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WO2018174066A1 - Conductive particles, conductive material, and connection structure - Google Patents

Conductive particles, conductive material, and connection structure Download PDF

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Publication number
WO2018174066A1
WO2018174066A1 PCT/JP2018/011068 JP2018011068W WO2018174066A1 WO 2018174066 A1 WO2018174066 A1 WO 2018174066A1 JP 2018011068 W JP2018011068 W JP 2018011068W WO 2018174066 A1 WO2018174066 A1 WO 2018174066A1
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WO
WIPO (PCT)
Prior art keywords
solder
electrode
particles
conductive
conductive particles
Prior art date
Application number
PCT/JP2018/011068
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French (fr)
Japanese (ja)
Inventor
敬士 久保田
敬三 西岡
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2018517647A priority Critical patent/JPWO2018174066A1/en
Priority to CN201880004430.7A priority patent/CN109983544A/en
Publication of WO2018174066A1 publication Critical patent/WO2018174066A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

Definitions

  • the present invention relates to conductive particles containing solder.
  • the present invention also relates to a conductive material and a connection structure using the conductive particles.
  • Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
  • anisotropic conductive material conductive particles are dispersed in a binder.
  • the anisotropic conductive material is used for obtaining various connection structures.
  • Examples of the connection using the anisotropic conductive material include a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), and a semiconductor.
  • Examples include connection between a 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.
  • 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 describes an anisotropic conductive material containing conductive particles and a resin component that cannot be cured at the melting point of the conductive particles.
  • the conductive particles tin (Sn), indium (In), bismuth (Bi), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd), gallium (Ga) ), Silver (Ag), thallium (Tl) and other metals, and alloys of these metals.
  • Patent Document 1 a resin heating step for heating the anisotropic conductive material to a temperature higher than the melting point of the conductive particles and at which the curing of the resin component is not completed, and a resin component curing step for curing the resin component The electrical connection between the electrodes is described.
  • Patent Document 1 describes that mounting is performed with the temperature profile shown in FIG.
  • conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive material is heated.
  • Patent Document 2 includes an adhesive tape (conductive material) that includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent are present in the resin layer. Is disclosed.
  • Patent Document 3 discloses conductive particles including particles and a conductive coating formed on the surface of the particles by an electroless plating method.
  • the conductive coating includes a nickel plating coating, a tin plating coating, and a bismuth plating coating formed in order from the inside by electroless plating.
  • the conductive coating has a silver plating coating on the outermost surface.
  • the conductive particles can be used for anisotropic conductive materials.
  • conductive particles or solder particles are likely to be oxidized, and the impact resistance of the connection portion between the connected electrodes may not be sufficiently increased.
  • the impact resistance of the connection portion is not sufficiently high, a crack or the like may occur in the connection portion due to an impact such as dropping of the substrate. As a result, it is difficult to sufficiently improve the conduction reliability between the electrodes.
  • SAC silver-copper alloy
  • conductive particles comprising solder particles having a melting point of less than 200 ° C. and a coating portion disposed on the surface of the solder particles, wherein the coating portion contains silver.
  • the solder particles include tin and bismuth.
  • the content of the silver is 1% by weight or more and 20% by weight or less in 100% by weight of the conductive particles.
  • the surface area covered by the coating portion on the surface of the solder particles is 80% or more in the entire surface area of the solder particles of 100%.
  • the thickness of the covering portion is 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the conductive particle includes a metal part containing nickel between the outer surface of the solder particle and the covering part.
  • a conductive material including the above-described conductive particles and a thermosetting compound.
  • the content of the conductive particles exceeds 50% by weight in 100% by weight of the conductive material.
  • thermosetting compound includes a thermosetting compound having a polyether skeleton.
  • the conductive material includes a flux having a melting point of 50 ° C. or higher and 140 ° C. or lower.
  • the viscosity at 25 ° C. is 20 Pa ⁇ s or more and 600 Pa ⁇ s or less.
  • the conductive material is a conductive paste.
  • 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 first connection target member and a connection part connecting the second connection target member wherein the material of the connection part includes the conductive particles described above, and 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 electrode and the second electrode face each other in the stacking direction of the first electrode, the connection portion, and the second electrode.
  • 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.
  • the conductive particles according to the present invention include solder particles having a melting point of less than 200 ° C. and a covering portion disposed on the surface of the solder particles.
  • coated part contains silver. Since the conductive particle according to the present invention has the above-described configuration, it can be easily mounted at a low temperature, and the impact resistance of the connection portion can be effectively enhanced.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
  • 2A to 2C are cross-sectional views for explaining each step of an example of a method for manufacturing a connection structure using a conductive material according to an embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing a modification of the connection structure.
  • FIG. 4 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 5 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • the electroconductive particle which concerns on this invention is equipped with a solder particle and the coating
  • fusing point of the said solder particle is less than 200 degreeC.
  • coated part contains silver.
  • the present invention since the above configuration is provided, it can be easily mounted at a low temperature, and the impact resistance of the connection portion can be effectively increased.
  • connection structure when the connection structure is manufactured, after a conductive material containing conductive particles is arranged on a connection target member such as a substrate by screen printing or the like, it is left for a certain period until the electrodes are electrically connected.
  • metal ions may be eluted from the conductive particles while being left for a certain period of time.
  • the eluted metal ions may accelerate the curing of the thermosetting compound in the conductive material and may increase the viscosity of the conductive material.
  • the solder in the conductive particles cannot be efficiently arranged on the electrodes, and the conduction reliability between the electrodes may be lowered.
  • the conductive material containing the conductive particles is placed and left for a certain period of time, the conductive material is prevented from thickening and the solder in the conductive particles on the electrode is prevented. Can be arranged efficiently, and the conduction reliability between the electrodes can be sufficiently enhanced.
  • the present invention since it corresponds to an electrode having a narrow electrode width and inter-electrode width, even if the particle diameter of the solder particles is reduced, the surface of the solder particles can be prevented from being oxidized, and the solder wettability can be reduced. Can keep good.
  • a conventional conductive material when the electrode width or the inter-electrode width is narrow, there is a tendency that it is difficult to gather solder on the electrodes.
  • the present invention even if the electrode width or the inter-electrode width is narrow, the solder in the conductive particles can be sufficiently gathered on the electrodes.
  • the conductive particles have a covering portion containing silver.
  • the plurality of conductive particles are likely to gather between the upper and lower electrodes, and the plurality of conductive particles are It can arrange
  • the present invention it is possible to prevent displacement between the electrodes.
  • the alignment between the first electrode and the second electrode is performed. Even in a shifted state, the shift can be corrected and the first electrode and the second electrode can be connected (self-alignment effect).
  • FIG. 4 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the 4 includes a solder particle 22 and a covering portion 23 disposed on the surface of the solder particle 22.
  • the conductive particle 21 illustrated in FIG. The melting point of the solder particles 22 is less than 200 ° C.
  • the covering portion 23 contains silver.
  • the covering portion 23 covers the surface of the solder particle 22.
  • the conductive particles 21 are coated particles in which the surface of the solder particles 22 is coated with the coating portion 23.
  • the covering portion may completely cover the surface of the solder particles, or may not completely cover the surface of the solder particles.
  • the solder particles may have a portion that is not covered by the covering portion.
  • FIG. 5 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
  • the conductive particle 31 includes a metal part 32 between the solder particle 22 and the covering part 23.
  • the metal part 32 covers the surface of the solder particle 22.
  • the covering portion 23 covers the surface of the metal portion 32.
  • the covering portion 23 contains silver.
  • the metal part 32 contains nickel.
  • the conductive particle 31 is a coated particle in which the surface of the solder particle 22 is coated with the metal portion 32 and the covering portion 23.
  • the particle diameter of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably. Is 30 ⁇ m or less, more preferably 20 ⁇ m or less, particularly preferably 15 ⁇ m or less, and most preferably 10 ⁇ m or less. When the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be arranged more efficiently on the electrode.
  • the particle diameter of the conductive particles is particularly preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the particle diameter of the conductive particles indicates a number average particle diameter.
  • the particle diameter of the conductive particles may be determined by, for example, observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value of the particle diameter of each conductive particle, or measuring a laser diffraction particle size distribution. It is calculated by doing.
  • the particle diameter variation coefficient (CV value) of the conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less.
  • CV value of the particle diameter of the conductive particles may be less than 5%.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the conductive particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
  • solder particles As for the said solder particle, 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 outer surface are solder.
  • the conductive particles are conductive on the electrodes. Particles are difficult to collect.
  • the solder bonding property between the conductive particles is low, the conductive particles that have moved onto the electrodes tend to move out of the electrodes, and the effect of suppressing displacement between the electrodes also tends to be low.
  • the solder is preferably a metal (low melting point metal) having a melting point of 450 ° C. or lower.
  • the solder particles are preferably metal particles (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 less than 200 ° C., further preferably 160 ° C. or lower.
  • the melting point of the solder particles is less than 200 ° C.
  • the solder particles are preferably a low melting point solder having a melting point of less than 200 ° C., and more preferably a low melting point solder having a melting point of less than 150 ° C.
  • the solder particles preferably contain tin and bismuth.
  • the content of tin in 100% by weight of metal contained in the solder particles is preferably 30% by weight or more, more preferably 40% by weight or more, further preferably 70% by weight or more, and particularly preferably 90% by weight or more. .
  • the connection reliability between the solder portion and the electrode is further enhanced.
  • the content of bismuth is preferably 40% by weight or more, more preferably 45% by weight or more, still more preferably 48% by weight or more, and particularly preferably 50% by weight or more.
  • the connection reliability between the solder portion and the electrode is further enhanced.
  • the content of tin and bismuth 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). Can be measured.
  • ICP-AES high frequency inductively coupled plasma emission spectrometer
  • EDX-800HS fluorescent X-ray analyzer
  • the solder is melted and joined to the electrodes, and the solder portion conducts between the electrodes.
  • the connection resistance is lowered.
  • the bonding strength between the solder part and the electrode is increased.
  • peeling between the solder part and the electrode is less likely to occur, and the conduction reliability and the connection reliability are further improved.
  • the low melting point metal constituting the solder particles is not particularly limited as long as the melting point is less than 200 ° C.
  • the low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy.
  • the low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, or tin-indium alloy because of its excellent wettability 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.
  • Preferred is a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which has a low melting point and is lead-free. 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, Metals such as molybdenum and palladium may be included.
  • the solder particles preferably contain nickel, copper, antimony, aluminum, or zinc.
  • 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 particle diameter of the solder particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably. It is 30 ⁇ m or less, more preferably 20 ⁇ m or less, particularly preferably 15 ⁇ m or less, and most preferably 10 ⁇ m or less.
  • the particle size of the solder particles is particularly preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the particle size of the solder particles indicates a number average particle size.
  • the particle size of the solder particles is, for example, observing 50 arbitrary solder particles with an electron microscope or an optical microscope, calculating an average value of the particle size of each solder particle, or performing a laser diffraction particle size distribution measurement. Is required.
  • the coefficient of variation (CV value) of the particle size of the solder particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less.
  • the variation coefficient of the particle diameter of the solder particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrode.
  • the CV value of the particle diameter of the solder particles may be less than 5%.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle diameter of solder particles Dn: Average value of particle diameter of solder particles
  • the shape of the solder particles is not particularly limited.
  • the solder particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
  • coated part is arrange
  • coated part contains silver.
  • coated part may contain only silver and may contain metals other than silver.
  • a metal other than silver contained in the covering portion is not particularly limited, and examples thereof include gold, copper, nickel, palladium, and titanium.
  • the content of the silver in 100% by weight of the conductive particles is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, particularly preferably 11% by weight or more, preferably It is 20 weight% or less, More preferably, it is 15 weight% or less, More preferably, it is 13 weight% or less.
  • the silver content is not less than the above lower limit and not more than the above upper limit, it can be more easily mounted at a low temperature, and the impact resistance of the connecting portion can be further effectively improved.
  • the surface area of the solder particles is covered by the covering portion on the surface of the solder particles in 100% of the entire surface area of the solder particles.
  • the surface area (coverage) is preferably 80% or more, more preferably 90% or more.
  • the upper limit of the said coverage is not specifically limited. The coverage may be 100% or less.
  • the coverage can be calculated by performing Ag mapping and conducting image analysis by conducting SEM-EDX analysis on the conductive particles.
  • the thickness of the covering portion is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less.
  • coated part means the thickness of the coating
  • the thickness of the covering portion is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more, particularly preferably 1.5 ⁇ m or more. Yes, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the covering portion is formed only of silver, when the thickness of the covering portion is not less than the above lower limit and not more than the above upper limit, it can be more easily mounted at a low temperature, and the impact resistance of the connection portion Can be increased more effectively.
  • the covering portion may be a single layer or two or more layers (multilayer).
  • the thickness of the covering portion means the thickness of the entire covering portion.
  • the thickness of the covering portion can be calculated from the difference between the particle diameter of the solder particles and the particle diameter of the conductive particles.
  • the ratio of the thickness of the covering portion to the particle diameter of the solder particles Is preferably 0.001 or more, more preferably 0.01 or more, preferably 5 or less, more preferably 1 or less.
  • the conductive particles provided with the covering portion as a conductive material or the like, elution of metal ions from the conductive particles can be effectively prevented, and thickening of the conductive material can be effectively prevented.
  • the conductive particles are provided with the covering portion, the surface of the solder of the conductive particles can be effectively prevented from being oxidized, and the wettability of the solder can be further improved.
  • the solder of the solder particles in the conductive particles and the silver contained in the covering portion exist independently and are not alloyed.
  • the conductive particles before the conductive connection can be melted at the melting point of the solder particles. Since the solder particles are preferably low melting point solder having a melting point of less than 200 ° C., the conductive particles before conductive connection (mounting) can be melted at a relatively low temperature, and can be easily conductive connection at a low temperature. (Implementation) can be.
  • the solder of the solder particles in the conductive particles and the silver contained in the covering portion are alloyed by heat applied during the conductive connection (mounting).
  • the melting point of the connection part (solder part) after the conductive connection (mounting) becomes higher than the melting point of the solder particles, the impact resistance of the connection part (solder part) can be effectively increased. it can.
  • the conductive particles preferably include a metal part including nickel between the outer surface of the solder particles and the covering part.
  • the conductive particles preferably include a metal portion disposed on the surface of the solder particle and a covering portion disposed on the surface of the metal portion.
  • the metal part preferably contains nickel.
  • the metal part may contain a metal other than nickel.
  • a metal other than nickel contained in the metal part is not particularly limited, and examples thereof include gold, silver, copper, palladium, and titanium.
  • the thickness of the metal part is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less.
  • the thickness of the said metal part means thickness only the part with a metal part arrange
  • the thickness of the metal part is preferably from the viewpoint of more easily mounting at a low temperature and further enhancing the impact resistance of the connection part more effectively. Is 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the metal part may be a single layer or two or more layers (multilayer).
  • the thickness of the metal part means the thickness of the entire metal part.
  • the thickness of the metal part can be determined, for example, by observing the cross section of the conductive particles using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the ratio of the thickness of the metal portion to the particle diameter of the solder particles Is preferably 0.001 or more, more preferably 0.01 or more, preferably 5 or less, more preferably 1 or less.
  • the conductive material according to the present invention preferably includes the above-described conductive particles and a thermosetting compound.
  • the conductive material is preferably liquid at 25 ° C., and preferably a conductive paste.
