WO2015133343A1 - 導電ペースト、接続構造体及び接続構造体の製造方法 - Google Patents

導電ペースト、接続構造体及び接続構造体の製造方法 Download PDF

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Publication number
WO2015133343A1
WO2015133343A1 PCT/JP2015/055343 JP2015055343W WO2015133343A1 WO 2015133343 A1 WO2015133343 A1 WO 2015133343A1 JP 2015055343 W JP2015055343 W JP 2015055343W WO 2015133343 A1 WO2015133343 A1 WO 2015133343A1
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WO
WIPO (PCT)
Prior art keywords
conductive paste
electrode
solder particles
solder
temperature
Prior art date
Application number
PCT/JP2015/055343
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English (en)
French (fr)
Japanese (ja)
Inventor
敬士 久保田
石澤　英亮
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.)
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201580002410.2A priority Critical patent/CN105684096B/zh
Priority to JP2015512828A priority patent/JP5851071B1/ja
Priority to KR1020167006636A priority patent/KR102393302B1/ko
Publication of WO2015133343A1 publication Critical patent/WO2015133343A1/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
    • H01B1/20—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
    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • 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
    • 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
    • B23K35/262—Sn as the principal constituent
    • 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
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • 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
    • B23K35/40—Making wire or rods for soldering or welding
    • 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
    • H05K3/341—Surface mounted components
    • H05K3/3431—Leadless components
    • H05K3/3436—Leadless components having an array of bottom contacts, e.g. pad grid array or ball grid array components
    • 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
    • H05K3/3485—Applying solder paste, slurry or powder
    • 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
    • H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
    • 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
    • H05K3/3494—Heating methods for reflowing of solder
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1163—Chemical reaction, e.g. heating solder by exothermic reaction
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/36—Assembling printed circuits with other printed circuits
    • H05K3/361—Assembling flexible printed circuits with other printed circuits
    • H05K3/363—Assembling flexible printed circuits with other printed circuits by soldering
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a conductive paste containing solder particles.
  • the present invention also relates to a connection structure using the conductive paste and a method for manufacturing the connection structure.
  • 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 Document 1 includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent include the resin layer.
  • An adhesive tape present therein is disclosed. This adhesive tape is in the form of a film, not a paste.
  • Patent Document 1 discloses a bonding method using the above-mentioned 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
  • the adhesive tape described in Patent Document 1 is a film, not a paste. For this reason, it is difficult to efficiently arrange the solder powder on the electrodes (lines). For example, in the adhesive tape described in Patent Document 1, a part of the solder powder is easily placed in a region (space) where no electrode is formed. Solder powder disposed in a region where no electrode is formed does not contribute to conduction between the electrodes.
  • the solder powder may not be efficiently disposed on the electrodes (lines).
  • An object of the present invention is to provide a conductive paste that can efficiently arrange solder particles on electrodes and can improve conduction reliability between the electrodes. Moreover, this invention is providing the manufacturing method of the connection structure and connection structure using the said electrically conductive paste.
  • the differential scanning includes a thermosetting component and a plurality of solder particles, and the thermosetting component and the solder particles are each heated at a temperature rising rate of 10 ° C./min.
  • the exothermic peak top temperature in the main curing of the thermosetting component is higher than the endothermic peak top temperature in the melting of the solder particles, and the exothermic peak in the main curing of the thermosetting component.
  • a conductive paste having an absolute value of a difference between a top temperature and an endothermic peak top temperature in melting of the solder particles of 10 ° C or higher and 70 ° C or lower.
  • the heat generation start temperature of the curable component is higher than the endothermic peak top temperature in the melting of the solder particles, and the difference between the heat generation start temperature of the thermosetting component and the endothermic peak top temperature in the melting of the solder particles
  • the absolute value is 5 ° C. or more and 50 ° C. or less.
  • thermosetting component is heated at the temperature increase rate of 10 degree-C / min, and differential scanning calorimetry is performed.
  • the exothermic peak top temperature in the main curing of the thermosetting component is higher than the activation temperature of the flux.
  • the conductive paste includes a flux, and when the differential scanning calorimetry is performed by heating the solder particles at a heating rate of 10 ° C./min, The endothermic peak top temperature in melting the solder particles is higher than the activation temperature of the flux.
  • the said electrically conductive paste contains a flux
  • each of the said thermosetting component and the said solder particle are heated at the temperature increase rate of 10 degree-C / min, and a differential scanning calorie
  • the exothermic peak top temperature in the main curing of the thermosetting component is higher than the activation temperature of the flux
  • the endothermic peak top temperature in the melting of the solder particles is the activation temperature of the flux. Higher than.
