be increased. For this reason, the conduction
  • the first and second connection target members are not particularly limited.
  • the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and circuit boards such as printed boards, flexible printed boards, glass epoxy boards, and glass boards. Examples include parts.
  • the conductive material is preferably a conductive material used for connecting electronic components.
  • the conductive material is preferably a liquid and is a conductive material that is applied to the upper surface of the connection target member in a liquid state.
  • the arrangement state of the solder portion in the connection portion in the connection structure is in the stacking direction of the first electrode, the connection portion, and the second electrode.
  • 50% or more of the area of the portion where the first electrode and the second electrode face each other is 100% (preferably Is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, particularly preferably 90% or more, and most preferably 100%).
  • the first electrode and the second electrode in 100% of the solder portion in the connection portion
  • the proportion of the solder portion in the connection portion arranged in the facing portion is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, particularly preferably 95% or more, and most preferably. Is 99% or more.
  • 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 silver electrode, a SUS electrode, a molybdenum electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum 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.
  • the first electrode or the second electrode is preferably a copper electrode. Both the first electrode and the second electrode are preferably copper electrodes.
  • Thermosetting compound 1 bisphenol A type epoxy compound, “YL980” manufactured by Mitsubishi Chemical Corporation
  • Thermosetting compound 2 epoxy resin, “EXA-4850-150” manufactured by DIC
  • Thermosetting agent A imidazole compound, “2P-4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Adhesion imparting agent “KBE-403” manufactured by Shin-Etsu Chemical Co., Ltd. Flux: “Glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.
  • Conductive particles 1 200 g of SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 ⁇ m), 10 g of a silane coupling agent having an isocyanate group (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.), and 70 g of acetone. Weighed into a three-necked flask. While stirring at room temperature, 0.25 g of dibutyltin laurate, which is a reaction catalyst between the hydroxyl group on the solder particle surface and the isocyanate group, was added, and the mixture was heated at 60 ° C. for 30 minutes under stirring in a nitrogen atmosphere. Thereafter, 50 g of methanol was added, and the mixture was heated at 60 ° C. for 10 minutes under stirring in a nitrogen atmosphere.
  • SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter
  • the mixture was cooled to room temperature, the solder particles were filtered with a filter paper, and the solvent was removed by vacuum drying at room temperature for 1 hour.
  • ester group of monoethyl adipate was reacted with the silanol group derived from the silane coupling agent by a transesterification reaction to form a covalent bond.
  • adipic acid was added and reacted at 60 ° C. for 1 hour to add adipic acid to the remaining ethyl ester group that had not reacted with the silanol group of monoethyl adipate.
  • the molecular weight of the polymer formed on the solder surface was 0.1N hydrochloric acid, the solder was dissolved, the polymer was recovered by filtration, and the weight average molecular weight was determined by GPC.
  • the zeta potential of the obtained solder particles was uniformly dispersed by applying ultrasonic waves to 0.05 g of solder particles coated with an anionic polymer and 10 g of methanol. This was measured by an electrophoretic measurement method using “Delsamax PRO” manufactured by Beckman Coulter.
  • the CV value was measured with a laser diffraction particle size distribution measuring device (“LA-920” manufactured by Horiba, Ltd.).
  • conductive particles 1 were obtained.
  • the CV value was 20%
  • the surface zeta potential was 0.9 mV
  • the molecular weight Mw of the polymer was 9800.
  • Conductive particles 2 In the step of obtaining the conductive particles 1, the conductive particles 2 were obtained in the same manner except that monoethyl adipate was changed to monoethyl glutarate and adipic acid was changed to glutaric acid. In the obtained conductive particles 2, the CV value was 20%, the surface zeta potential was 0.92 mV, and the molecular weight Mw of the polymer was 9600.
  • Conductive particles 3 In the step of obtaining the conductive particles 1, the conductive particles 3 were obtained in the same manner except that monoethyl adipate was changed to monoethyl sebacate and adipic acid was changed to sebacic acid. In the obtained conductive particles 3, the CV value was 20%, the surface zeta potential was 0.88 mV, and the molecular weight Mw of the polymer was 12000.