  • the viscosity ( ⁇ 25) at 25 ° C. of the conductive material is preferably 20 Pa ⁇ s or more, more preferably 30 Pa ⁇ s or more. , Preferably 600 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less.
  • the said viscosity ((eta) 25) can be suitably adjusted with the kind and compounding quantity of a compounding component.
  • the viscosity ( ⁇ 25) can be measured under conditions of 25 ° C. and 5 rpm using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.).
  • the viscosity ( ⁇ mp) of the conductive material at the melting point of the conductive particles is preferably 0.1 Pa ⁇ s or more, more preferably 0. It is 5 Pa ⁇ s or more, preferably 5 Pa ⁇ s or less, more preferably 1 Pa ⁇ s or less.
  • the viscosity ( ⁇ mp) can be appropriately adjusted according to the type and amount of the compounding component.
  • the melting point of the conductive particles is a temperature that tends to affect the movement of the conductive particles onto the electrode of the solder.
  • the viscosity ( ⁇ mp) of the conductive material at the melting point of the conductive particles is, for example, strain control 1 rad, frequency 1 Hz, temperature rising rate 20 ° C./min, measurement temperature range 40 ° C. using STRESSTECH (manufactured by REOLOGICA). It can be measured under the condition of the melting point of the conductive particles. In this measurement, the viscosity at the melting point of the conductive particles is defined as the viscosity ( ⁇ mp) of the conductive material.
  • the conductive material can be used as a conductive paste and a conductive film.
  • the conductive paste is preferably an anisotropic conductive paste, and the conductive film is preferably an anisotropic conductive film. From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the conductive material is preferably a conductive paste.
  • the conductive material is preferably used for electrical connection of electrodes.
  • the conductive material is preferably a circuit connection material.
  • the content of the conductive particles in the conductive material of 100% by weight preferably exceeds 50% by weight.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 50% by weight or more, more preferably 70% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less. .
  • the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and a large number of conductive particles are arranged between the electrodes. And the conduction reliability is further enhanced. From the viewpoint of further improving the conduction reliability, the content of the conductive particles is preferably large.
  • (meth) acryl means one or both of “acryl” and “methacryl”
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”.
  • the conductive material preferably contains a thermosetting compound.
  • the thermosetting compound is a compound that can be cured by heating.
  • examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds.
  • the thermosetting compound is preferably an epoxy compound or an episulfide compound. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.
  • the thermosetting compound preferably includes a thermosetting compound having a polyether skeleton.
  • thermosetting compound having a polyether skeleton examples include a compound having a glycidyl ether group at both ends of an alkyl chain having 3 to 12 carbon atoms and a polyether skeleton having 2 to 4 carbon atoms.
  • examples thereof include polyether type epoxy compounds having structural units in which 2 to 10 are bonded continuously.
  • thermosetting compound includes a thermosetting compound having a triazine skeleton. Is preferred.
  • thermosetting compound having a triazine skeleton examples include triazine triglycidyl ether and the like. PAS, TEPIC-VL, TEPIC-UC) and the like.
  • the above-mentioned epoxy compound includes an aromatic epoxy compound.
  • the epoxy compound is preferably a crystalline epoxy compound such as a resorcinol type epoxy compound, a naphthalene type epoxy compound, a biphenyl type epoxy compound, or a benzophenone type epoxy compound.
  • the epoxy compound is preferably an epoxy compound that is solid at normal temperature (23 ° C.) and has a melting temperature equal to or lower than the melting point of the solder.
  • the melting temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and preferably 40 ° C. or higher.
  • the first connection target member and the second connection target are high when the connection target member is bonded to each other when the viscosity is high and acceleration is applied by impact such as conveyance.
  • the positional deviation with respect to the member can be suppressed.
  • the viscosity of the conductive material can be greatly reduced by the heat during curing, and the aggregation of solder in the conductive particles can be efficiently advanced.
  • the thermosetting compound preferably includes a thermosetting compound that is liquid at 25 ° C.
  • examples of the thermosetting compound that is liquid at 25 ° C. include epoxy compounds and episulfide compounds.
  • the content of the thermosetting compound in 100% by weight of the conductive material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and preferably 99% by weight or less. More preferably, it is 98 weight% or less, More preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less.
  • the content of the thermosetting compound is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles is more efficiently arranged on the electrodes, and the displacement between the electrodes is further suppressed, and the electrodes The conduction reliability between them can be further enhanced. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting compound is large.
  • the conductive material preferably contains a thermosetting agent.
  • the conductive material preferably contains a thermosetting agent together with the thermosetting compound.
  • the thermosetting agent thermosets the thermosetting compound.
  • examples of the thermosetting agent include an imidazole curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a thermal cation curing agent, and a thermal radical generator.
  • the said thermosetting agent only 1 type may be used and 2 or more types may be used together.
  • the thermosetting agent is preferably an imidazole curing agent, a thiol curing agent, or an amine curing agent. Further, from the viewpoint of enhancing the storage stability when the thermosetting compound and the thermosetting agent are mixed, the thermosetting agent is preferably a latent curing agent.
  • the latent curing agent is preferably a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent.
  • the said thermosetting agent may be coat
  • the imidazole curing agent is not particularly limited.
  • Examples of the imidazole curing agent include 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-triazine isocyanuric acid adducts Etc.
  • the thiol curing agent is not particularly limited.
  • Examples of the thiol curing agent include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.
  • the amine curing agent is not particularly limited.
  • examples of the amine curing agent include hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane, bis (4 -Aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone and the like.
  • the thermal cationic curing agent is not particularly limited.
  • Examples of the thermal cationic curing agent include iodonium-based cationic curing agents, oxonium-based cationic curing agents, and sulfonium-based cationic curing agents.
  • Examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate.
  • Examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate.
  • Examples of the sulfonium-based cationic curing agent include tri-p-tolylsulfonium hexafluorophosphate.
  • the thermal radical generator is not particularly limited.
  • the thermal radical generator include azo compounds and organic peroxides.
  • the azo compound include azobisisobutyronitrile (AIBN).
  • AIBN azobisisobutyronitrile
  • the organic peroxide include di-tert-butyl peroxide and methyl ethyl ketone peroxide.
  • the reaction initiation temperature of the thermosetting agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 150 ° C. Hereinafter, it is particularly preferably 140 ° C. or lower.
  • the reaction start temperature of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles is more efficiently arranged on the electrode.
  • the reaction initiation temperature of the thermosetting agent is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder in the conductive particles, and is higher by 5 ° C. or more. More preferably, it is more preferably 10 ° C. or higher.
  • the reaction start temperature of the thermosetting agent means the temperature at which the exothermic peak of DSC starts to rise.
  • the content of the thermosetting agent is not particularly limited.
  • the content of the thermosetting agent with respect to 100 parts by weight of the thermosetting compound is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less, more preferably 75 parts by weight or less. It is easy to fully harden a thermosetting compound as content of a thermosetting agent is more than the said minimum.
  • the content of the thermosetting agent is not more than the above upper limit, it is difficult for an excess thermosetting agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further enhanced.
  • the conductive material preferably contains a flux.
  • the flux is not particularly limited.
  • the flux generally used for soldering etc. can be used.
  • Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an amine compound, and an organic compound.
  • Examples include acid and rosin.
  • 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.
  • organic acid having two or more carboxyl groups examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
  • amine compound examples include cyclohexylamine, dicyclohexylamine, benzylamine, benzhydrylamine, imidazole, benzimidazole, phenylimidazole, carboxybenzimidazole, benzotriazole, carboxybenzotriazole, and the like.
  • the above rosins are rosins whose main component is abietic acid.
  • the rosins include abietic acid and acrylic modified rosin.
  • the flux is preferably a rosin, and more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further enhanced.
  • the melting point (activation temperature) of the flux is preferably 10 ° C. or higher, more preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 200 ° C. or lower, more preferably 190 ° C. Hereinafter, it is more preferably 160 ° C. or lower, further preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower.
  • the melting point (activation temperature) of the flux is preferably 80 ° C. or higher and 190 ° C. or lower.
  • the melting point (activation temperature) of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • Examples of the flux having a melting point (activation temperature) 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.), dicarboxylic acids such as suberic acid (melting point 142 ° C.), benzoic acid (melting point 122 ° C.), malic acid (melting point 130 ° C.) and the like.
  • the boiling point of the flux is preferably 200 ° C. or lower.
  • the melting point of the flux is preferably higher than the melting point of the solder in the conductive particles, and more preferably 5 ° C. or higher. More preferably, it is 10 ° C. or higher.
  • the melting point of the flux is preferably higher than the reaction start temperature of the thermosetting agent, and more preferably 5 ° C or higher. More preferably, it is 10 ° C. or higher.
  • the flux may be dispersed in the conductive material or may be adhered on the surface of the conductive particles.
  • the melting point of the flux is higher than the melting point of the solder in the conductive particles, the solder in the conductive particles can be efficiently aggregated on the electrode portion. This is because, when heat is applied at the time of joining, when the electrode formed on the connection target member is compared with the portion of the connection target member around the electrode, the thermal conductivity of the electrode portion is that of the connection target member portion around the electrode. Due to the fact that it is higher than the thermal conductivity, the temperature rise of the electrode portion is fast. At the stage where the melting point of the solder exceeds the melting point of the conductive particles, the inside of the conductive particles dissolves, but the oxide film formed on the surface does not reach the melting point (activation temperature) of the flux and is not removed.
  • the temperature of the electrode portion since the temperature of the electrode portion first reaches the melting point (activation temperature) of the flux, the oxide film on the surface of the conductive particles that has come preferentially on the electrode is removed, and the solder in the conductive particles becomes the electrode. Can spread on the surface of the surface. Thereby, the solder in electroconductive particle can be efficiently aggregated on an electrode.
  • the content of the flux is preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less.
  • the conductive material may not contain flux. When the content of the flux 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 surfaces of the conductive particles and the electrodes, and the oxide film formed on the surfaces of the conductive particles and the electrodes. Can be more effectively removed.
  • the conductive material is Insulating particles are preferably included.
  • the insulating particles may not be attached to the surface of the solder particles.
  • the insulating particles are preferably present apart from the solder particles.
  • the particle diameter of the insulating particles is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 25 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the particle diameter of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between the connection target members connected by the cured material of the conductive material and the interval between the connection target members connected by the solder portion are It becomes even more moderate.
  • the material for the insulating particles includes an insulating resin and an insulating inorganic substance.
  • the insulating resin include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, cross-linked thermoplastic resins, thermosetting resins, and water-soluble resins. Can be mentioned.
  • Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer.
  • Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate.
  • Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof.
  • Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers.
  • thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose.
  • a water-soluble resin is preferable, and polyvinyl alcohol is more preferable.
  • Examples of the insulating inorganic material include silica and organic-inorganic hybrid particles.
  • the particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle
  • Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the content of the insulating particles in 100% by weight of the conductive material is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 10% by weight or less, more preferably 5% by weight. % Or less.
  • the conductive material may not include the insulating particles. When the content of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between connection target members connected by the cured material of the conductive material and the interval between connection target members connected by the solder portion are It becomes even more moderate.
  • the conductive material may be, for example, a coupling agent, a light-shielding agent, a reactive diluent, an antifoaming agent, a leveling agent, a filler, an extender, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, or a coloring agent.
  • Various additives such as an agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be included.
  • connection structure includes a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection object member and the connection part which has connected the said 2nd connection object member are provided.
  • the material of the connection portion includes the conductive particles described above.
  • the connection portion is the above-described conductive particle or the above-described conductive material.
  • the connection portion is formed of the conductive particles described above or the conductive material described above.
  • the connection portion is preferably a cured product of the conductive material described above.
  • the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
  • the conductive particles or the conductive material described above is used to form the conductive particles or the conductive particles on the surface of the first connection target member having at least one first electrode on the surface.
  • the manufacturing method of the connection structure includes a second connection target having at least one second electrode on the surface of the conductive particle or the conductive material opposite to the first connection target member side.
  • the connection part connecting the first connection target member and the second connection target member is formed by heating the conductive material to a temperature equal to or higher than the melting point of the conductive particles.
  • a step of electrically connecting the first electrode and the second electrode with a solder portion in the connection portion, the conductive electrode or the conductive material is heated above the curing temperature of the thermosetting compound.
  • the specific conductive particles or the specific conductive material is used. Therefore, the conductive particles gather between the first electrode and the second electrode. It is easy to efficiently arrange the conductive particles on the electrode (line). Moreover, it is difficult for some of the conductive particles to be disposed in a region (space) where no electrode is formed, and the amount of conductive 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.
  • the conductive material is not a conductive film, It is preferable to use a conductive paste.
  • the thickness of the solder part between the electrodes is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less.
  • the solder wetted area on the surface of the electrode is preferably 50% or more, more preferably 70% or more, and preferably 100% or less.
  • the conductive particles or the conductive material in the step of arranging the second connection target member and the step of forming the connection portion, the conductive particles or the conductive material is not pressurized,
  • the weight of the second connection target member is preferably added.
  • the conductive particles or the conductive material may include a pressurized pressure that exceeds the force of the weight of the second connection target member. Is preferably not added. In these cases, the uniformity of the amount of solder can be further enhanced in the plurality of solder portions.
  • the thickness of the solder portion can be increased more effectively, and a plurality of conductive particles are likely to gather between the electrodes, and the plurality of conductive particles are arranged more efficiently on the electrodes (lines). be able to.
  • the electrical connection between the laterally adjacent electrodes that should not be connected can be further prevented, and the insulation reliability can be further improved.
  • a conductive paste is used instead of a conductive film, it becomes easy to adjust the thicknesses of the connection part and the solder part depending on the amount of the conductive paste applied.
  • the conductive film in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film having a different thickness or to prepare a conductive film having a predetermined thickness. There is.
  • the melt viscosity of the conductive film compared with the conductive paste, the melt viscosity of the conductive film cannot be sufficiently lowered at the melting temperature of the conductive particles, and the aggregation of the solder in the conductive particles tends to be hindered.
  • FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
  • connection structure 1 shown in FIG. 1 is a connection that connects a first connection target member 2, a second connection target member 3, and the first connection target member 2 and the second connection target member 3.
  • Part 4 is formed of the conductive material described above.
  • the conductive material includes a thermosetting compound, a thermosetting agent, and conductive particles.
  • a conductive paste is used as the conductive material.
  • connection part 4 has a solder part 4A in which a plurality of conductive particles gather and are joined to each other, and a cured part 4B in which a thermosetting compound 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.
  • electroconductive particle does not exist in the connection part 4, in the area
  • a region (cured product portion 4B portion) different from the solder portion 4A there are no conductive particles separated from the solder portion 4A. If the amount is small, conductive particles may be present in a region (cured product portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a. .
  • connection structure 1 As shown in FIG. 1, in the connection structure 1, after a plurality of conductive particles gather between the first electrode 2a and the second electrode 3a and the plurality of conductive particles melt, the conductive particles The melted material solidifies after the surface of the electrode wets and spreads to form the solder portion 4A. For this reason, the connection area of 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts, and the 2nd electrode 3a becomes large. This also increases the conduction reliability and connection reliability in the connection structure 1. In addition, when a flux is contained in the conductive material, the flux is generally gradually deactivated 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, 3a are opposed is a part of the solder part 4XA and is not a conductive particle separated from the solder part 4XA.
  • the amount of conductive particles separated from the solder portion can be reduced, but the conductive particles separated from the solder portion may exist in the cured product portion.