  • the content of the solder particles is 10 wt% or more and 70 wt% or less in 100 wt% of the conductive paste.
  • the viscosity at 25 ° C. is 10 Pa ⁇ s or more and 800 Pa ⁇ s or less.
  • the minimum value of the viscosity in the temperature region below the melting point of the solder particles is 0.1 Pa ⁇ s or more and 10 Pa ⁇ s or less.
  • 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
  • the connection part is formed of the above-described conductive paste
  • the first electrode and the second electrode A connection structure is provided in which an electrode is electrically connected by a solder portion in the connection portion.
  • the first connection target member and the second connection target member are disposed so as to face each other, and by heating the conductive paste to a temperature equal to or higher than the melting point of the solder particles and equal to or higher than the curing temperature of the thermosetting component.
  • a step of electrically connecting the first electrode and the second electrode with a solder portion in the connection portion How to manufacture connection structures There is provided.
  • connection portion in the step of arranging the second connection target member and the step of forming the connection portion, no pressure is applied, and the conductive paste includes The weight of the second connection target member is added.
  • the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board.
  • the conductive paste according to the present invention includes a thermosetting component and a plurality of solder particles, and each of the thermosetting component and the solder particles is heated at a rate of temperature increase of 10 ° C./min to perform differential scanning calorimetry.
  • the exothermic peak top temperature in the main curing of the thermosetting component is higher than the endothermic peak top temperature in the melting of the solder particles, and the exothermic peak top temperature in the main curing of the thermosetting component. Since the absolute value of the difference between the temperature and the endothermic peak top temperature in melting of the solder particles is 10 ° C. or higher and 70 ° C. or lower, the solder particles are efficiently placed on the electrodes when the electrodes are electrically connected. It is possible to improve the conduction reliability between the electrodes.
  • FIG. 1 is a partially cutaway front sectional view schematically showing a connection structure obtained using a conductive paste according to an embodiment of the present invention.
  • FIGS. 2A to 2C are diagrams for explaining each step of an example of a method of manufacturing a connection structure using the conductive paste according to the embodiment of the present invention.
  • FIG. 3 is a partially cutaway front sectional view showing a modified example of the connection structure.
  • FIG. 4 is a schematic diagram illustrating an example of a relationship between an exothermic peak in main curing of a thermosetting component and an endothermic peak in melting of solder particles in differential scanning calorimetry.
  • 5A and 5B are images showing an example of a connection structure using the conductive paste included in the embodiment of the present invention, and FIGS.
  • FIGS. 6A and 6B are images showing an example of a connection structure using a conductive paste that is not included in the embodiment of the present invention
  • FIGS. 6A and 6B are images.
  • FIG. 6C is a cross-sectional image
  • FIG. 6C is a planar image.
  • the conductive paste according to the present invention includes a thermosetting component and a plurality of solder particles.
  • the thermosetting component when the differential scanning calorimetry is performed by heating the thermosetting component and the solder particles at a heating rate of 10 ° C./min, the thermosetting component
  • the exothermic peak top temperature in the curing is higher than the endothermic peak top temperature in the melting of the solder particles, and the exothermic peak top temperature in the main curing of the thermosetting component, and the endothermic peak top temperature in the melting of the solder particles
  • the absolute value of the difference is 10 ° C. or higher and 70 ° C. or lower.
  • thermosetting component is heated at a heating rate of 10 ° C./min, and differential scanning calorimetry (DSC) is performed.
  • the solder particles are heated at a heating rate of 10 ° C./min, and differential scanning calorimetry (DSC) is performed.
  • DSC differential scanning calorimetry
  • the exothermic peak top P1t temperature in the main curing of the thermosetting component is higher than the endothermic peak top P2t temperature in the melting of the solder particles. Is also expensive.
  • the absolute value of the difference between the exothermic peak top P1t temperature and the endothermic peak top P2t temperature is 10 ° C. or higher and 70 ° C. or lower.
  • the exothermic peak top P1t and the endothermic peak top P2t indicate temperatures at which the exothermic amount or endothermic amount at the exothermic peak P1 or the endothermic peak P2 is the highest.
  • the exothermic peak P1 is a portion where the calorific value starts to rise from the base line B1 (the temperature at that portion is the calorific start temperature), and after reaching the exothermic peak top P1t, the calorific value decreases and reaches the baseline B1.
  • the part up to is shown.
  • the endothermic peak P2 is a portion where the endothermic amount starts to rise from the baseline B2 (the temperature at that portion is the endothermic start temperature), and after reaching the endothermic peak top P2t, the endothermic amount decreases to reach the baseline B2.
  • the exothermic peak P1 indicating the exothermic peak top P1t temperature in the main curing of the thermosetting component is preferably the main exothermic peak having the highest calorific value.