  • Conductive particles 4 In the step of obtaining the conductive particles 1, the conductive particles 4 were obtained in the same manner except that monoethyl adipate was changed to monoethyl suberate and adipic acid was changed to suberic acid. In the obtained conductive particles 4, the CV value was 20%, the surface zeta potential was 0.90 mV, and the molecular weight Mw of the polymer was 9600.
  • Conductive particles 5 A reaction solution was prepared by dissolving 10 g of mercaptoacetic acid in 400 ml of methanol. Next, 200 g of SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 ⁇ m) were added to the reaction solution, and the mixture was stirred at 25 ° C. for 2 hours. After washing with methanol, the particles were filtered to obtain solder particles having (thio) carboxyl groups on the surface.
  • SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 ⁇ m) were added to the reaction solution, and the mixture was stirred at 25 ° C. for 2 hours. After washing with methanol, the particles were filtered to obtain solder particles having (thio) carboxyl groups on the surface.
  • a 30% polyethyleneimine P-70 solution having a weight average molecular weight of about 70,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was diluted with ultrapure water to obtain a 0.3% by weight polyethyleneimine aqueous solution.
  • 200 g of the solder particles having the (thio) carboxyl group were added to a 0.3 wt% polyethyleneimine aqueous solution and stirred at 25 ° C. for 15 minutes.
  • the solder particles were filtered, put in 1000 g of pure water, and stirred at 25 ° C. for 5 minutes. Further, the solder particles were filtered and washed with 1000 g of ultrapure water twice to remove unimsorbed polyethyleneimine. Thereafter, the solder particles were dispersed in 400 ml of methanol, 10 g of adipic acid was added, and the mixture was reacted at 60 ° C. for 1 hour in a nitrogen atmosphere with stirring.
  • the obtained conductive particles 5 had a CV value of 20% and a surface zeta potential of 0.60 mV.
  • Conductive particles 6 A reaction solution was prepared by dissolving 150 g of polyacrylic acid (“AC-10P” manufactured by Toa Gosei Co., Ltd.) in 400 ml of methanol. Next, 200 g of SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 ⁇ m) were added to the reaction solution, and the mixture was stirred at 25 ° C. for 2 hours. After washing with methanol, the particles were filtered to obtain solder particles having polyacrylic acid on the surface.
  • AC-10P polyacrylic acid
  • SnBi solder particles SnBi solder particles
  • a 30% polyethyleneimine P-70 solution having a weight average molecular weight of about 70,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was diluted with ultrapure water to obtain a 0.3% by weight polyethyleneimine aqueous solution.
  • 200 g of the solder particles having a carboxyl group were added to a 0.3 wt% polyethyleneimine aqueous solution and stirred at 25 ° C. for 15 minutes.
  • the solder particles were filtered, put in 1000 g of pure water, and stirred at 25 ° C. for 5 minutes. Further, the solder particles were filtered and washed with 1000 g of ultrapure water twice to remove unimsorbed polyethyleneimine. Thereafter, the solder particles were dispersed in 400 ml of methanol, 10 g of adipic acid was added, and the mixture was reacted at 60 ° C. for 1 hour in a nitrogen atmosphere with stirring.
  • the obtained conductive particles 6 had a CV value of 20% and a surface zeta potential of 0.70 mV.
  • Conductive particles A SnBi solder particles (“DS-10” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter (median diameter) 12 ⁇ m)
  • Conductive particles B (resin core solder-coated particles, prepared by the following procedure): Divinylbenzene resin particles (“Micropearl SP-210” manufactured by Sekisui Chemical Co., Ltd., average particle size 10 ⁇ m, softening point 330 ° C., 10% K value (23 ° C.) 3.8 GPa) were electroless nickel plated, A base nickel plating layer having a thickness of 0.1 ⁇ m was formed on the surface. Next, the resin particles on which the base nickel plating layer was formed were subjected to electrolytic copper plating to form a 1 ⁇ m thick copper layer.