  • connection structure 1X If the use amount of the conductive particles is reduced, it becomes easy to obtain the connection structure 1. If the usage-amount of electroconductive particle is increased, it will become easy to obtain the connection structure 1X.
  • connection structure 1, 1X when the part which 1st electrode 2a and 2nd electrode 3a oppose in the lamination direction of 1st electrode 2a, connection part 4, 4X, and 2nd electrode 3a is seen
  • the solder portions 4A and 4XA in the connection portions 4 and 4X are arranged in 50% or more of the area of 100% of the facing portion between the first electrode 2a and the second electrode 3a.
  • the solder portions 4A and 4XA in the connection portions 4 and 4X satisfy the above-described preferable mode, the conduction reliability can be further improved.
  • the solder portion in the connecting portion is arranged in 50% or more of the area of 100% of the portion facing the two electrodes.
  • the solder portion in the connection portion is disposed in 60% or more of 100% of the area of the portion facing the two electrodes.
  • the solder portion in the connecting portion is arranged in 70% or more of the area of 100% of the portion facing the two electrodes.
  • the solder portion in the connecting portion is disposed in 80% or more of 100% of the area facing the two electrodes.
  • the solder portion in the connection portion is disposed in 90% or more of the area of 100% of the portion facing the two electrodes.
  • connection portion 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, It is preferable that 60% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other. 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, More preferably, 70% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other.
  • connection portion, and the second electrode 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, More preferably, 90% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other. 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, It is particularly preferable that 95% or more of the solder portion in the connection portion is disposed at a portion where the electrode and the second electrode face each other.
  • connection portion 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, It is most preferable that 99% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other.
  • solder part in the connection part satisfies the above-described preferable aspect, the conduction reliability can be further improved.
  • connection structure 1 using the conductive material Next, an example of a method for manufacturing the connection structure 1 using the conductive material according to the embodiment of the present invention will be described.
  • the first connection target member 2 having the first electrode 2a on the surface (upper surface) is prepared.
  • a conductive material 11 including a thermosetting component 11B and a plurality of conductive particles 11A is disposed on the surface of the first connection target member 2 (first Process).
  • the used conductive material 11 contains a thermosetting compound and a thermosetting agent as the thermosetting component 11B.
  • the conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided. After the arrangement of the conductive material 11, the conductive particles 11A are arranged both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
  • the arrangement method of the conductive material 11 is not particularly limited, and examples thereof include application by a dispenser, screen printing, and discharge by an inkjet device.
  • the 2nd connection object member 3 which has the 2nd electrode 3a on the surface (lower surface) is prepared.
  • the 2nd connection object member 3 is arrange
  • the second connection target member 3 is disposed from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.
  • the conductive material 11 is heated above the melting point of the conductive particles 11A (third step).
  • the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (thermosetting compound).
  • the conductive particles 11A that existed in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect).
  • the conductive paste is used instead of the conductive film, the conductive particles 11A are more effectively collected between the first electrode 2a and the second electrode 3a.
  • the conductive particles 11A are melted and joined to each other.
  • the thermosetting component 11B is thermoset. As a result, as shown in FIG.
  • connection portion 4 that connects the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11.
  • the connection part 4 is formed of the conductive material 11
  • the solder part 4A is formed by joining the plurality of conductive particles 11A
  • the cured part 4B is formed by thermosetting the thermosetting component 11B. If the conductive particles 11A are sufficiently moved, the first electrode 2a and the second electrode 2a are moved after the movement of the conductive particles 11A that are not positioned between the first electrode 2a and the second electrode 3a starts. The temperature does not have to be kept constant until the movement of the conductive particles 11A between the electrodes 3a is completed.
  • the solder of the solder particles in the conductive particles 11A and the silver contained in the covering portion of the conductive particles 11A are not alloyed.
  • the conductive material 11 when the conductive material 11 is heated in the third step, the conductive material 11 may be heated to a temperature higher than the melting point of the solder particles, and the conductive particles 11A can be melted at a relatively low temperature.
  • the portion 4A can be formed.
  • the solder part 4A formed by joining a plurality of conductive particles 11A the solder of the solder particles in the conductive particles 11A and the silver contained in the covering part of the conductive particles 11A. Alloyed. For this reason, melting
  • the weight of the second connection target member 3 is added to the conductive material 11.
  • the conductive particles 11A are more effectively collected between the first electrode 2a and the second electrode 3a when the connection portion 4 is formed.
  • the conductive particles 11A try to gather between the first electrode 2a and the second electrode 3a. The tendency for the action to be inhibited increases.
  • the first electrode and the second electrode are overlapped. Even in a state where the alignment is shifted, the shift can be corrected and the first electrode and the second electrode can be connected (self-alignment effect). This is because the molten solder self-aggregating between the first electrode and the second electrode is in contact with the solder between the first electrode and the second electrode and the other components of the conductive material. This is because the area having the smallest area is more stable in terms of energy, and therefore the force to make the connection structure with alignment, which is the connection structure having the smallest area, works. At this time, it is desirable that the conductive material is not cured, and that the viscosity of components other than the conductive particles of the conductive material is sufficiently low at that temperature and time.
  • connection structure 1 shown in FIG. 1 is obtained.
  • the second step and the third step may be performed continuously.
  • the laminated body of the 1st connection object member 2, the electrically-conductive material 11, and the 2nd connection object member 3 which are obtained is moved to a heating part, and the said 3rd connection object is carried out.
  • You may perform a process.
  • the laminate In order to perform the heating, the laminate may be disposed on a heating member, or the laminate may be disposed in a heated space.
  • the heating temperature in the third step is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, preferably 450 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower.
  • the heating method in the third step a method of heating the entire connection structure using a reflow furnace or an oven above the melting point of the conductive particles and the curing temperature of the thermosetting compound, or connecting The method of heating only the connection part of a structure locally is mentioned.
  • instruments used in the method of locally heating include a hot plate, a heat gun that applies hot air, a soldering iron, and an infrared heater.
  • the metal directly under the connection is made of a metal with high thermal conductivity, and other places where heating is not preferred are made of a material with low thermal conductivity such as a fluororesin.
  • the upper surface of the hot plate is preferably formed.
  • the first and second connection target members are not particularly limited. Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor chip, a semiconductor package, LED chip, LED package, a capacitor
  • the first and second connection target members are preferably electronic components.
  • At least one of the first connection target member and the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board.
  • the second connection target member is preferably a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. Resin films, flexible printed boards, flexible flat cables, and rigid flexible boards have the property of being highly flexible and relatively lightweight. When a conductive film is used for the connection of such connection target members, the solder in the conductive particles tends not to collect on the electrodes.
  • the solder in the conductive particles can be efficiently collected on the electrodes,
  • the conduction reliability can be sufficiently increased.
  • the conduction reliability between the electrodes by not applying pressure is improved. The improvement effect can be obtained more effectively.
  • the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode.
  • the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode.
  • the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
  • the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
  • the trivalent metal element include Sn, Al, and Ga.
  • the first electrode and the second electrode are arranged in an area array or a peripheral.
  • the area array is a structure in which electrodes are arranged in a grid pattern on the surface on which the electrodes of the connection target members are arranged.
  • the peripheral is a structure in which electrodes are arranged on the outer periphery of a connection target member.
  • the solder in the conductive particles may be aggregated along the direction perpendicular to the comb, whereas in the area array or peripheral structure, the surface on which the electrodes are arranged In this case, it is necessary that the solder in the conductive particles uniformly aggregate on the entire surface. For this reason, in the conventional method, the amount of solder tends to be non-uniform, whereas in the method of the present invention, the solder in the conductive particles can be arranged more efficiently on the electrode, The solder in the conductive particles can be uniformly aggregated.
  • Thermosetting compound Thermosetting compound 1: Resorcinol type epoxy compound, “Epolite TDC-LC” manufactured by Kyoeisha Chemical Co., epoxy equivalent 120 g / eq
  • Thermosetting compound 2 Epoxy compound, “EP-3300” manufactured by ADEKA, epoxy equivalent 160 g / eq
  • Latent epoxy thermosetting agent 1 “Fujicure 7000” manufactured by T & K TOKA
  • Latent epoxy thermosetting agent 2 “HXA-3922HP” manufactured by Asahi Kasei E-Materials
  • Flux 1 “Glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.
  • Conductive particles 1 solder particles, melting point 139 ° C., using the solder particles selected from Mitsui Kinzoku “Sn42Bi58”, conductive particles having a coating portion formed by electroless plating, particle diameter: 31 ⁇ m, (Thickness: 0.5 ⁇ m)
  • Conductive particles with a coating formed by electroless plating 50 g of solder particles having a particle size of 30 ⁇ m were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate and 1000 g of ion-exchanged water was prepared, and 50 g of solder particles from which the oxide film had been removed was added and mixed to obtain a suspension. To the obtained suspension, 30 g of thiomalic acid, 80 g of N-acetylimidazole and 10 g of sodium hypophosphite were added and mixed to obtain a plating solution. A coating portion was formed by electroless plating by adjusting the pH of the obtained plating solution to 9 using an ammonia solution of 10% by weight and performing electroless plating at 25 ° C. for 20 minutes. Conductive particles were obtained.
  • Conductive particles 2 (SnBi solder particles, melting point 139 ° C., using the solder particles selected from Mitsui Kinzoku “Sn42Bi58”, conductive particles having a metal part and a covering part formed by electroless plating, particle diameter: 33 ⁇ m, (Metal part thickness: 1 ⁇ m, coating part thickness: 0.5 ⁇ m)
  • Conductive particles having a metal part and a covering part formed by electroless plating 50 g of solder particles having a particle size of 30 ⁇ m were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. Using 50 g of solder particles from which the oxide film had been removed, palladium was attached by a two-component activation method to obtain solder particles with palladium attached to the surface. A solution containing 20 g of nickel sulfate and 1000 g of ion-exchanged water was prepared, and 30 g of solder particles with palladium attached to the surface were mixed and mixed to obtain a first suspension.
  • first plating solution 30 g of citric acid, 80 g of sodium hypophosphite, and 10 g of acetic acid were added and mixed to obtain a first plating solution.
  • the pH of the obtained first plating solution is adjusted to 10 with an ammonia solution of 10% by weight, and electroless plating is performed at 60 ° C. for 20 minutes.
  • the formed conductive particles were obtained.
  • a solution containing 5 g of silver nitrate and 1000 g of ion-exchanged water was prepared, and 50 g of conductive particles having a metal part formed therein were mixed and mixed to obtain a second suspension.
  • the resulting second suspension was mixed with 30 g of succinimide, 80 g of N-acetylimidazole and 5 g of glyoxylic acid to obtain a second plating solution.
  • the pH of the obtained second plating solution to 9 using an ammonia solution of 10% by weight and performing electroless plating at 20 ° C. for 20 minutes, the metal part and The electroconductive particle in which the coating part was formed was obtained.
  • Conductive particles 3 (SnBi solder particles, melting point 139 ° C., solder particles selected from Mitsui Kinzoku Co., Ltd. “Sn42Bi58”, conductive particles having a coating part formed by electrolytic plating, particle diameter: 32 ⁇ m, coating part thickness : 1 ⁇ m)
  • Conductive particles having a coating formed by electrolytic plating 50 g of solder particles having a particle size of 30 ⁇ m were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate, 1000 g of ion-exchanged water, 5 g of 1,3-dibromo-5,5-dimethylhydantoin, and 3 g of thiomalic acid was prepared, and 50 g of solder particles from which the oxide film had been removed were put in the solution. Mix to obtain a suspension. Conductivity in which a coating portion was formed by electrolytic plating by performing electrolytic plating under the conditions of anode: platinum, cathode: phosphorous copper, current density: 1 A / dm 2 using the obtained suspension. Particles were obtained.
  • Conductive particles 4 SAC particles, melting point 218 ° C., “M705” manufactured by Senju Metal Co., Ltd., particle diameter: 30 ⁇ m
  • Conductive particles 5 solder particles, melting point 139 ° C., solder particles selected from Mitsui Kinzoku Co., Ltd. “Sn42Bi58”, conductive particles having a coating portion formed by electrolytic plating, particle diameter: 35 ⁇ m, thickness of the coating portion : 2.5 ⁇ m
  • Conductive particles having a coating formed by electrolytic plating 50 g of solder particles having a particle size of 30 ⁇ m were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate, 1000 g of ion-exchanged water, 5 g of 1,3-dibromo-5,5-dimethylhydantoin, and 3 g of thiomalic acid was prepared, and 50 g of solder particles from which the oxide film had been removed were put in the solution. Mix to obtain a suspension. Conductivity in which a coating portion was formed by electrolytic plating by performing electrolytic plating under the conditions of anode: platinum, cathode: phosphorous copper, current density: 3 A / dm 2 using the obtained suspension. Particles were obtained.
  • Conductive particles 6 solder particles, melting point 139 ° C., using solder particles selected from Mitsui Kinzoku “Sn42Bi58”, conductive particles having a coating portion formed by electrolytic plating, particle diameter: 33 ⁇ m, thickness of the coating portion : 1.5 ⁇ m
  • Conductive particles having a coating formed by electrolytic plating 50 g of solder particles having a particle size of 30 ⁇ m were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate, 1000 g of ion-exchanged water, 5 g of 1,3-dibromo-5,5-dimethylhydantoin, and 3 g of thiomalic acid was prepared. 50 g of solder particles from which the oxide film has been removed were added to the solution and mixed to obtain a suspension. Conductivity in which a coating portion was formed by electrolytic plating by performing electrolytic plating under the conditions of anode: platinum, cathode: phosphorous copper, current density: 2 A / dm 2 using the obtained suspension. Particles were obtained.
  • Conductive particles 7 solder particles, melting point 139 ° C., using the solder particles selected from “L20-30050” manufactured by Senju Metal Co., Ltd., conductive particles having a coating portion formed by electroless plating, particle diameter: 31 ⁇ m, coating Part thickness: 0.08 ⁇ m
  • Conductive particles with a coating formed by electroless plating 50 g of solder particles having a particle size of 30 ⁇ m were placed in a solution containing 1 g of nitrilotriacetic acid and 50 g of 10 wt% sodium hydroxide, stirred at 50 ° C. for 5 minutes, and washed with water to remove the oxide film on the solder surface. . In a solution containing 2 g of palladium sulfate and 100 g of ion-exchanged water, 50 g of solder particles from which the oxide film had been removed was put, and palladium was adhered to the surface of the solder particles.
  • ion exchange water 10 g of ethylenediaminetetraacetic acid, 10 g of nitrilotriacetic acid, 30 g of sodium hydrogen phosphate, 30 g of sodium hydroxide, 3 g of silver nitrate, and 1 g of polyethylene glycol (polyethylene glycol 1000) are mixed.
  • a plating solution was obtained.
  • the resulting plating solution was adjusted to have a pH of 8 using a 10 wt% ammonia solution.
  • 50 g of solder particles to which palladium is attached and 6 g of sodium borohydride are placed in a plating solution, and electroless plating is performed at 25 ° C. for 20 minutes. Sex particles were obtained.
  • Conductive particles 8 (SnBi solder particles, melting point 139 ° C., solder particles selected from Senju Metal Co., Ltd. “L20-30050”, conductive particles having a coating formed by electroless plating, particle diameter: 31 ⁇ m, coating Part thickness: 0.12 ⁇ m)
  • Conductive particles with a coating formed by electroless plating 50 g of solder particles having a particle size of 30 ⁇ m were placed in a solution containing 1 g of nitrilotriacetic acid and 50 g of 10 wt% sodium hydroxide, stirred at 50 ° C. for 5 minutes, and washed with water to remove the oxide film on the solder surface. . In a solution containing 2 g of palladium sulfate and 100 g of ion-exchanged water, 50 g of solder particles from which the oxide film had been removed was put, and palladium was adhered to the surface of the solder particles.