  • the type of thermosetting compound, the type of thermosetting agent, and the solder particles in the thermosetting component What is necessary is just to adjust suitably the composition of these.
  • the conductive paste according to the present invention since the above-described configuration is adopted, when the electrodes are electrically connected, a plurality of solder particles are easily collected between the electrodes, and the plurality of solder particles are placed on the electrodes (lines). Can be arranged efficiently. Moreover, it is difficult for some of the plurality of solder particles to be disposed in a region (space) where no electrode is formed, and the amount of solder particles disposed in a region where no electrode is formed can be considerably reduced. 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.
  • the exothermic peak top temperature in the main curing of the thermosetting component and the endothermic peak top temperature in the melting of the solder particles satisfy the above-described relationship.
  • the exothermic peak top temperature in the main curing of the thermosetting component and the endothermic peak top temperature in the melting of the solder particles satisfy the relationship described above, excessive flow of the thermosetting component is caused after the solder particles are collected. Since it is suppressed, it becomes difficult for the solder particles to become discrete. For this reason, it is considered that the solder particles are efficiently arranged on the electrode.
  • thermosetting component is preferably higher than the endothermic peak top temperature in melting of the solder particles, and more preferably 5 ° C. or higher.
  • the absolute value of the difference between the heat generation start temperature of the thermosetting component and the endothermic peak top temperature in the melting of the solder particles is preferably 5 ° C. or more. More preferably, it is 10 ° C. or higher, preferably 50 ° C. or lower, more preferably 35 ° C. or lower.
  • the conductive paste according to the present invention can be suitably used for the following manufacturing method of the connection structure according to the present invention.
  • a conductive paste, a first connection target member, and a second connection target member are used.
  • the conductive material used in the method for manufacturing a connection structure according to the present invention is not a conductive film but a conductive paste.
  • the conductive paste includes a plurality of solder particles and a thermosetting component.
  • the first connection target member has at least one first electrode on the surface.
  • the second connection target member has at least one second electrode on the surface.
  • the step of disposing the conductive paste according to the present invention on the surface of the first connection target member, and the first connection target member side of the conductive paste include: On the opposite surface, the step of disposing the second connection object member so that the first electrode and the second electrode face each other, the melting point of the solder particles or higher, and the thermosetting component By heating the conductive paste above the curing temperature, a connection portion connecting the first connection target member and the second connection target member is formed by the conductive paste, and the first And electrically connecting the second electrode and the second electrode with a solder portion in the connection portion.
  • connection structure 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 paste.
  • the weight of the target member is preferably added.
  • the conductive paste in the step of arranging the second connection target member and the step of forming the connection portion, has a weight force of the second connection target member. It is preferable not to apply a pressure higher than.
  • the plurality of solder particles are easily collected between the first electrode and the second electrode, and the plurality of solder particles are collected on the electrode ( Line). Moreover, it is difficult for some of the plurality of solder particles to be disposed in a region (space) where no electrode is formed, and the amount of solder particles 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.
  • a conductive paste is used instead of a conductive film. The inventors have found that they need to be used.
  • the connection portion is Solder particles arranged in a region (space) where no electrode is formed before being formed are more easily collected between the first electrode and the second electrode, and a plurality of solder particles are separated into electrodes (lines).
  • the inventors have also found that they can be arranged efficiently above.
  • a configuration in which a conductive paste is used instead of a conductive film and a configuration in which the weight of the second connection target member is added to the conductive paste without applying pressure are used in combination. This has a great meaning in order to obtain the effects of the present invention at a higher level.
  • WO2008 / 023452A1 describes that it is preferable to pressurize with a predetermined pressure at the time of bonding from the viewpoint of efficiently moving the solder powder to the electrode surface, and the pressurizing pressure further ensures the solder area.
  • the pressure is set to 0 MPa or more, preferably 1 MPa or more.
  • a predetermined pressure may be applied to the adhesive tape by its own weight.
  • the pressure applied intentionally to the adhesive tape may be 0 MPa, but there is no difference between the effect when the pressure exceeding 0 MPa is applied and when the pressure is set to 0 MPa. Not listed.
  • the thickness of the connecting portion can be adjusted as appropriate 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.
  • FIG. 1 schematically shows a connection structure obtained by using a conductive paste according to an embodiment of the present invention in a partially cutaway front sectional view.
  • 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 a conductive paste containing a thermosetting component and a plurality of solder particles. In this conductive paste, the exothermic peak top temperature in the main curing of the thermosetting component and the endothermic peak top temperature in the melting of the solder particles satisfy the relationship described above.