  • Divinylbenzene resin particles (“Micropearl SP-210” manufactured by Sekisui Chemical Co., Ltd., average particle size 10 ⁇ m, softening point 330 ° C., 10% K value (23 ° C.) 3.8 GPa) were electroless nickel plated, A base nickel plating layer having a thickness of 0.1 ⁇ m was formed on the
  • electrolytic plating was performed using an electrolytic plating solution containing tin and bismuth to form a 2 ⁇ m thick solder layer.
  • Conductive particles (average particle size 16 ⁇ m, CV value 20%, resin core solder-coated particles) were prepared.
  • conductive particle B a compound having two carboxyl groups, “glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.
  • glutaric acid a compound having two carboxyl groups, “glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.
  • p-toluenesulfonic acid As a catalyst, By stirring for 8 hours while dehydrating in a toluene solvent at 90 ° C., conductive particles in which a group containing a carboxyl group was covalently bonded to the surface of the solder were obtained.
  • This conductive particle B This conductive particle B.
  • the overlapping area of the glass epoxy substrate and the flexible printed board was 1.5 cm ⁇ 4 mm, and the number of connected electrodes was 75 pairs.
  • the anisotropic conductive paste immediately after fabrication was applied to the upper surface of the glass epoxy substrate so as to have a thickness of 50 ⁇ m to form an anisotropic conductive paste layer.
  • the anisotropic conductive paste containing the solvent was solvent-dried.
  • the flexible printed circuit board was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other.
  • a pressure heating head is placed on the upper surface of the semiconductor chip and a pressure of 2.0 MPa is applied to melt the solder.
  • the anisotropic conductive paste layer was hardened at 185 degreeC, and the connection structure A was obtained.
  • connection structure B The glass epoxy substrate prepared in the connection structure A was exposed at 230 ° C. for 40 seconds or more to oxidize the copper electrode.
  • a connection structure B was obtained in the same manner as the connection structure A except that an oxidized glass epoxy substrate was used.
  • connection structure C was obtained in the same manner as the connection structure B except that the electrode material of the glass epoxy substrate was changed from copper to aluminum.
  • connection structure D In the production of the connection structure B, the copper electrode of the glass epoxy substrate was subjected to preflux (OSP: Organic Solderability Preservative) treatment with Toughace F2 (manufactured by Shikoku Kasei Kogyo Co., Ltd.). A connection structure D was obtained in the same manner except that the electrodes were changed.
  • OSP Organic Solderability Preservative
  • connection structures A to D Presence / absence of voids
  • whether or not voids are generated in the cured layer formed by the anisotropic conductive paste layer is visually observed from the lower surface side of the transparent glass substrate. did.
  • the presence or absence of voids was determined according to the following criteria.
  • the oxide of the electrode is larger in the connection structure B than in the connection structure A, voids tend to be generated.
  • solder placement accuracy on electrode 1 In the obtained connection structures A to D, when 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 viewed, The ratio X of the area where the solder part in the connection part is arranged in 100% of the area of the part where the 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 connection structure, when the portion where the first electrode and the second electrode face each other in the direction orthogonal to the stacking direction of the first electrode, the connection portion, and the second electrode is seen, The ratio Y of the solder part in the connection part arrange
  • 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%
  • Example using a solder particle was shown, it was arrange
  • SYMBOLS 1 Conductive particle 1a ... Surface 2 ... Resin particle 2a ... Surface 3 ... Conductive layer 4 ... 1st conductive layer 4a ... Outer surface 5 ... Solder layer 5a ... Molten solder layer part 11 ... Conductive particle 12 ... Solder layer DESCRIPTION OF SYMBOLS 16 ... Conductive particle 21 ... Connection structure 22 ... 1st connection object member 22a ... Surface 22b ... 1st electrode 23 ... 2nd connection object member 23a ... Surface 23b ... 2nd electrode 24 ... Connection part

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US20210229222A1 (en) * 2018-06-26 2021-07-29 Showa Denko Materials Co., Ltd. Solder particles and method for producing solder particles
WO2024010060A1 (ja) * 2022-07-08 2024-01-11 積水化学工業株式会社 導電ペースト、ｒｆｉｄインレイ、ｒｆｉｄインレイの製造方法、チップを接着するための導電ペーストの使用、及びｒｆｉｄインレイを得るための導電ペーストの使用

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