  • ion-exchanged water 10 g of tetrasodium ethylenediaminetetraacetate, 10 g of disodium nitrilotriacetate, 30 g of sodium hydrogen phosphate, 30 g of sodium hydroxide, 7 g of silver methanesulfonate, and 1 g of polyethylene glycol (polyethylene glycol 1000) And mixed to obtain a plating solution.
  • the obtained plating solution was adjusted using a 10 wt% sulfuric acid solution so that the pH was 3. 50 g of solder particles to which palladium is attached and 6 g of oxalic acid are placed in a plating solution, and electroless plating is performed at 25 ° C. for 20 minutes, whereby conductive particles having a coating portion formed by electroless plating are obtained. Obtained.
  • Conductive particles 9 solder particles, melting point 139 ° C., using the solder particles selected from Senju Metal Co., Ltd. “L20-30050”, conductive particles with covering portions formed by electroless plating, particle diameter: 31 ⁇ m, covering Part thickness: 0.15 ⁇ m
  • Conductive particles with a coating formed by electroless plating 50 g of solder particles having a particle size of 30 ⁇ m were placed in a solution containing 1 g of nitrilotriacetic acid and 50 g of 10 wt% sodium hydroxide, stirred at 50 ° C. for 5 minutes, and washed with water to remove the oxide film on the solder surface. . In a solution containing 2 g of palladium sulfate and 100 g of ion-exchanged water, 50 g of solder particles from which the oxide film had been removed was put, and palladium was adhered to the surface of the solder particles.
  • ion-exchanged water 10 g of tetrasodium ethylenediaminetetraacetate, 10 g of disodium nitrilotriacetate, 30 g of sodium hydrogen phosphate, 30 g of sodium hydroxide, 7 g of silver methanesulfonate, and 1 g of polyethylene glycol (polyethylene glycol 1000) And mixed to obtain a plating solution.
  • the obtained plating solution was adjusted to have a pH of 7 using a 10 wt% sodium hydroxide solution.
  • 50 g of solder particles to which palladium is attached and 6 g of formic acid are put in a plating solution and electroless plating is performed at 40 ° C. for 20 minutes to obtain conductive particles having a coating portion formed by electroless plating. It was.
  • Metal part thickness and coating part thickness The thickness of the metal part and the thickness of the covering part were measured by the method described above.
  • Examples 1 to 8 and Comparative Example 1 (1) Production of conductive material The components shown in Table 1 below are blended in the blending amounts shown in Table 1 below, and the conductive material (anisotropic conductive paste) is mixed and defoamed with a planetary stirrer. Obtained.
  • connection structure area array substrate
  • connection structure under condition A As a second connection target member, a copper electrode of 250 ⁇ m at a pitch of 400 ⁇ m is arranged in an area array on the surface of a semiconductor chip body (size 5 ⁇ 5 mm, thickness 0.4 mm), and a passivation film ( A semiconductor chip on which polyimide, a thickness of 5 ⁇ m, and an opening diameter of the electrode portion of 200 ⁇ m were formed was prepared.
  • the number of copper electrodes is 10 ⁇ 10 in total per 100 semiconductor chips.
  • the same pattern is formed on the surface of the glass epoxy substrate body (size 20 ⁇ 20 mm, thickness 1.2 mm, material FR-4) with respect to the electrode of the second connection target member.
  • positioned was prepared.
  • the level difference between the surface of the copper electrode and the surface of the solder resist film is 15 ⁇ m, and the solder resist film protrudes from the copper electrode.
  • the conductive material (anisotropic conductive paste) immediately after fabrication was applied to the upper surface of the glass epoxy substrate so as to have a thickness of 100 ⁇ m, thereby forming an anisotropic conductive paste layer.
  • a semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other.
  • the weight of the semiconductor chip is added to the anisotropic conductive paste layer.
  • the anisotropic conductive paste layer was heated so that the temperature became 139 ° C. (melting point of solder) after 5 seconds from the start of temperature increase. Further, 15 seconds after the start of temperature increase, the anisotropic conductive paste layer was heated to 160 ° C. to cure the anisotropic conductive paste layer, thereby obtaining a connection structure. No pressure was applied during heating.
  • connection structure under condition B A connection structure (area array substrate) was produced in the same manner as in Condition A except that the following changes were made.
  • the viscosity ( ⁇ 25) at 25 ° C. of the conductive material (anisotropic conductive paste) immediately after production was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and 5 rpm. . ⁇ 25 was determined according to the following criteria.
  • ⁇ 25 is less than 20 Pa ⁇ s ⁇ : ⁇ 25 is 20 Pa ⁇ s or more and 600 Pa ⁇ s or less ⁇ : ⁇ 25 exceeds 600 Pa ⁇ s
  • Viscosity ( ⁇ mp) of conductive material (anisotropic conductive paste) at melting point of conductive particles Strain control 1 rad using STRESSTECH (manufactured by REOLOGICA) as the conductive material (anisotropic conductive paste) immediately after production. The measurement was performed under the conditions of a frequency of 1 Hz, a heating rate of 20 ° C./min, and a measurement temperature range of 40 ° C. to the melting point of the conductive particles. In this measurement, the viscosity at the melting point of the conductive particles was read and used as the viscosity ( ⁇ mp) of the conductive material (anisotropic conductive paste) at the melting point of the conductive particles. ⁇ mp was determined according to the following criteria.
  • ⁇ mp is less than 0.1 Pa ⁇ s ⁇ : ⁇ mp is 0.1 Pa ⁇ s or more and 5 Pa ⁇ s or less ⁇ : ⁇ mp is more than 5 Pa ⁇ s
  • ⁇ : ⁇ 2 / ⁇ 1 is less than 2 ⁇ : ⁇ 2 / ⁇ 1 is 2 or more and less than 3 ⁇ : ⁇ 2 / ⁇ 1 is 3 or more
  • Solder wettability A conductive material (anisotropic conductive paste) was prepared after standing for 3 days at 25 ° C. and 50% humidity used in the evaluation of (3) above. Using these conductive materials (anisotropic conductive paste), the wettability of the solder was evaluated. Solder wettability was evaluated as follows. Solder wettability was determined according to the following criteria.
  • ⁇ The ratio of the solder wet area to the gold electrode is 70% or more.
  • ⁇ The ratio of the solder wet area to the gold electrode is 40% or more and less than 70%.
  • X The ratio of the solder wet area to the gold electrode is less than 40%.
  • solder placement accuracy on the electrode In the connection structure obtained under the conditions A and B, the first electrode and the second electrode in the stacking direction of the first electrode, the connection portion, and the second electrode.
  • the ratio X of the area where the solder portion in the connecting portion is arranged in the area of 100% of the portion facing the first electrode and the second electrode is evaluated.
  • the placement accuracy of the solder on the electrode was determined according to the following criteria.
  • Ratio X is 70% or more ⁇ : Ratio X is 60% or more and less than 70% ⁇ : Ratio X is 50% or more and less than 60% X: Ratio X is less than 50%
  • ⁇ 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 ⁇
  • Impact resistance The connection structure used for the evaluation of (6) above was prepared. These connection structures were dropped from a position having a height of 70 cm, and the impact resistance was evaluated by confirming the conduction reliability in the same manner as in the evaluation of (6) above. Impact resistance was determined according to the following criteria based on the rate of increase in resistance value from the average value of connection resistance obtained in the evaluation of (6) above.

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  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Powder Metallurgy (AREA)

Abstract

Provided are conductive particles which can be easily mounted at low temperatures, and which are capable of effectively improving impact resistance of connection parts. Conductive particles according to the present invention are provided with: solder particles having a melting point lower than 200˚C; and coating parts which are provided to the surfaces of the solder particles. The coating parts include silver.

Description

導電性粒子、導電材料及び接続構造体Conductive particles, conductive materials, and connection structures
　本発明は、はんだを含む導電性粒子に関する。また、本発明は、上記導電性粒子を用いた導電材料及び接続構造体に関する。 The present invention relates to conductive particles containing solder. The present invention also relates to a conductive material and a connection structure using the conductive particles.
　異方性導電ペースト及び異方性導電フィルム等の異方性導電材料が広く知られている。上記異方性導電材料では、バインダー中に導電性粒子が分散されている。 Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder.
　上記異方性導電材料は、各種の接続構造体を得るために用いられる。上記異方性導電材料による接続としては、例えば、フレキシブルプリント基板とガラス基板との接続（ＦＯＧ（Ｆｉｌｍ　ｏｎ　Ｇｌａｓｓ））、半導体チップとフレキシブルプリント基板との接続（ＣＯＦ（Ｃｈｉｐ　ｏｎ　Ｆｉｌｍ））、半導体チップとガラス基板との接続（ＣＯＧ（Ｃｈｉｐ　ｏｎ　Ｇｌａｓｓ））、並びにフレキシブルプリント基板とガラスエポキシ基板との接続（ＦＯＢ（Ｆｉｌｍ　ｏｎ　Ｂｏａｒｄ））等が挙げられる。 The anisotropic conductive material is used for obtaining various connection structures. Examples of the connection using the anisotropic conductive material include a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), and a semiconductor. Examples include connection between a chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), and the like.
　上記異方性導電材料により、例えば、フレキシブルプリント基板の電極とガラスエポキシ基板の電極とを電気的に接続する際には、ガラスエポキシ基板上に、導電性粒子を含む異方性導電材料を配置する。次に、フレキシブルプリント基板を積層して、加熱及び加圧する。これにより、異方性導電材料を硬化させて、導電性粒子を介して電極間を電気的に接続して、接続構造体を得る。 For example, when electrically connecting the electrode of the flexible printed circuit board and the electrode of the glass epoxy substrate by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is disposed on the glass epoxy substrate. To do. Next, a flexible printed circuit board is laminated, and heated and pressurized. As a result, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.
　上記異方性導電材料等の導電材料が下記の特許文献１～３に開示されている。 Conductive materials such as the above anisotropic conductive materials are disclosed in the following Patent Documents 1 to 3.
　下記の特許文献１には、導電性粒子と、該導電性粒子の融点で硬化が完了しない樹脂成分とを含む異方性導電材料が記載されている。上記導電性粒子としては、具体的には、錫（Ｓｎ）、インジウム（Ｉｎ）、ビスマス（Ｂｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、鉛（Ｐｂ）、カドミウム（Ｃｄ）、ガリウム（Ｇａ）、銀（Ａｇ）及びタリウム（Ｔｌ）等の金属や、これらの金属の合金が挙げられている。 The following Patent Document 1 describes an anisotropic conductive material containing conductive particles and a resin component that cannot be cured at the melting point of the conductive particles. Specifically, as the conductive particles, tin (Sn), indium (In), bismuth (Bi), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd), gallium (Ga) ), Silver (Ag), thallium (Tl) and other metals, and alloys of these metals.
　特許文献１では、上記導電性粒子の融点よりも高く、かつ上記樹脂成分の硬化が完了しない温度に、異方性導電材料を加熱する樹脂加熱ステップと、上記樹脂成分を硬化させる樹脂成分硬化ステップとを経て、電極間を電気的に接続することが記載されている。また、特許文献１には、特許文献１の図８に示された温度プロファイルで実装を行うことが記載されている。特許文献１では、異方性導電材料が加熱される温度にて硬化が完了しない樹脂成分内で、導電性粒子が溶融する。 In Patent Document 1, a resin heating step for heating the anisotropic conductive material to a temperature higher than the melting point of the conductive particles and at which the curing of the resin component is not completed, and a resin component curing step for curing the resin component The electrical connection between the electrodes is described. Patent Document 1 describes that mounting is performed with the temperature profile shown in FIG. In Patent Document 1, conductive particles melt in a resin component that is not completely cured at a temperature at which the anisotropic conductive material is heated.
　下記の特許文献２には、熱硬化性樹脂を含む樹脂層と、はんだ粉と、硬化剤とを含み、上記はんだ粉と上記硬化剤とが上記樹脂層中に存在する接着テープ（導電材料）が開示されている。 Patent Document 2 below includes an adhesive tape (conductive material) that includes a resin layer containing a thermosetting resin, solder powder, and a curing agent, and the solder powder and the curing agent are present in the resin layer. Is disclosed.
　下記の特許文献３には、粒子と、該粒子の表面に無電解メッキ法により形成された導電性被膜とを備える導電性粒子が開示されている。上記導電性被膜は、無電解メッキにより内側から順に形成されたニッケルメッキ被膜、錫メッキ被膜、及びビスマスメッキ被膜を有する。また、上記導電性被膜は、最外側の表面に銀メッキ被膜を有する。上記導電性粒子は、異方性導電材料に用いることができる。 The following Patent Document 3 discloses conductive particles including particles and a conductive coating formed on the surface of the particles by an electroless plating method. The conductive coating includes a nickel plating coating, a tin plating coating, and a bismuth plating coating formed in order from the inside by electroless plating. The conductive coating has a silver plating coating on the outermost surface. The conductive particles can be used for anisotropic conductive materials.
特開２００４－２６０１３１号公報JP 2004-260131 A ＷＯ２００８／０２３４５２Ａ１WO2008 / 023452A1 ＷＯ２００６／０８５４８１Ａ１WO2006 / 085481A1
　従来の導電材料では、導電性粒子又ははんだ粒子が酸化されやすく、接続される電極間の接続部の耐衝撃性を十分に高めることができないことがある。特に、導電材料を用いた実装後の基板等において、接続部の耐衝撃性が十分に高くない場合には、基板の落下等の衝撃により接続部にクラック等が発生することがある。結果として、電極間の導通信頼性を十分に高めることは困難である。 In conventional conductive materials, conductive particles or solder particles are likely to be oxidized, and the impact resistance of the connection portion between the connected electrodes may not be sufficiently increased. In particular, in a substrate or the like after mounting using a conductive material, if the impact resistance of the connection portion is not sufficiently high, a crack or the like may occur in the connection portion due to an impact such as dropping of the substrate. As a result, it is difficult to sufficiently improve the conduction reliability between the electrodes.
　接続部の耐衝撃性を高める方法として、従来の導電性粒子又ははんだ粒子の代わりに、ＳＡＣ（スズ－銀－銅合金）粒子を用いる方法が挙げられる。しかしながら、ＳＡＣ粒子は融点が２００℃以上であり、低温で実装することは困難である。 As a method for improving the impact resistance of the connecting portion, there is a method using SAC (tin-silver-copper alloy) particles instead of conventional conductive particles or solder particles. However, SAC particles have a melting point of 200 ° C. or higher and are difficult to mount at low temperatures.
　本発明の目的は、低温で容易に実装することができ、さらに、接続部の耐衝撃性を効果的に高めることができる導電性粒子を提供することである。また、本発明の目的は、上記導電性粒子を用いた導電材料及び接続構造体を提供することである。 An object of the present invention is to provide conductive particles that can be easily mounted at a low temperature and that can effectively increase the impact resistance of a connection portion. Another object of the present invention is to provide a conductive material and a connection structure using the conductive particles.