  • the connecting portion 4 includes a solder portion 4A in which a plurality of solder particles are gathered and joined to each other, and a cured product portion 4B in which a thermosetting component is 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 As shown in FIG. 1, in the connection structure 1, after a plurality of solder particles are melted, the molten solder particles are wetted and spread on the surface of the electrode to solidify to form a solder portion 4 ⁇ / b> A. 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 solder particles, the solder portion 4A, the first electrode 2a, and the solder portion 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 4A and the second electrode 3a increases. For this reason, the conduction
  • the conductive paste 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 1 If the amount of solder particles used is reduced, the connection structure 1 can be easily obtained. If the amount of the solder particles used is increased, it becomes easy to obtain the connection structure 1X.
  • connection structure 1 using the conductive paste 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 paste 11 including a thermosetting component 11B and a plurality of solder particles 11A is disposed on the surface of the first connection target member 2 (first Process).
  • the conductive paste 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided.
  • the solder particles 11A are disposed both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
  • the arrangement method of the conductive paste 11 is not particularly limited, and examples thereof include application with a dispenser, screen printing, and ejection with 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 paste 11 is heated above the melting point of the solder particles 11A and above the curing temperature of the thermosetting component 11B (third step). That is, the conductive paste 11 is heated to a temperature lower than the melting point of the solder particles 11A and the curing temperature of the thermosetting component 11B. At the time of this heating, the solder 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 paste is used instead of the conductive film, the solder particles 11A are effectively collected between the first electrode 2a and the second electrode 3a. Also, the solder particles 11A are melted and joined together. Further, the thermosetting component 11B is thermoset.
  • connection portion 4 connecting the first connection target member 2 and the second connection target member 3 is formed with the conductive paste 11.
  • the connection part 4 is formed by the conductive paste 11
  • the solder part 4A is formed by joining a plurality of solder particles 11A
  • the cured part 4B is formed by thermosetting the thermosetting component 11B. If the solder particles 3 move quickly, the first electrode 2a and the second electrode are moved after the movement of the solder particles 3 that are not positioned between the first electrode 2a and the second electrode 3a starts. It is not necessary to keep the temperature constant until the movement of the solder particles 3 is completed.
  • a preheating step may be provided in the first half of the third step.
  • This preheating step is a temperature at which the thermosetting component 11B is not substantially thermally cured at a temperature equal to or higher than the melting temperature of the solder in a state where the weight of the second connection target member 3 is added to the conductive paste 11. This refers to the process of heating for 5 to 60 seconds.
  • 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 obtained 1st connection object member 2, the electrically conductive paste 11, and the 2nd connection object member 3 is moved to a heating part, and said 3rd said 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.
  • connection structures 1 and 1X the first electrode 2a and the second electrode 3a are arranged in the stacking direction of the first electrode 2a, the connection portion 4, and the second electrode 3a.
  • the solder portions 4A in the connection portions 4A, 4X are not less than 50% in the area 100% of the portions facing the first electrode 2a and the second electrode 3a. It is preferable to obtain a connection structure 1, 1X in which 4XA is arranged.
  • the heating temperature in the third step is not particularly limited as long as it is higher than the melting point of the solder particles and higher than the curing temperature of the thermosetting component.
  • the heating temperature is preferably 130 ° 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.
  • the temperature of the preheating step is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, preferably less than 160 ° C., more preferably 150 ° C. or lower.
  • the said 1st connection object member should just have at least 1 1st electrode.
  • the first connection target member preferably has a plurality of first electrodes.
  • the said 2nd connection object member should just have at least 1 2nd electrode.
  • the second connection target member preferably has a plurality of second electrodes.
  • the first and second connection target members are not particularly limited. Specific examples of the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and resin films, printed boards, flexible printed boards, flexible flat cables, rigid flexible boards, glass epoxies. Examples thereof include electronic components such as circuit boards such as substrates and glass substrates.
  • 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 a solder particle not to gather on an electrode.
  • the conductive paste according to the present invention is used, even if a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board is used, the solder particles can be efficiently collected on the electrode. And the reliability of conduction between the electrodes can be sufficiently enhanced.
  • 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.
  • the first and second connection target members may be a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board.
  • 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 molybdenum 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.
  • the distance D1 of the connecting portion at a position where the first electrode and the second electrode face each other is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the distance D1 is equal to or greater than the lower limit, the connection reliability between the connection portion and the connection target member is further increased.
  • the distance D1 is less than or equal to the above upper limit, solder particles are more likely to gather on the electrodes when the connection portion is formed, and the conduction reliability between the electrodes is further enhanced.
  • the distance D1 is preferably 10 ⁇ m or more, more preferably 12 ⁇ m or more.