　本発明の広い局面によれば、融点が２００℃未満のはんだ粒子と、前記はんだ粒子の表面上に配置された被覆部とを備え、前記被覆部が、銀を含む、導電性粒子が提供される。 According to a broad aspect of the present invention, there is provided conductive particles comprising solder particles having a melting point of less than 200 ° C. and a coating portion disposed on the surface of the solder particles, wherein the coating portion contains silver. The
　本発明に係る導電性粒子のある特定の局面では、前記はんだ粒子が、スズ及びビスマスを含む。 In a specific aspect of the conductive particles according to the present invention, the solder particles include tin and bismuth.
　本発明に係る導電性粒子のある特定の局面では、導電性粒子１００重量％中、前記銀の含有量が、１重量％以上、２０重量％以下である。 In a specific aspect of the conductive particles according to the present invention, the content of the silver is 1% by weight or more and 20% by weight or less in 100% by weight of the conductive particles.
　本発明に係る導電性粒子のある特定の局面では、前記はんだ粒子の表面積全体１００％中、前記はんだ粒子の表面の前記被覆部により覆われている表面積が、８０％以上である。 In a specific aspect of the conductive particles according to the present invention, the surface area covered by the coating portion on the surface of the solder particles is 80% or more in the entire surface area of the solder particles of 100%.
　本発明に係る導電性粒子のある特定の局面では、前記被覆部の厚みが、０．１μｍ以上、５μｍ以下である。 In a specific aspect of the conductive particle according to the present invention, the thickness of the covering portion is 0.1 μm or more and 5 μm or less.
　本発明に係る導電性粒子のある特定の局面では、前記導電性粒子が、前記はんだ粒子の外表面と前記被覆部との間に、ニッケルを含む金属部を備える。 In a specific aspect of the conductive particle according to the present invention, the conductive particle includes a metal part containing nickel between the outer surface of the solder particle and the covering part.
　本発明の広い局面によれば、上述した導電性粒子と、熱硬化性化合物とを含む、導電材料が提供される。 According to a wide aspect of the present invention, there is provided a conductive material including the above-described conductive particles and a thermosetting compound.
　本発明に係る導電材料のある特定の局面では、導電材料１００重量％中、前記導電性粒子の含有量が、５０重量％を超える。 In a specific aspect of the conductive material according to the present invention, the content of the conductive particles exceeds 50% by weight in 100% by weight of the conductive material.
　本発明に係る導電材料のある特定の局面では、前記熱硬化性化合物が、ポリエーテル骨格を有する熱硬化性化合物を含む。 In a specific aspect of the conductive material according to the present invention, the thermosetting compound includes a thermosetting compound having a polyether skeleton.
　本発明に係る導電材料のある特定の局面では、前記導電材料が、融点が５０℃以上、１４０℃以下であるフラックスを含む。 In a specific aspect of the conductive material according to the present invention, the conductive material includes a flux having a melting point of 50 ° C. or higher and 140 ° C. or lower.
　本発明に係る導電材料のある特定の局面では、２５℃での粘度が、２０Ｐａ・ｓ以上、６００Ｐａ・ｓ以下である。 In a specific aspect of the conductive material according to the present invention, the viscosity at 25 ° C. is 20 Pa · s or more and 600 Pa · s or less.
　本発明に係る導電材料のある特定の局面では、前記導電材料が、導電ペーストである。 In a specific aspect of the conductive material according to the present invention, the conductive material is a conductive paste.
　本発明の広い局面によれば、少なくとも１つの第１の電極を表面に有する第１の接続対象部材と、少なくとも１つの第２の電極を表面に有する第２の接続対象部材と、前記第１の接続対象部材と、前記第２の接続対象部材とを接続している接続部とを備え、前記接続部の材料が、上述した導電性粒子を含み、前記第１の電極と前記第２の電極とが、前記接続部中のはんだ部により電気的に接続されている、接続構造体が提供される。 According to a wide aspect of the present invention, a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection target member and a connection part connecting the second connection target member, wherein the material of the connection part includes the conductive particles described above, and 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.
　本発明に係る接続構造体のある特定の局面では、前記第１の電極と前記接続部と前記第２の電極との積層方向に前記第１の電極と前記第２の電極との対向し合う部分をみたときに、前記第１の電極と前記第２の電極との対向し合う部分の面積１００％中の５０％以上に、前記接続部中のはんだ部が配置されている。 In a specific aspect of the connection structure according to the present invention, 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. When the portion is viewed, 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.
　本発明に係る導電性粒子は、融点が２００℃未満のはんだ粒子と、上記はんだ粒子の表面上に配置された被覆部とを備える。本発明に係る導電性粒子では、上記被覆部が、銀を含む。本発明に係る導電性粒子では、上記の構成が備えられているので、低温で容易に実装することができ、さらに、接続部の耐衝撃性を効果的に高めることができる。 The conductive particles according to the present invention include solder particles having a melting point of less than 200 ° C. and a covering portion disposed on the surface of the solder particles. In the electroconductive particle which concerns on this invention, the said coating | coated part contains silver. Since the conductive particle according to the present invention has the above-described configuration, it can be easily mounted at a low temperature, and the impact resistance of the connection portion can be effectively enhanced.
図１は、本発明の一実施形態に係る導電材料を用いて得られる接続構造体を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention. 図２（ａ）～（ｃ）は、本発明の一実施形態に係る導電材料を用いて、接続構造体を製造する方法の一例の各工程を説明するための断面図である。2A to 2C are cross-sectional views for explaining each step of an example of a method for manufacturing a connection structure using a conductive material according to an embodiment of the present invention. 図３は、接続構造体の変形例を示す断面図である。FIG. 3 is a cross-sectional view showing a modification of the connection structure. 図４は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。FIG. 4 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention. 図５は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。FIG. 5 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
　以下、本発明の詳細を説明する。 Hereinafter, the details of the present invention will be described.
　（導電性粒子）
　本発明に係る導電性粒子は、はんだ粒子と、該はんだ粒子の表面上に配置された被覆部とを備える。本発明に係る導電性粒子では、上記はんだ粒子の融点は、２００℃未満である。本発明に係る導電性粒子では、上記被覆部は、銀を含む。 (Conductive particles)
The electroconductive particle which concerns on this invention is equipped with a solder particle and the coating | coated part arrange | positioned on the surface of this solder particle. In the electroconductive particle which concerns on this invention, melting | fusing point of the said solder particle is less than 200 degreeC. In the electroconductive particle which concerns on this invention, the said coating | coated part contains silver.
　本発明では、上記の構成が備えられているので、低温で容易に実装することができ、さらに、接続部の耐衝撃性を効果的に高めることができる。 In the present invention, since the above configuration is provided, it can be easily mounted at a low temperature, and the impact resistance of the connection portion can be effectively increased.
　また、接続構造体の作製時には、スクリーン印刷等によって基板等の接続対象部材上に導電性粒子を含む導電材料が配置された後、電極間が電気的に接続されるまでに、一定期間放置されることがある。従来の導電性粒子では、例えば、一定期間放置されている間に、導電性粒子から金属イオンが溶出することがある。溶出した金属イオンは、導電材料中の熱硬化性化合物等の硬化を促進させ、導電材料を増粘させることがある。結果として、電極上に導電性粒子におけるはんだを効率的に配置することができず、電極間の導通信頼性が低下することがある。本発明では、上記の構成が採用されているので、導電性粒子を含む導電材料が配置された後に一定期間放置されても、導電材料の増粘を防止し、電極上に導電性粒子におけるはんだを効率的に配置することができ、電極間の導通信頼性を十分に高めることができる。 Further, when the connection structure is manufactured, after a conductive material containing conductive particles is arranged on a connection target member such as a substrate by screen printing or the like, it is left for a certain period until the electrodes are electrically connected. Sometimes. In the conventional conductive particles, for example, metal ions may be eluted from the conductive particles while being left for a certain period of time. The eluted metal ions may accelerate the curing of the thermosetting compound in the conductive material and may increase the viscosity of the conductive material. As a result, the solder in the conductive particles cannot be efficiently arranged on the electrodes, and the conduction reliability between the electrodes may be lowered. In the present invention, since the above configuration is adopted, even if the conductive material containing the conductive particles is placed and left for a certain period of time, the conductive material is prevented from thickening and the solder in the conductive particles on the electrode is prevented. Can be arranged efficiently, and the conduction reliability between the electrodes can be sufficiently enhanced.
　さらに、本発明では、電極幅及び電極間幅が狭い電極に対応するために、はんだ粒子の粒子径を小さくしても、はんだ粒子の表面の酸化を防止することができ、はんだの濡れ性を良好に保つことができる。従来の導電材料では、電極幅又は電極間幅が狭い場合に、電極上にはんだを寄せ集め難い傾向がある。本発明では、電極幅又は電極間幅が狭くても、電極上に導電性粒子におけるはんだを十分に寄せ集めることができる。 Furthermore, in the present invention, since it corresponds to an electrode having a narrow electrode width and inter-electrode width, even if the particle diameter of the solder particles is reduced, the surface of the solder particles can be prevented from being oxidized, and the solder wettability can be reduced. Can keep good. In a conventional conductive material, when the electrode width or the inter-electrode width is narrow, there is a tendency that it is difficult to gather solder on the electrodes. In the present invention, even if the electrode width or the inter-electrode width is narrow, the solder in the conductive particles can be sufficiently gathered on the electrodes.
　本発明では、上記のような効果を得るために、上記導電性粒子が銀を含む被覆部を備えることは大きく寄与する。 In the present invention, in order to obtain the above-described effect, it is greatly contributed that the conductive particles have a covering portion containing silver.
　また、本発明では、上記の構成が備えられているので、電極間を電気的に接続した場合に、複数の導電性粒子が、上下の対向した電極間に集まりやすく、複数の導電性粒子を電極（ライン）上に効率的に配置することができる。また、複数の導電性粒子の一部が、電極が形成されていない領域（スペース）に配置され難く、電極が形成されていない領域に配置される導電性粒子の量をかなり少なくすることができる。従って、電極間の導通信頼性を高めることができる。しかも、接続されてはならない横方向に隣接する電極間の電気的な接続を防ぐことができ、絶縁信頼性を高めることができる。 In the present invention, since the above-described configuration is provided, when the electrodes are electrically connected, the plurality of conductive particles are likely to gather between the upper and lower electrodes, and the plurality of conductive particles are It can arrange | position efficiently on an electrode (line). Moreover, it is difficult for some of the plurality of conductive particles to be disposed in a region (space) where no electrode is formed, and the amount of conductive 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.
　さらに、本発明では、電極間の位置ずれを防ぐことができる。本発明では、導電性粒子を含む導電材料を上面に配置した第１の接続対象部材に、第２の接続対象部材を重ね合わせた際に、第１の電極と第２の電極とのアライメントがずれた状態でも、そのずれを補正して、第１の電極と第２の電極とを接続させることができる（セルフアライメント効果）。 Furthermore, in the present invention, it is possible to prevent displacement between the electrodes. In the present invention, when the second connection target member is superimposed on the first connection target member having the conductive material containing conductive particles disposed on the upper surface, the alignment between the first electrode and the second electrode is performed. Even in a shifted state, the shift can be corrected and the first electrode and the second electrode can be connected (self-alignment effect).
　図４は、本発明の第１の実施形態に係る導電性粒子を示す断面図である。 FIG. 4 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
　図４に示す導電性粒子２１は、はんだ粒子２２と、はんだ粒子２２の表面上に配置された被覆部２３とを備える。はんだ粒子２２の融点は、２００℃未満である。被覆部２３は、銀を含む。被覆部２３は、はんだ粒子２２の表面を被覆している。導電性粒子２１は、はんだ粒子２２の表面が被覆部２３により被覆された被覆粒子である。上記被覆部は、上記はんだ粒子の表面を完全に被覆していてもよく、上記はんだ粒子の表面を完全に被覆していなくてもよい。上記はんだ粒子は、上記被覆部によって被覆されていない部分を有していてもよい。 4 includes a solder particle 22 and a covering portion 23 disposed on the surface of the solder particle 22. The conductive particle 21 illustrated in FIG. The melting point of the solder particles 22 is less than 200 ° C. The covering portion 23 contains silver. The covering portion 23 covers the surface of the solder particle 22. The conductive particles 21 are coated particles in which the surface of the solder particles 22 is coated with the coating portion 23. The covering portion may completely cover the surface of the solder particles, or may not completely cover the surface of the solder particles. The solder particles may have a portion that is not covered by the covering portion.
　図５は、本発明の第２の実施形態に係る導電性粒子を示す断面図である。 FIG. 5 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
　図５に示す導電性粒子３１は、はんだ粒子２２と、はんだ粒子２２の表面上に配置された金属部３２と、金属部３２の表面上に配置された被覆部２３とを備える。導電性粒子３１は、はんだ粒子２２と被覆部２３との間に、金属部３２を備える。金属部３２は、はんだ粒子２２の表面を被覆している。被覆部２３は、金属部３２の表面を被覆している。被覆部２３は、銀を含む。金属部３２は、ニッケルを含む。導電性粒子３１は、はんだ粒子２２の表面が金属部３２及び被覆部２３により被覆された被覆粒子である。 5 includes a solder particle 22, a metal part 32 disposed on the surface of the solder particle 22, and a covering part 23 disposed on the surface of the metal part 32. The conductive particle 31 illustrated in FIG. The conductive particle 31 includes a metal part 32 between the solder particle 22 and the covering part 23. The metal part 32 covers the surface of the solder particle 22. The covering portion 23 covers the surface of the metal portion 32. The covering portion 23 contains silver. The metal part 32 contains nickel. The conductive particle 31 is a coated particle in which the surface of the solder particle 22 is coated with the metal portion 32 and the covering portion 23.
　上記導電性粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上、さらに好ましくは３μｍ以上、特に好ましくは５μｍ以上であり、好ましくは１００μｍ以下、より好ましくは４０μｍ以下、より一層好ましくは３０μｍ以下、さらに好ましくは２０μｍ以下、特に好ましくは１５μｍ以下、最も好ましくは１０μｍ以下である。上記導電性粒子の粒子径が、上記下限以上及び上記上限以下であると、導電性粒子におけるはんだを電極上により一層効率的に配置することができる。上記導電性粒子の粒子径は、５μｍ以上、３０μｍ以下であることが特に好ましい。 The particle diameter of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm or more, particularly preferably 5 μm or more, preferably 100 μm or less, more preferably 40 μm or less, and even more preferably. Is 30 μm or less, more preferably 20 μm or less, particularly preferably 15 μm or less, and most preferably 10 μm or less. When the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be arranged more efficiently on the electrode. The particle diameter of the conductive particles is particularly preferably 5 μm or more and 30 μm or less.
　上記導電性粒子の粒子径は、数平均粒子径を示す。導電性粒子の粒子径は、例えば、任意の導電性粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、各導電性粒子の粒子径の平均値を算出することや、レーザー回折式粒度分布測定を行うことにより求められる。 The particle diameter of the conductive particles indicates a number average particle diameter. The particle diameter of the conductive particles may be determined by, for example, observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating an average value of the particle diameter of each conductive particle, or measuring a laser diffraction particle size distribution. It is calculated by doing.
　上記導電性粒子の粒子径の変動係数（ＣＶ値）は、好ましくは５％以上、より好ましくは１０％以上であり、好ましくは４０％以下、より好ましくは３０％以下である。上記導電性粒子の粒子径の変動係数が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができる。但し、上記導電性粒子の粒子径のＣＶ値は、５％未満であってもよい。 The particle diameter variation coefficient (CV value) of the conductive particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less. When the coefficient of variation of the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrode. However, the CV value of the particle diameter of the conductive particles may be less than 5%.
　上記変動係数（ＣＶ値）は、以下のようにして測定できる。 The coefficient of variation (CV value) can be measured as follows.
　ＣＶ値（％）＝（ρ／Ｄｎ）×１００
　ρ：導電性粒子の粒子径の標準偏差
　Ｄｎ：導電性粒子の粒子径の平均値 CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of particle diameter of conductive particles Dn: Average value of particle diameter of conductive particles
　上記導電性粒子の形状は特に限定されない。上記導電性粒子の形状は、球状であってもよく、扁平状等の球形状以外の形状であってもよい。 The shape of the conductive particles is not particularly limited. The conductive particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
　以下、導電性粒子のその他の詳細を説明する。 Hereinafter, other details of the conductive particles will be described.
　（はんだ粒子）
　上記はんだ粒子は、中心部分及び外表面のいずれもがはんだにより形成されている。上記はんだ粒子は、中心部分及び外表面のいずれもがはんだである粒子である。上記はんだ粒子の代わりに、はんだ以外の材料から形成された基材粒子と該基材粒子の表面上に配置されたはんだ部とを備える導電性粒子を用いた場合には、電極上に導電性粒子が集まり難くなる。また、導電性粒子同士のはんだ接合性が低いために、電極上に移動した導電性粒子が電極外に移動しやすくなる傾向があり、電極間の位置ずれの抑制効果も低くなる傾向がある。 (Solder particles)
As for the said solder particle, 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 outer surface are solder. In place of the solder particles, when conductive particles including base particles formed from a material other than solder and solder portions arranged on the surface of the base particles are used, the conductive particles are conductive on the electrodes. Particles are difficult to collect. In addition, since the solder bonding property between the conductive particles is low, the conductive particles that have moved onto the electrodes tend to move out of the electrodes, and the effect of suppressing displacement between the electrodes also tends to be low.
　上記はんだは、融点が４５０℃以下である金属（低融点金属）であることが好ましい。上記はんだ粒子は、融点が４５０℃以下である金属粒子（低融点金属粒子）であることが好ましい。上記低融点金属粒子は、低融点金属を含む粒子である。該低融点金属とは、融点が４５０℃以下の金属を示す。低融点金属の融点は好ましくは３００℃以下、より好ましくは２００℃未満、さらに好ましくは１６０℃以下である。 The solder is preferably a metal (low melting point metal) having a melting point of 450 ° C. or lower. The solder particles are preferably metal particles (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 less than 200 ° C., further preferably 160 ° C. or lower.
　本発明に係る導電性粒子では、上記はんだ粒子の融点は、２００℃未満である。低温でより一層容易に実装する観点からは、上記はんだ粒子は、融点が２００℃未満の低融点はんだであることが好ましく、融点が１５０℃未満の低融点はんだであることがより好ましい。 In the conductive particles according to the present invention, the melting point of the solder particles is less than 200 ° C. From the viewpoint of more easily mounting at a low temperature, the solder particles are preferably a low melting point solder having a melting point of less than 200 ° C., and more preferably a low melting point solder having a melting point of less than 150 ° C.
　低温でより一層容易に実装する観点からは、上記はんだ粒子は、スズ及びビスマスを含むことが好ましい。上記はんだ粒子に含まれる金属１００重量％中、スズの含有量は、好ましくは３０重量％以上、より好ましくは４０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは９０重量％以上である。上記はんだ粒子におけるスズの含有量が、上記下限以上であると、はんだ部と電極との接続信頼性がより一層高くなる。上記はんだ粒子に含まれる金属１００重量％中、ビスマスの含有量は、好ましくは４０重量％以上、より好ましくは４５重量％以上、さらに好ましくは４８重量％以上、特に好ましくは５０重量％以上である。上記はんだ粒子におけるビスマスの含有量が、上記下限以上であると、はんだ部と電極との接続信頼性がより一層高くなる。 From the viewpoint of more easily mounting at low temperature, the solder particles preferably contain tin and bismuth. The content of tin in 100% by weight of metal contained in the solder particles is preferably 30% by weight or more, more preferably 40% by weight or more, further preferably 70% by weight or more, and particularly preferably 90% by weight or more. . When the tin content 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. In 100% by weight of the metal contained in the solder particles, the content of bismuth is preferably 40% by weight or more, more preferably 45% by weight or more, still more preferably 48% by weight or more, and particularly preferably 50% by weight or more. . When the content of bismuth in the solder particles is equal to or more than the lower limit, the connection reliability between the solder portion and the electrode is further enhanced.
　上記スズ及びビスマスの含有量は、高周波誘導結合プラズマ発光分光分析装置（堀場製作所社製「ＩＣＰ－ＡＥＳ」）、又は蛍光Ｘ線分析装置（島津製作所社製「ＥＤＸ－８００ＨＳ」）等を用いて測定することができる。 The content of tin and bismuth 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). Can be measured.
　上記はんだ粒子を用いることで、はんだが溶融して電極に接合し、はんだ部が電極間を導通させる。例えば、はんだ部と電極とが点接触ではなく面接触しやすいため、接続抵抗が低くなる。また、上記はんだ粒子の使用により、はんだ部と電極との接合強度が高くなる結果、はんだ部と電極との剥離がより一層生じ難くなり、導通信頼性及び接続信頼性がより一層高くなる。 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. Moreover, as a result of the use of the solder particles, the bonding strength between the solder part and the electrode is increased. As a result, peeling between the solder part and the electrode is less likely to occur, and the conduction reliability and the connection reliability are further improved.
　上記はんだ粒子を構成する低融点金属は、融点が２００℃未満であれば特に限定されない。該低融点金属は、スズ、又はスズを含む合金であることが好ましい。該合金は、スズ－銀合金、スズ－銅合金、スズ－銀－銅合金、スズ－ビスマス合金、スズ－亜鉛合金、スズ－インジウム合金等が挙げられる。電極に対する濡れ性に優れることから、上記低融点金属は、スズ、スズ－銀合金、スズ－銀－銅合金、スズ－ビスマス合金、スズ－インジウム合金であることが好ましい。スズ－ビスマス合金、スズ－インジウム合金であることがより好ましい。 The low melting point metal constituting the solder particles is not particularly limited as long as the melting point is less than 200 ° C. The low melting point metal is preferably tin or an alloy containing tin. Examples of the alloy include a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, a tin-bismuth alloy, a tin-zinc alloy, and a tin-indium alloy. The low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, or tin-indium alloy because of its excellent wettability to the electrode. More preferred are a tin-bismuth alloy and a tin-indium alloy.
　上記はんだ粒子は、ＪＩＳ　Ｚ３００１：溶接用語に基づき、液相線が４５０℃以下である溶加材であることが好ましい。上記はんだ粒子の組成としては、例えば亜鉛、金、銀、鉛、銅、スズ、ビスマス、インジウム等を含む金属組成が挙げられる。低融点で鉛フリーであるスズ－インジウム系（１１７℃共晶）、又はスズ－ビスマス系（１３９℃共晶）が好ましい。すなわち、上記はんだ粒子は、鉛を含まないことが好ましく、スズとインジウムとを含むか、又はスズとビスマスとを含むことが好ましい。 The solder particles are preferably a filler material having a liquidus line of 450 ° C. or lower based on JIS Z3001: Welding terms. Examples of the composition of the solder particles include metal compositions containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like. Preferred is a tin-indium system (117 ° C. eutectic) or a tin-bismuth system (139 ° C. eutectic) which has a low melting point and is lead-free. That is, the solder particles preferably do not contain lead, and preferably contain tin and indium, or contain tin and bismuth.
　はんだ部と電極との接合強度をより一層高めるために、上記はんだ粒子は、ニッケル、銅、アンチモン、アルミニウム、亜鉛、鉄、金、チタン、リン、ゲルマニウム、テルル、コバルト、ビスマス、マンガン、クロム、モリブデン、パラジウム等の金属を含んでいてもよい。また、はんだ部と電極との接合強度をさらに一層高める観点からは、上記はんだ粒子は、ニッケル、銅、アンチモン、アルミニウム又は亜鉛を含むことが好ましい。はんだ部と電極との接合強度をより一層高める観点からは、接合強度を高めるためのこれらの金属の含有量は、はんだ粒子１００重量％中、好ましくは０．０００１重量％以上、好ましくは１重量％以下である。 In order to further increase the bonding strength between the solder part and the electrode, the solder particles include nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, Metals such as molybdenum and palladium may be included. 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.
　上記はんだ粒子の粒子径は、好ましくは０．５μｍ以上、より好ましくは１μｍ以上、さらに好ましくは３μｍ以上、特に好ましくは５μｍ以上であり、好ましくは１００μｍ以下、より好ましくは４０μｍ以下、より一層好ましくは３０μｍ以下、さらに好ましくは２０μｍ以下、特に好ましくは１５μｍ以下、最も好ましくは１０μｍ以下である。上記はんだ粒子の粒子径が、上記下限以上及び上記上限以下であると、導電性粒子におけるはんだを電極上により一層効率的に配置することができる。上記はんだ粒子の粒子径は、５μｍ以上、３０μｍ以下であることが特に好ましい。 The particle diameter of the solder particles is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm or more, particularly preferably 5 μm or more, preferably 100 μm or less, more preferably 40 μm or less, and even more preferably. It is 30 μm or less, more preferably 20 μm or less, particularly preferably 15 μm or less, and most preferably 10 μm or less. When the particle diameter of the solder particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrode. The particle size of the solder particles is particularly preferably 5 μm or more and 30 μm or less.
　上記はんだ粒子の粒子径は、数平均粒子径を示す。はんだ粒子の粒子径は、例えば、任意のはんだ粒子５０個を電子顕微鏡又は光学顕微鏡にて観察し、各はんだ粒子の粒子径の平均値を算出することや、レーザー回折式粒度分布測定を行うことにより求められる。 The particle size of the solder particles indicates a number average particle size. The particle size of the solder particles is, for example, observing 50 arbitrary solder particles with an electron microscope or an optical microscope, calculating an average value of the particle size of each solder particle, or performing a laser diffraction particle size distribution measurement. Is required.
　上記はんだ粒子の粒子径の変動係数（ＣＶ値）は、好ましくは５％以上、より好ましくは１０％以上であり、好ましくは４０％以下、より好ましくは３０％以下である。上記はんだ粒子の粒子径の変動係数が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができる。但し、上記はんだ粒子の粒子径のＣＶ値は、５％未満であってもよい。 The coefficient of variation (CV value) of the particle size of the solder particles is preferably 5% or more, more preferably 10% or more, preferably 40% or less, more preferably 30% or less. When the variation coefficient of the particle diameter of the solder particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrode. However, the CV value of the particle diameter of the solder particles may be less than 5%.
　上記変動係数（ＣＶ値）は、以下のようにして測定できる。 The coefficient of variation (CV value) can be measured as follows.
　ＣＶ値（％）＝（ρ／Ｄｎ）×１００
　ρ：はんだ粒子の粒子径の標準偏差
　Ｄｎ：はんだ粒子の粒子径の平均値 CV value (%) = (ρ / Dn) × 100
ρ: Standard deviation of particle diameter of solder particles Dn: Average value of particle diameter of solder particles
　上記はんだ粒子の形状は特に限定されない。上記はんだ粒子の形状は、球状であってもよく、扁平状等の球形状以外の形状であってもよい。 The shape of the solder particles is not particularly limited. The solder particles may have a spherical shape or a shape other than a spherical shape such as a flat shape.
　（被覆部）
　上記被覆部は、上記はんだ粒子の表面上に配置されている。上記被覆部は、銀を含む。上記被覆部は、銀のみを含んでいてもよく、銀以外の金属を含んでいてもよい。上記被覆部に含まれる銀以外の金属は特に限定されず、金、銅、ニッケル、パラジウム、及びチタン等が挙げられる。 (Coating part)
The said coating | coated part is arrange | positioned on the surface of the said solder particle. The said coating | coated part contains silver. The said coating | coated part may contain only silver and may contain metals other than silver. A metal other than silver contained in the covering portion is not particularly limited, and examples thereof include gold, copper, nickel, palladium, and titanium.
　導電性粒子１００重量％中、上記銀の含有量は、好ましくは１重量％以上、より好ましくは５重量％以上、さらに好ましくは１０重量％以上、特に好ましくは１１重量％以上であり、好ましくは２０重量％以下、より好ましくは１５重量％以下、さらに好ましくは１３重量％以下である。上記銀の含有量が、上記下限以上及び上記上限以下であると、低温でより一層容易に実装することができ、接続部の耐衝撃性をより一層効果的に高めることができる。 The content of the silver in 100% by weight of the conductive particles is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, particularly preferably 11% by weight or more, preferably It is 20 weight% or less, More preferably, it is 15 weight% or less, More preferably, it is 13 weight% or less. When the silver content is not less than the above lower limit and not more than the above upper limit, it can be more easily mounted at a low temperature, and the impact resistance of the connecting portion can be further effectively improved.
　低温でより一層容易に実装する観点、及び接続部の耐衝撃性をより一層効果的に高める観点からは、上記はんだ粒子の表面積全体１００％中、上記はんだ粒子の表面の上記被覆部により覆われている表面積（被覆率）は、好ましくは８０％以上、より好ましくは９０％以上である。上記被覆率の上限は特に限定されない。上記被覆率は、１００％以下であってもよい。 From the viewpoint of more easily mounting at a low temperature and from the viewpoint of further effectively increasing the impact resistance of the connection portion, the surface area of the solder particles is covered by the covering portion on the surface of the solder particles in 100% of the entire surface area of the solder particles. The surface area (coverage) is preferably 80% or more, more preferably 90% or more. The upper limit of the said coverage is not specifically limited. The coverage may be 100% or less.
　上記被覆率は、上記導電性粒子をＳＥＭ－ＥＤＸ分析することで、Ａｇマッピングを行い、画像解析することで算出することができる。 The coverage can be calculated by performing Ag mapping and conducting image analysis by conducting SEM-EDX analysis on the conductive particles.
　低温でより一層容易に実装する観点、及び接続部の耐衝撃性をより一層効果的に高める観点からは、上記被覆部の厚みは、好ましくは０．１μｍ以上、より好ましくは１μｍ以上であり、好ましくは５μｍ以下、より好ましくは２μｍ以下である。なお、上記被覆部の厚みは、上記はんだ粒子の表面上に配置された被覆部がある部分のみの被覆部の厚みを意味する。上記はんだ粒子の表面上に配置された被覆部がない部分については、被覆部の厚みを算出する際に考慮されない。 From the viewpoint of more easily mounting at a low temperature and from the viewpoint of further effectively increasing the impact resistance of the connection portion, the thickness of the covering portion is preferably 0.1 μm or more, more preferably 1 μm or more, Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less. In addition, the thickness of the said coating | coated part means the thickness of the coating | coated part only of the part with the coating | coated part arrange | positioned on the surface of the said solder particle. A portion where there is no covering portion arranged on the surface of the solder particle is not considered when calculating the thickness of the covering portion.
　上記被覆部が銀のみから形成されている場合において、上記被覆部の厚みは、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上、さらに好ましくは１μｍ以上、特に好ましくは１．５μｍ以上であり、好ましくは５μｍ以下、より好ましくは２μｍ以下である。上記被覆部が銀のみから形成されている場合において、上記被覆部の厚みが、上記下限以上及び上記上限以下であると、低温でより一層容易に実装することができ、接続部の耐衝撃性をより一層効果的に高めることができる。 In the case where the covering portion is formed only of silver, the thickness of the covering portion is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, particularly preferably 1.5 μm or more. Yes, preferably 5 μm or less, more preferably 2 μm or less. In the case where the covering portion is formed only of silver, when the thickness of the covering portion is not less than the above lower limit and not more than the above upper limit, it can be more easily mounted at a low temperature, and the impact resistance of the connection portion Can be increased more effectively.