  • the viscosity ⁇ 1 at 25 ° C. of the conductive paste is preferably 10 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, and further preferably 100 Pa ⁇ s or more, preferably Is 800 Pa ⁇ s or less, more preferably 600 Pa ⁇ s or less, and still more preferably 500 Pa ⁇ s or less.
  • the viscosity can be appropriately adjusted depending on the type and amount of the compounding component. Further, the use of a filler can make the viscosity relatively high.
  • the viscosity can be measured under conditions of 25 ° C. and 5 rpm using, for example, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • the minimum value of viscosity of the conductive paste (minimum melt viscosity value) in a temperature range of 25 ° C. or higher and the melting point of the solder particles (solder) is preferably 0.1 Pa ⁇ s or higher, more preferably 0. .2 Pa ⁇ s or more, preferably 10 Pa ⁇ s or less, more preferably 1 Pa ⁇ s or less.
  • the minimum value of the viscosity is not less than the above lower limit and not more than the above upper limit, the solder particles can be arranged more efficiently on the electrode.
  • the minimum value of the above viscosity is STRESSTECH (manufactured by EOLOGICA), etc., strain control 1 rad, frequency 1 Hz, heating rate 20 ° C./min, measurement temperature range 40 to 200 ° C. (however, the melting point of solder particles is 200 ° C. In the case of exceeding the upper limit of the temperature, the melting point of the solder particles is taken into account). From the measurement result, the minimum value of the viscosity in the temperature region of the solder particle melting point or lower is evaluated.
  • the conductive paste includes a thermosetting component and a plurality of solder particles.
  • the thermosetting component preferably includes a curable compound (thermosetting compound) that can be cured by heating, and a thermosetting agent.
  • the conductive paste preferably contains a flux.
  • solder particles have solder on a conductive outer surface. As for the said solder particle, both a center part and an electroconductive outer surface are formed with the solder.
  • the solder is preferably a low melting point metal having a melting point of 450 ° C. or lower.
  • the solder particles are preferably low melting point metal particles having a melting point of 450 ° C. or lower.
  • 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 particles include tin.
  • the content of tin is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
  • the content of tin in the solder particles is equal to or higher than the lower limit, the connection reliability between the solder portion and the electrode is further enhanced.
  • 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
  • solder particles By using the above solder particles, the solder is melted and joined to the electrodes, and the solder portion conducts between the electrodes. For example, since the solder portion and the electrode are not in point contact but in surface contact, the connection resistance is lowered. In addition, the use of solder particles increases the bonding strength between the solder portion and the electrode. As a result, peeling between the solder portion and the electrode is further less likely to occur, and the conduction reliability and the connection reliability are effectively increased.
  • the low melting point metal constituting 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 solder particles are preferably a filler material having a liquidus line of 450 ° C. or lower based on JIS Z3001: Welding terms.
  • the composition of the solder particles include metal compositions 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 particles preferably do not contain lead, and preferably contain tin and indium, or contain tin and bismuth.
  • the solder particles include nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium. Further, it may contain a metal such as molybdenum and palladium. Moreover, from the viewpoint of further increasing the bonding strength between the solder portion and the electrode, the solder particles preferably contain nickel, copper, antimony, aluminum, or zinc. From the viewpoint of further increasing the bonding strength between the solder part and the electrode, the content of these metals for increasing the bonding strength is preferably 0.0001% by weight or more, preferably 1% by weight in 100% by weight of the solder particles. % Or less.
  • the average particle diameter of the solder particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably 30 ⁇ m.
  • it is 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 solder particles is particularly preferably 3 ⁇ m or more and 30 ⁇ m or less.
  • the average particle diameter” of the solder particles indicates the number average particle diameter.
  • the average particle diameter of the solder particles is obtained, for example, by observing 50 arbitrary solder particles with an electron microscope or an optical microscope and calculating an average value.
  • the content of the solder particles in 100% by weight of the conductive paste 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, and most preferably 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 solder particles is not less than the above lower limit and not more than the above upper limit, it is possible to more efficiently arrange the solder particles on the electrodes, and it is easy to arrange many solder particles between the electrodes, The conduction reliability is further increased. From the viewpoint of further improving the conduction reliability, it is preferable that the content of the solder particles is large.
  • thermosetting component examples 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 paste and further improving the connection reliability.
  • the content of the thermosetting compound 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. Is 98% by weight or less, more preferably 90% by weight or less, and particularly preferably 80% by weight or less. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting component is large.
  • thermosetting agent thermosetting component
  • the thermosetting agent thermosets the thermosetting compound.
  • examples of the thermosetting agent include an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, an acid anhydride, a thermal cation initiator, and a thermal radical generator.
  • the said thermosetting agent only 1 type may be used and 2 or more types may be used together.
  • an imidazole curing agent, a polythiol curing agent, or an amine curing agent is preferable because the conductive paste can be cured more rapidly at a low temperature.
  • a latent curing agent is preferable.
  • the latent curing agent is preferably a latent imidazole curing agent, a latent polythiol 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 polythiol curing agent is not particularly limited, and examples thereof include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .
  • the solubility parameter of the polythiol curing agent is preferably 9.5 or more, and preferably 12 or less.
  • the solubility parameter is calculated by the Fedors method.
  • the solubility parameter of trimethylolpropane tris-3-mercaptopropionate is 9.6, and the solubility parameter of dipentaerythritol hexa-3-mercaptopropionate is 11.4.
  • 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 curing agent 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 or lower, Especially preferably, it is 140 degrees C or less.
  • 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 particles are 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 in the solder particles, more preferably 5 ° C. or more, more preferably 10 It is more preferable that the temperature is higher than ° C.
  • the reaction start temperature of the thermosetting agent means a temperature at which the exothermic peak of DSC starts to rise (that is, the above heat generation start temperature).
  • 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, more preferably 100 parts by weight with respect to 100 parts by weight of the thermosetting compound. Part or less, more preferably 75 parts by weight or less.
  • the content of the thermosetting agent is at least the above lower limit, it is easy to sufficiently cure the conductive paste.
  • 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 paste preferably contains a flux.
  • the flux is not particularly limited.
  • a flux generally used for soldering or the like can be used.
  • 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.
  • 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 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 160 ° C. or lower, even more preferably 150 ° C. or lower, still more preferably. 140 ° C. or lower.
  • the melting point of the flux is preferably 80 ° C. or higher and 190 ° C. or lower.
  • the melting point of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • Examples of the flux having a melting point of 80 ° C. or higher and 190 ° C. or lower include succinic acid (melting point 186 ° C.), glutaric acid (melting point 96 ° C.), adipic acid (melting point 152 ° C.), pimelic acid (melting point 104 ° C.), suberic acid
  • Examples thereof include dicarboxylic acids such as (melting point 142 ° C.), benzoic acid (melting point 122 ° C.), and malic acid (melting point 130 ° C.).
  • the boiling point of the flux is preferably 200 ° C. or lower.
  • the melting point of the flux is preferably lower than the melting point of the solder in the solder particles, more preferably 5 ° C. or more, more preferably 10 ° C. or more. Is more preferable.
  • the melting point of the flux is preferably lower than the reaction peak of the thermosetting agent, more preferably 5 ° C. or more, more preferably 10 ° C. or more. Is more preferable.
  • the flux may be dispersed in the conductive paste or may be adhered on the surface of the solder particles.
  • the flux is preferably a flux that releases cations by heating.
  • a flux that releases cations upon heating the solder particles can be arranged more efficiently on the electrode.
  • the heat generation start temperature of the thermosetting component is higher than the activation temperature (melting point) of the flux. Is preferred. From the viewpoint of more efficiently arranging the solder particles on the electrodes and further improving the conduction reliability between the electrodes, the endothermic peak top temperature in melting of the solder particles is higher than the activation temperature (melting point) of the flux. It is preferable. From the viewpoint of further efficiently arranging the solder particles on the electrodes and further improving the conduction reliability between the electrodes, the heat generation starting temperature of the thermosetting component is higher than the activation temperature (melting point) of the flux. And the endothermic peak top temperature in melting of the solder particles is preferably higher than the activation temperature (melting point) of the flux.
  • the difference between the heat generation start temperature of the thermosetting component and the activation temperature (melting point) of the flux is The absolute value is preferably 10 ° C or higher, more preferably 20 ° C or higher, preferably 80 ° C or lower, more preferably 70 ° C or lower. From the viewpoint of more efficiently arranging the solder particles on the electrodes and further improving the conduction reliability between the electrodes, the difference between the endothermic peak top temperature in melting of the solder particles and the active temperature (melting point) of the flux The absolute value of is preferably 1 ° C. or higher, more preferably 20 ° C. or higher, preferably 60 ° C. or lower, more preferably 50 ° C. or lower.
  • 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 paste may not contain a 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.
  • the conductive paste is, 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.
  • various additives such as an antistatic agent and a flame retardant may be included.
  • Polymer A Synthesis of reaction product (polymer A) of bisphenol F with 1,6-hexanediol diglycidyl ether and bisphenol F type epoxy resin: 72 parts by weight of bisphenol F (containing 4,4′-methylene bisphenol, 2,4′-methylene bisphenol and 2,2′-methylene bisphenol in a weight ratio of 2: 3: 1), 1,6-hexanediol 70 parts by weight of glycidyl ether and 30 parts by weight of bisphenol F type epoxy resin (“EPICLON EXA-830CRP” manufactured by DIC) were placed in a three-necked flask and dissolved at 150 ° C. under a nitrogen flow.