　また、上記被覆部は、単層であってもよく、２層以上の層（多層）であってもよい。上記被覆部が２層以上の層（多層）である場合には、上記被覆部の厚みは、上記被覆部全体の厚みを意味する。 Further, the covering portion may be a single layer or two or more layers (multilayer). When the covering portion is a layer (multilayer) of two or more layers, the thickness of the covering portion means the thickness of the entire covering portion.
　上記被覆部の厚みは、上記はんだ粒子の粒子径と上記導電性粒子の粒子径との差により算出することができる。 The thickness of the covering portion can be calculated from the difference between the particle diameter of the solder particles and the particle diameter of the conductive particles.
　低温でより一層容易に実装する観点、及び接続部の耐衝撃性をより一層効果的に高める観点からは、上記被覆部の厚みの上記はんだ粒子の粒子径に対する比（被覆部の厚み／はんだ粒子の粒子径）は、好ましくは０．００１以上、より好ましくは０．０１以上であり、好ましくは５以下、より好ましくは１以下である。 From the viewpoint of more easily mounting at a low temperature, and from the viewpoint of further effectively improving the impact resistance of the connecting portion, the ratio of the thickness of the covering portion to the particle diameter of the solder particles (the thickness of the covering portion / solder particles) Is preferably 0.001 or more, more preferably 0.01 or more, preferably 5 or less, more preferably 1 or less.
　上記被覆部を備える導電性粒子を導電材料等に用いることで、導電性粒子からの金属イオンの溶出を効果的に防止することができ、導電材料の増粘を効果的に防止することができる。また、導電性粒子が上記被覆部を備えることで、導電性粒子のはんだの表面の酸化を効果的に防止することができ、はんだの濡れ性をより一層良好に保つことができる。 By using the conductive particles provided with the covering portion as a conductive material or the like, elution of metal ions from the conductive particles can be effectively prevented, and thickening of the conductive material can be effectively prevented. . In addition, since the conductive particles are provided with the covering portion, the surface of the solder of the conductive particles can be effectively prevented from being oxidized, and the wettability of the solder can be further improved.
　さらに、導電接続（実装）前においては、導電性粒子における上記はんだ粒子のはんだと上記被覆部に含まれる銀とはそれぞれ独立して存在しており、合金化していないことが好ましい。この場合には、導電接続前の導電性粒子は、上記はんだ粒子の融点で溶融させることができる。上記はんだ粒子は、融点が２００℃未満の低融点はんだであることが好ましいことから、導電接続（実装）前の導電性粒子は、比較的低温で溶融させることができ、低温で容易に導電接続（実装）することができる。また、導電接続（実装）後においては、導電接続（実装）時に付与される熱により、導電性粒子における上記はんだ粒子のはんだと上記被覆部含まれる銀とが、合金化していることが好ましい。この場合には、導電接続（実装）後の接続部（はんだ部）の融点が、上記はんだ粒子の融点よりも高くなるので、接続部（はんだ部）の耐衝撃性を効果的に高めることができる。 Furthermore, before the conductive connection (mounting), it is preferable that the solder of the solder particles in the conductive particles and the silver contained in the covering portion exist independently and are not alloyed. In this case, the conductive particles before the conductive connection can be melted at the melting point of the solder particles. Since the solder particles are preferably low melting point solder having a melting point of less than 200 ° C., the conductive particles before conductive connection (mounting) can be melted at a relatively low temperature, and can be easily conductive connection at a low temperature. (Implementation) can be. In addition, after the conductive connection (mounting), it is preferable that the solder of the solder particles in the conductive particles and the silver contained in the covering portion are alloyed by heat applied during the conductive connection (mounting). In this case, since the melting point of the connection part (solder part) after the conductive connection (mounting) becomes higher than the melting point of the solder particles, the impact resistance of the connection part (solder part) can be effectively increased. it can.
　（金属部）
　上記導電性粒子は、上記はんだ粒子の外表面と上記被覆部との間に、ニッケルを含む金属部を備えることが好ましい。上記導電性粒子は、上記はんだ粒子の表面上に配置された金属部と、上記金属部の表面上に配置された被覆部とを備えることが好ましい。上記導電性粒子が、上記の好ましい態様を満足することで、低温でより一層容易に実装することができ、接続部の耐衝撃性をより一層効果的に高めることができる。 (Metal part)
The conductive particles preferably include a metal part including nickel between the outer surface of the solder particles and the covering part. The conductive particles preferably include a metal portion disposed on the surface of the solder particle and a covering portion disposed on the surface of the metal portion. When the conductive particles satisfy the above preferred embodiment, the conductive particles can be more easily mounted at a low temperature, and the impact resistance of the connection portion can be further effectively improved.
　上記金属部は、ニッケルを含むことが好ましい。上記金属部は、ニッケル以外の金属を含んでいてもよい。上記金属部に含まれるニッケル以外の金属は特に限定されず、金、銀、銅、パラジウム、及びチタン等が挙げられる。 The metal part preferably contains nickel. The metal part may contain a metal other than nickel. A metal other than nickel contained in the metal part is not particularly limited, and examples thereof include gold, silver, copper, palladium, and titanium.
　低温でより一層容易に実装する観点、及び接続部の耐衝撃性をより一層効果的に高める観点からは、上記金属部の厚みは、好ましくは０．１μｍ以上、より好ましくは１μｍ以上であり、好ましくは５μｍ以下、より好ましくは２μｍ以下である。なお、上記金属部の厚みは、上記はんだ粒子の表面上に配置された金属部がある部分のみの金属部を厚みを意味する。上記はんだ粒子の表面上に配置された金属部がない部分については、金属部の厚みを算出する際に考慮されない。 From the viewpoint of more easily mounting at a low temperature, and from the viewpoint of more effectively increasing the impact resistance of the connection part, the thickness of the metal part is preferably 0.1 μm or more, more preferably 1 μm or more, Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less. In addition, the thickness of the said metal part means thickness only the part with a metal part arrange | positioned on the surface of the said solder particle. A portion where there is no metal portion disposed on the surface of the solder particle is not considered when calculating the thickness of the metal portion.
　上記金属部がニッケルのみから形成されている場合において、低温でより一層容易に実装する観点、及び接続部の耐衝撃性をより一層効果的に高める観点からは、上記金属部の厚みは、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上、さらに好ましくは１μｍ以上であり、好ましくは５μｍ以下、より好ましくは２μｍ以下である。 In the case where the metal part is formed only from nickel, the thickness of the metal part is preferably from the viewpoint of more easily mounting at a low temperature and further enhancing the impact resistance of the connection part more effectively. Is 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, preferably 5 μm or less, more preferably 2 μm or less.
　また、上記金属部は、単層であってもよく、２層以上の層（多層）であってもよい。上記金属部が２層以上の層（多層）である場合には、上記金属部の厚みは、上記金属部全体の厚みを意味する。 The metal part may be a single layer or two or more layers (multilayer). When the metal part is a layer (multilayer) of two or more layers, the thickness of the metal part means the thickness of the entire metal part.
　上記金属部の厚みは、例えば、透過型電子顕微鏡（ＴＥＭ）を用いて、導電性粒子の断面を観察することにより求めることができる。 The thickness of the metal part can be determined, for example, by observing the cross section of the conductive particles using a transmission electron microscope (TEM).
　低温でより一層容易に実装する観点、及び接続部の耐衝撃性をより一層効果的に高める観点からは、上記金属部の厚みの上記はんだ粒子の粒子径に対する比（金属部の厚み／はんだ粒子の粒子径）は、好ましくは０．００１以上、より好ましくは０．０１以上であり、好ましくは５以下、より好ましくは１以下である。 From the viewpoint of more easily mounting at a low temperature and from the viewpoint of further effectively increasing the impact resistance of the connection portion, the ratio of the thickness of the metal portion to the particle diameter of the solder particles (the thickness of the metal portion / solder particles) Is preferably 0.001 or more, more preferably 0.01 or more, preferably 5 or less, more preferably 1 or less.
　（導電材料）
　本発明に係る導電材料は、上述した導電性粒子と熱硬化性化合物とを含むことが好ましい。 (Conductive material)
The conductive material according to the present invention preferably includes the above-described conductive particles and a thermosetting compound.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記導電材料は、２５℃で液状であることが好ましく、導電ペーストであることが好ましい。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the conductive material is preferably liquid at 25 ° C., and preferably a conductive paste.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記導電材料の２５℃での粘度（η２５）は、好ましくは２０Ｐａ・ｓ以上、より好ましくは３０Ｐａ・ｓ以上であり、好ましくは６００Ｐａ・ｓ以下、より好ましくは３００Ｐａ・ｓ以下である。上記粘度（η２５）は、配合成分の種類及び配合量により適宜調整することができる。 From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrode, the viscosity (η25) at 25 ° C. of the conductive material is preferably 20 Pa · s or more, more preferably 30 Pa · s or more. , Preferably 600 Pa · s or less, more preferably 300 Pa · s or less. The said viscosity ((eta) 25) can be suitably adjusted with the kind and compounding quantity of a compounding component.
　上記粘度（η２５）は、例えば、Ｅ型粘度計（東機産業社製「ＴＶＥ２２Ｌ」）等を用いて、２５℃及び５ｒｐｍの条件で測定することができる。 The viscosity (η25) can be measured under conditions of 25 ° C. and 5 rpm using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.).
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記導電性粒子の融点における上記導電材料の粘度（ηｍｐ）は、好ましくは０．１Ｐａ・ｓ以上、より好ましくは０．５Ｐａ・ｓ以上であり、好ましくは５Ｐａ・ｓ以下、より好ましくは１Ｐａ・ｓ以下である。上記粘度（ηｍｐ）は、配合成分の種類及び配合量により適宜調整することができる。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the viscosity (ηmp) of the conductive material at the melting point of the conductive particles is preferably 0.1 Pa · s or more, more preferably 0. It is 5 Pa · s or more, preferably 5 Pa · s or less, more preferably 1 Pa · s or less. The viscosity (ηmp) can be appropriately adjusted according to the type and amount of the compounding component.
　導電性粒子の融点は、導電性粒子におけるはんだの電極上への移動に影響しやすい温度である。 The melting point of the conductive particles is a temperature that tends to affect the movement of the conductive particles onto the electrode of the solder.
　上記導電性粒子の融点における上記導電材料の粘度（ηｍｐ）は、例えば、ＳＴＲＥＳＳＴＥＣＨ（ＲＥＯＬＯＧＩＣＡ社製）等を用いて、歪制御１ｒａｄ、周波数１Ｈｚ、昇温速度２０℃／分、測定温度範囲４０℃～導電性粒子の融点の条件で測定することができる。この測定において、導電性粒子の融点での粘度を導電材料の粘度（ηｍｐ）とする。 The viscosity (ηmp) of the conductive material at the melting point of the conductive particles is, for example, strain control 1 rad, frequency 1 Hz, temperature rising rate 20 ° C./min, measurement temperature range 40 ° C. using STRESSTECH (manufactured by REOLOGICA). It can be measured under the condition of the melting point of the conductive particles. In this measurement, the viscosity at the melting point of the conductive particles is defined as the viscosity (ηmp) of the conductive material.
　上記導電材料は、導電ペースト及び導電フィルム等として使用され得る。上記導電ペーストは異方性導電ペーストであることが好ましく、上記導電フィルムは異方性導電フィルムであることが好ましい。電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記導電材料は、導電ペーストであることが好ましい。上記導電材料は、電極の電気的な接続に好適に用いられる。上記導電材料は、回路接続材料であることが好ましい。 The conductive material can be used as a conductive paste and a conductive film. The conductive paste is preferably an anisotropic conductive paste, and the conductive film is preferably an anisotropic conductive film. From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the conductive material is preferably a conductive paste. The conductive material is preferably used for electrical connection of electrodes. The conductive material is preferably a circuit connection material.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記導電材料１００重量％中、上記導電性粒子の含有量は、５０重量％を超えることが好ましい。上記導電材料１００重量％中、上記導電性粒子の含有量が、５０重量％を超える場合に、低温での実装性、及び接続部の耐衝撃性の向上効果がより一層発揮される。上記導電材料１００重量％中、上記導電性粒子の含有量は、好ましくは５０重量％以上、より好ましくは７０重量％以上であり、好ましくは９０重量％以下、より好ましくは８０重量％以下である。上記導電性粒子の含有量が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置することができ、電極間に導電性粒子を多く配置することが容易であり、導通信頼性がより一層高くなる。導通信頼性をより一層高める観点からは、上記導電性粒子の含有量は多い方が好ましい。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the content of the conductive particles in the conductive material of 100% by weight preferably exceeds 50% by weight. When the content of the conductive particles exceeds 50% by weight in 100% by weight of the conductive material, the effect of improving the mountability at low temperatures and the impact resistance of the connection portion is further exhibited. The content of the conductive particles in 100% by weight of the conductive material is preferably 50% by weight or more, more preferably 70% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less. . When the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles can be more efficiently arranged on the electrodes, and a large number of conductive particles are arranged between the electrodes. And the conduction reliability is further enhanced. From the viewpoint of further improving the conduction reliability, the content of the conductive particles is preferably large.
　以下、導電材料に含まれる各成分を説明する。なお、本明細書中において、「（メタ）アクリル」は「アクリル」と「メタクリル」との一方又は双方を意味し、「（メタ）アクリレート」は「アクリレート」と「メタクリレート」との一方又は双方を意味する。 Hereinafter, each component included in the conductive material will be described. In the present specification, “(meth) acryl” means one or both of “acryl” and “methacryl”, and “(meth) acrylate” means one or both of “acrylate” and “methacrylate”. Means.
　（熱硬化性化合物）
　上記導電材料は、熱硬化性化合物を含むことが好ましい。上記熱硬化性化合物は、加熱により硬化可能な化合物である。上記熱硬化性化合物としては、オキセタン化合物、エポキシ化合物、エピスルフィド化合物、（メタ）アクリル化合物、フェノール化合物、アミノ化合物、不飽和ポリエステル化合物、ポリウレタン化合物、シリコーン化合物及びポリイミド化合物等が挙げられる。導電材料の硬化性及び粘度をより一層良好にし、接続信頼性をより一層高める観点から、上記熱硬化性化合物は、エポキシ化合物又はエピスルフィド化合物であることが好ましい。上記熱硬化性化合物は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Thermosetting compound)
The conductive material preferably contains a thermosetting compound. The thermosetting compound is a compound that can be cured by heating. Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. From the viewpoint of further improving the curability and viscosity of the conductive material and further improving the connection reliability, the thermosetting compound is preferably an epoxy compound or an episulfide compound. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記熱硬化性化合物は、ポリエーテル骨格を有する熱硬化性化合物を含むことが好ましい。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the thermosetting compound preferably includes a thermosetting compound having a polyether skeleton.
　上記ポリエーテル骨格を有する熱硬化性化合物としては、炭素数３～１２のアルキル鎖の両末端にグリシジルエーテル基を有する化合物、並びに炭素数２～４のポリエーテル骨格を有し、該ポリエーテル骨格２～１０個が連続して結合した構造単位を有するポリエーテル型エポキシ化合物等が挙げられる。 Examples of the thermosetting compound having a polyether skeleton include a compound having a glycidyl ether group at both ends of an alkyl chain having 3 to 12 carbon atoms and a polyether skeleton having 2 to 4 carbon atoms. Examples thereof include polyether type epoxy compounds having structural units in which 2 to 10 are bonded continuously.