  • bisphenol F type epoxy resin (“EPICLON EXA-830CRP” manufactured by DIC)
  • the reaction product (Polymer A) contains a hydroxyl group derived from bisphenol F, 1,6-hexanediol diglycidyl ether, and an epoxy group of bisphenol F type epoxy resin. It was confirmed that it has a structural unit bonded to the main chain and has an epoxy group at both ends.
  • the weight average molecular weight of the reaction product (polymer A) obtained by GPC was 10,000, and the number average molecular weight was 3,500.
  • Polymer B both end epoxy group rigid skeleton phenoxy resin, “YX6900BH45” manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 16000
  • Thermosetting compound 1 Resorcinol type epoxy compound, “EX-201” manufactured by Nagase ChemteX Corporation
  • Thermosetting compound 2 Naphthalene type epoxy compound, “HP-4032D” manufactured by DIC
  • Thermosetting compound 3 bisphenol F type epoxy resin, “EVA-830CRP” manufactured by DIC
  • Thermosetting agent Pentaerythritol tetrakis (3-mercaptobutyrate), “Karenz MT PE1” manufactured by Showa Denko KK
  • Flux 1 Glutaric acid, manufactured by Wako Pure Chemical Industries
  • Flux 2 Adipic acid, manufactured by Wako Pure Chemical Industries
  • Latent epoxy thermosetting agent T & K TOKA "Fujicure 7000"
  • Latent thermosetting agent Microcapsule type, “HXA-3932HP” manufactured by Asahi Kasei E-Materials
  • Solder particles 1 Sn-58Bi solder particles, melting point 139 ° C., “10-25” manufactured by Mitsui Mining & Smelting Co., Ltd., average particle size 10 ⁇ m
  • Solder particles 2 Sn-37Pb solder particles, melting point 183 ° C., “10-25” manufactured by Mitsui Mining & Smelting Co., Ltd., average particle size 12 ⁇ m
  • Solder particles 3 200 g of solder powder, 40 g of adipic acid and 70 g of acetone are weighed in a three-necked flask, and 0.3 g of dibutyltin oxide, which is a dehydration condensation catalyst between the hydroxyl group of the solder powder and the carboxyl group of glutaric acid, is added. , Reacted at 60 ° C. for 4 hours. Then, it collect
  • the solder powder, 50 g of glutaric acid, 200 g of toluene, and 0.3 g of para-toluenesulfonic acid were weighed in a three-necked flask and reacted at 120 ° C. for 3 hours while evacuating and refluxing. . At this time, the reaction was carried out while removing water produced by dehydration condensation using a Dean-Stark extraction device.
  • solder powder was collected by filtration, washed with hexane, and dried. Thereafter, the obtained solder powder was pulverized with a ball mill, and a sieve was selected so as to obtain a predetermined CV value. Thus, solder particles 3 were obtained.
  • conductive particles 1 Production method of conductive particles 1: Divinylbenzene resin particles having an average particle diameter of 10 ⁇ m (“Micropearl SP-210” manufactured by Sekisui Chemical Co., Ltd.) were subjected to electroless nickel plating to form a base nickel plating layer having a thickness of 0.1 ⁇ m on the surface of the resin particles. 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. Furthermore, electrolytic plating was performed using an electrolytic plating solution containing tin and bismuth to form a solder layer having a thickness of 3 ⁇ m.
  • Conductive particles 1 were prepared.
  • Phenoxy resin (“YP-50S” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
  • FR-4 substrate having a copper electrode pattern (copper electrode thickness 10 ⁇ m) having an L / S of 50 ⁇ m / 50 ⁇ m on the upper surface
  • Second connection object member the flexible printed circuit board (2nd connection object member) which has a copper electrode pattern (copper electrode thickness 10 micrometers) whose L / S is 50 micrometers / 50 micrometers on the lower surface was prepared.
  • 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 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 a temperature of 185 ° C., the solder was melted and the anisotropic conductive paste layer was cured at 185 ° C. to obtain a first connection structure.
  • Glass epoxy substrate (FR-4 substrate) having a copper electrode pattern (copper electrode thickness 10 ⁇ m) having L / S of 75 ⁇ m / 75 ⁇ m on the upper surface (First connection object member) was prepared.
  • the flexible printed circuit board (2nd connection object member) which has a copper electrode pattern (copper electrode thickness 10 micrometers) whose L / S is 75 micrometers / 75 micrometers on the lower surface 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.
  • 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.
  • Electrode size / space between electrodes is 100 ⁇ m / 100 ⁇ m (for the third connection structure), 75 ⁇ m / 75 ⁇ m (for the second connection structure), 50 ⁇ m / 50 ⁇ m (for the first connection structure), 5 mm
  • a square semiconductor chip thickness 400 ⁇ m
  • a glass epoxy substrate size 30 ⁇ 30 mm thickness 0.4 mm
  • phenoxy resin (“YP-50S” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was dissolved in methyl ethyl ketone (MEK) so that the solid content was 50% by weight to obtain a solution.
  • MEK methyl ethyl ketone
  • Ingredients other than the phenoxy resin shown in Table 2 below were blended with the blending amounts shown in Table 2 below and the total amount of the above solution, and after stirring for 5 minutes at 2000 rpm using a planetary stirrer, a bar coater was used. It was coated on a release PET (polyethylene terephthalate) film so that the thickness after drying was 30 ⁇ m.
  • An anisotropic conductive film was obtained by removing MEK by vacuum drying at room temperature.
  • the 1st, 2nd, 3rd connection structure was obtained like Example 1 except having used an anisotropic conductive film.
  • Second, and third connection structures were obtained in the same manner as in Comparative Example 1 except that the flexible printed board was changed to a semiconductor chip.
  • Viscosity The viscosity ⁇ 1 at 25 ° C. of the anisotropic conductive paste was measured under the conditions of 25 ° C. and 5 rpm using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • Minimum melt viscosity The minimum melt viscosity of the anisotropic conductive paste in the temperature range from 25 ° C. to the melting point of the solder particles or the melting point of the solder on the surface of the conductive particles was measured.
  • thermosetting components in the anisotropic conductive pastes of Examples and Comparative Examples were blended. Using a differential scanning calorimeter (“Q2000” manufactured by TA Instruments), the obtained thermosetting component was heated at a rate of temperature increase of 10 ° C./min, in the main curing of the thermosetting component. An exothermic peak P1 was measured.
  • solder particles were heated at a heating rate of 10 ° C./min, and the endothermic peak P2 in the melting of the solder particles was measured.
  • Tables 1 and 2 below show 1) exothermic peak top temperature P1t in the main curing of the thermosetting component, 2) endothermic peak top temperature P2t in the melting of the solder particles, and 3) exotherm in the main curing of the thermosetting component The starting temperature and 4) the endothermic starting temperature in melting of the solder particles are shown.
  • solder placement accuracy on electrodes In the cross sections (cross sections in the direction shown in FIG. 1) of the obtained first, second, and third connection structures, the solder is disposed between the electrodes in a total area of 100%. The area (%) of the solder remaining in the cured product away from the solder portion was evaluated. In addition, the average of the area in five cross sections was computed. The placement accuracy of the solder on the electrode was determined according to the following criteria.
  • connection resistance between the upper and lower electrodes was measured by the four-terminal method, respectively. .
  • 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.
  • ⁇ 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 ⁇
  • the second connection target member is a flexible printed circuit board
  • the second connection target member is It can be seen that the effect of improving the conduction reliability by using the conductive paste of the present invention can be obtained more effectively than in the case of a semiconductor chip.
  • connection structures obtained in Examples 1 to 14 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 was seen.
  • the solder portion in the connection portion is arranged in 50% or more of the area of 100% of the portion where the first electrode and the second electrode face each other.
  • FIGS. 5A and 5B show an example of a connection structure using the conductive paste included in the embodiment of the present invention.
  • 5A and 5B are cross-sectional images. 5A and 5B, it can be seen that there is no solder (solder particles) remaining in the cured product away from the solder portion arranged between the electrodes.
  • FIGS. 6A, 6B and 6C show an example of a connection structure using a conductive paste not included in the embodiment of the present invention.
  • 6A and 6B are cross-sectional images
  • FIG. 6C is a planar image.
  • 6 (a), 6 (b), and 6 (c) there are a plurality of solders (solder particles) left in the cured product apart from the solder portions arranged between the electrodes, on the side of the solder portions.
  • solders solders

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Non-Insulated Conductors (AREA)
  • Combinations Of Printed Boards (AREA)
  • Manufacturing Of Electrical Connectors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2015/055343 2014-03-07 2015-02-25 導電ペースト、接続構造体及び接続構造体の製造方法 WO2015133343A1 (ja)

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JP2017092424A (ja) * 2015-11-17 2017-05-25 積水化学工業株式会社 接続構造体の製造方法
JP2017091951A (ja) * 2015-11-16 2017-05-25 積水化学工業株式会社 導電材料及び接続構造体
JP2020023601A (ja) * 2018-08-06 2020-02-13 日立化成株式会社 伸縮性樹脂形成用熱硬化性組成物、伸縮性樹脂、及び半導体装置
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