　導電材料の硬化物の耐熱性をより一層高める観点、並びに導電材料の硬化物の誘電率をより一層低くする観点からは、上記熱硬化性化合物は、トリアジン骨格を有する熱硬化性化合物を含むことが好ましい。 From the viewpoint of further increasing the heat resistance of the cured material of the conductive material and further reducing the dielectric constant of the cured material of the conductive material, the thermosetting compound includes a thermosetting compound having a triazine skeleton. Is preferred.
　上記トリアジン骨格を有する熱硬化性化合物としてはトリアジントリグリシジルエーテル等が挙げられ、日産化学工業社製ＴＥＰＩＣシリーズ（ＴＥＰＩＣ－Ｇ、ＴＥＰＩＣ－Ｓ、ＴＥＰＩＣ－ＳＳ、ＴＥＰＩＣ－ＨＰ、ＴＥＰＩＣ－Ｌ、ＴＥＰＩＣ－ＰＡＳ、ＴＥＰＩＣ－ＶＬ、ＴＥＰＩＣ－ＵＣ）等が挙げられる。 Examples of the thermosetting compound having a triazine skeleton include triazine triglycidyl ether and the like. PAS, TEPIC-VL, TEPIC-UC) and the like.
　上記エポキシ化合物としては、芳香族エポキシ化合物が挙げられる。上記エポキシ化合物は、レゾルシノール型エポキシ化合物、ナフタレン型エポキシ化合物、ビフェニル型エポキシ化合物、ベンゾフェノン型エポキシ化合物等の結晶性エポキシ化合物であることが好ましい。上記エポキシ化合物は、常温（２３℃）で固体であり、かつ溶融温度がはんだの融点以下であるエポキシ化合物であることが好ましい。上記溶融温度は、好ましくは１００℃以下、より好ましくは８０℃以下であり、好ましくは４０℃以上である。上記の好ましいエポキシ化合物を用いることで、接続対象部材を貼り合わせた段階では、粘度が高く、搬送等の衝撃により加速度が付与された際に、第１の接続対象部材と、第２の接続対象部材との位置ずれを抑制することができる。さらに、上記の好ましいエポキシ化合物を用いることで、硬化時の熱により、導電材料の粘度を大きく低下させることができ、導電性粒子におけるはんだの凝集を効率よく進行させることができる。 The above-mentioned epoxy compound includes an aromatic epoxy compound. The epoxy compound is preferably a crystalline epoxy compound such as a resorcinol type epoxy compound, a naphthalene type epoxy compound, a biphenyl type epoxy compound, or a benzophenone type epoxy compound. The epoxy compound is preferably an epoxy compound that is solid at normal temperature (23 ° C.) and has a melting temperature equal to or lower than the melting point of the solder. The melting temperature is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and preferably 40 ° C. or higher. By using the preferable epoxy compound, the first connection target member and the second connection target are high when the connection target member is bonded to each other when the viscosity is high and acceleration is applied by impact such as conveyance. The positional deviation with respect to the member can be suppressed. Furthermore, by using the preferable epoxy compound, the viscosity of the conductive material can be greatly reduced by the heat during curing, and the aggregation of solder in the conductive particles can be efficiently advanced.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記熱硬化性化合物は、２５℃で液状である熱硬化性化合物を含むことが好ましい。上記２５℃で液状である熱硬化性化合物としては、エポキシ化合物及びエピスルフィド化合物等が挙げられる。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the thermosetting compound preferably includes a thermosetting compound that is liquid at 25 ° C. Examples of the thermosetting compound that is liquid at 25 ° C. include epoxy compounds and episulfide compounds.
　上記導電材料１００重量％中、上記熱硬化性化合物の含有量は、好ましくは２０重量％以上、より好ましくは４０重量％以上、さらに好ましくは５０重量％以上であり、好ましくは９９重量％以下、より好ましくは９８重量％以下、さらに好ましくは９０重量％以下、特に好ましくは８０重量％以下である。上記熱硬化性化合物の含有量が、上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだをより一層効率的に配置し、電極間の位置ずれをより一層抑制し、電極間の導通信頼性をより一層高めることができる。耐衝撃性をより一層高める観点からは、上記熱硬化性化合物の含有量は多い方が好ましい。 The content of the thermosetting compound in 100% by weight of the conductive material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, and preferably 99% by weight or less. More preferably, it is 98 weight% or less, More preferably, it is 90 weight% or less, Most preferably, it is 80 weight% or less. When the content of the thermosetting compound is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles is more efficiently arranged on the electrodes, and the displacement between the electrodes is further suppressed, and the electrodes The conduction reliability between them can be further enhanced. From the viewpoint of further improving the impact resistance, it is preferable that the content of the thermosetting compound is large.
　（熱硬化剤）
　上記導電材料は、熱硬化剤を含むことが好ましい。上記導電材料は、上記熱硬化性化合物とともに熱硬化剤を含むことが好ましい。上記熱硬化剤は、上記熱硬化性化合物を熱硬化させる。上記熱硬化剤としては、イミダゾール硬化剤、フェノール硬化剤、チオール硬化剤、アミン硬化剤、酸無水物硬化剤、熱カチオン硬化剤及び熱ラジカル発生剤等がある。上記熱硬化剤は、１種のみが用いられてもよく、２種以上が併用されてもよい。 (Thermosetting agent)
The conductive material preferably contains a thermosetting agent. The conductive material preferably contains a thermosetting agent together with the thermosetting compound. The thermosetting agent thermosets the thermosetting compound. Examples of the thermosetting agent include an imidazole curing agent, a phenol curing agent, a thiol curing agent, an amine curing agent, an acid anhydride curing agent, a thermal cation curing agent, and a thermal radical generator. As for the said thermosetting agent, only 1 type may be used and 2 or more types may be used together.
　導電材料を低温でより一層速やかに硬化可能とする観点からは、上記熱硬化剤は、イミダゾール硬化剤、チオール硬化剤、又はアミン硬化剤であることが好ましい。また、上記熱硬化性化合物と上記熱硬化剤とを混合したときの保存安定性を高める観点からは、上記熱硬化剤は、潜在性の硬化剤であることが好ましい。潜在性の硬化剤は、潜在性イミダゾール硬化剤、潜在性チオール硬化剤又は潜在性アミン硬化剤であることが好ましい。なお、上記熱硬化剤は、ポリウレタン樹脂又はポリエステル樹脂等の高分子物質で被覆されていてもよい。 From the viewpoint of enabling the conductive material to be cured more rapidly at a low temperature, the thermosetting agent is preferably an imidazole curing agent, a thiol curing agent, or an amine curing agent. Further, from the viewpoint of enhancing the storage stability when the thermosetting compound and the thermosetting agent are mixed, the thermosetting agent is preferably a latent curing agent. The latent curing agent is preferably a latent imidazole curing agent, a latent thiol curing agent, or a latent amine curing agent. In addition, the said thermosetting agent may be coat | covered with polymeric substances, such as a polyurethane resin or a polyester resin.
　上記イミダゾール硬化剤は、特に限定されない。上記イミダゾール硬化剤としては、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン及び２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物等が挙げられる。 The imidazole curing agent is not particularly limited. Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6. -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adducts Etc.
　上記チオール硬化剤は、特に限定されない。上記チオール硬化剤としては、トリメチロールプロパントリス－３－メルカプトプロピオネート、ペンタエリスリトールテトラキス－３－メルカプトプロピオネート及びジペンタエリスリトールヘキサ－３－メルカプトプロピオネート等が挙げられる。 The thiol curing agent is not particularly limited. Examples of the thiol curing agent include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate.
　上記アミン硬化剤は、特に限定されない。上記アミン硬化剤としては、ヘキサメチレンジアミン、オクタメチレンジアミン、デカメチレンジアミン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラスピロ［５．５］ウンデカン、ビス（４－アミノシクロヘキシル）メタン、メタフェニレンジアミン及びジアミノジフェニルスルホン等が挙げられる。 The amine curing agent is not particularly limited. Examples of the amine curing agent include hexamethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane, bis (4 -Aminocyclohexyl) methane, metaphenylenediamine, diaminodiphenylsulfone and the like.
　上記熱カチオン硬化剤は、特に限定されない。上記熱カチオン硬化剤としては、ヨードニウム系カチオン硬化剤、オキソニウム系カチオン硬化剤及びスルホニウム系カチオン硬化剤等が挙げられる。上記ヨードニウム系カチオン硬化剤としては、ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムヘキサフルオロホスファート等が挙げられる。上記オキソニウム系カチオン硬化剤としては、トリメチルオキソニウムテトラフルオロボラート等が挙げられる。上記スルホニウム系カチオン硬化剤としては、トリ－ｐ－トリルスルホニウムヘキサフルオロホスファート等が挙げられる。 The thermal cationic curing agent is not particularly limited. Examples of the thermal cationic curing agent include iodonium-based cationic curing agents, oxonium-based cationic curing agents, and sulfonium-based cationic curing agents. Examples of the iodonium-based cationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate. Examples of the oxonium-based cationic curing agent include trimethyloxonium tetrafluoroborate. Examples of the sulfonium-based cationic curing agent include tri-p-tolylsulfonium hexafluorophosphate.
　上記熱ラジカル発生剤は、特に限定されない。上記熱ラジカル発生剤としては、アゾ化合物及び有機過酸化物等が挙げられる。上記アゾ化合物としては、アゾビスイソブチロニトリル（ＡＩＢＮ）等が挙げられる。上記有機過酸化物としては、ジ－ｔｅｒｔ－ブチルペルオキシド及びメチルエチルケトンペルオキシド等が挙げられる。 The thermal radical generator is not particularly limited. Examples of the thermal radical generator include azo compounds and organic peroxides. Examples of the azo compound include azobisisobutyronitrile (AIBN). Examples of the organic peroxide include di-tert-butyl peroxide and methyl ethyl ketone peroxide.
　上記熱硬化剤の反応開始温度は、好ましくは５０℃以上、より好ましくは７０℃以上、さらに好ましくは８０℃以上であり、好ましくは２５０℃以下、より好ましくは２００℃以下、さらに好ましくは１５０℃以下、特に好ましくは１４０℃以下である。上記熱硬化剤の反応開始温度が上記下限以上及び上記上限以下であると、電極上に導電性粒子におけるはんだがより一層効率的に配置される。上記熱硬化剤の反応開始温度は８０℃以上、１４０℃以下であることが特に好ましい。 The reaction initiation temperature of the thermosetting agent is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 150 ° C. Hereinafter, it is particularly preferably 140 ° C. or lower. When the reaction start temperature of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the solder in the conductive particles is more efficiently arranged on the electrode. The reaction initiation temperature of the thermosetting agent is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記熱硬化剤の反応開始温度は、上記導電性粒子におけるはんだの融点よりも、高いことが好ましく、５℃以上高いことがより好ましく、１０℃以上高いことがさらに好ましい。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the reaction initiation temperature of the thermosetting agent is preferably higher than the melting point of the solder in the conductive particles, and is higher by 5 ° C. or more. More preferably, it is more preferably 10 ° C. or higher.
　上記熱硬化剤の反応開始温度は、ＤＳＣでの発熱ピークの立ち上がり開始の温度を意味する。 The reaction start temperature of the thermosetting agent means the temperature at which the exothermic peak of DSC starts to rise.
　上記熱硬化剤の含有量は特に限定されない。上記熱硬化性化合物１００重量部に対して、上記熱硬化剤の含有量は、好ましくは０．０１重量部以上、より好ましくは１重量部以上であり、好ましくは２００重量部以下、より好ましくは１００重量部以下、さらに好ましくは７５重量部以下である。熱硬化剤の含有量が上記下限以上であると、熱硬化性化合物を十分に硬化させることが容易である。熱硬化剤の含有量が上記上限以下であると、硬化後に硬化に関与しなかった余剰の熱硬化剤が残存し難くなり、かつ硬化物の耐熱性がより一層高くなる。 The content of the thermosetting agent is not particularly limited. The content of the thermosetting agent with respect to 100 parts by weight of the thermosetting compound is preferably 0.01 parts by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less, more preferably 75 parts by weight or less. It is easy to fully harden a thermosetting compound as content of a thermosetting agent is more than the said minimum. When the content of the thermosetting agent is not more than the above upper limit, it is difficult for an excess thermosetting agent that did not participate in curing after curing to remain, and the heat resistance of the cured product is further enhanced.
　（フラックス）
　上記導電材料は、フラックスを含むことが好ましい。フラックスの使用により、電極上に導電性粒子におけるはんだをより一層効率的に配置することができる。上記フラックスは特に限定されない。上記フラックスとして、はんだ接合等に一般的に用いられているフラックスを使用できる。 (flux)
The conductive material preferably contains a flux. By using the flux, the solder in the conductive particles can be arranged more efficiently on the electrode. The flux is not particularly limited. As said flux, the flux generally used for soldering etc. can be used.
　上記フラックスとしては、例えば、塩化亜鉛、塩化亜鉛と無機ハロゲン化物との混合物、塩化亜鉛と無機酸との混合物、溶融塩、リン酸、リン酸の誘導体、有機ハロゲン化物、ヒドラジン、アミン化合物、有機酸及び松脂等が挙げられる。上記フラックスは１種のみが用いられてもよく、２種以上が併用されてもよい。 Examples of the flux include zinc chloride, a mixture of zinc chloride and an inorganic halide, a mixture of zinc chloride and an inorganic acid, a molten salt, phosphoric acid, a derivative of phosphoric acid, an organic halide, hydrazine, an amine compound, and an organic compound. Examples include acid and rosin. As for the said flux, only 1 type may be used and 2 or more types may be used together.
　上記溶融塩としては、塩化アンモニウム等が挙げられる。上記有機酸としては、乳酸、クエン酸、ステアリン酸、グルタミン酸及びグルタル酸等が挙げられる。上記松脂としては、活性化松脂及び非活性化松脂等が挙げられる。上記フラックスは、カルボキシル基を２個以上有する有機酸、松脂であることが好ましい。上記フラックスは、カルボキシル基を２個以上有する有機酸であってもよく、松脂であってもよい。カルボキシル基を２個以上有する有機酸、松脂の使用により、電極間の導通信頼性がより一層高くなる。 Examples of the molten salt include ammonium chloride. Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid, and glutaric acid. Examples of the pine resin include activated pine resin and non-activated pine resin. The flux is preferably an organic acid having two or more carboxyl groups, pine resin. The flux may be an organic acid having two or more carboxyl groups, or pine resin. By using an organic acid having two or more carboxyl groups, pine resin, the conduction reliability between the electrodes is further enhanced.
　上記カルボキシル基を２個以上有する有機酸としては、例えば、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等が挙げられる。 Examples of the organic acid having two or more carboxyl groups include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
　上記アミン化合物としては、例えば、シクロヘキシルアミン、ジシクロヘキシルアミン、ベンジルアミン、ベンズヒドリルアミン、イミダゾール、ベンゾイミダゾール、フェニルイミダゾール、カルボキシベンゾイミダゾール、ベンゾトリアゾールカルボキシベンゾトリアゾール等が挙げられる。 Examples of the amine compound include cyclohexylamine, dicyclohexylamine, benzylamine, benzhydrylamine, imidazole, benzimidazole, phenylimidazole, carboxybenzimidazole, benzotriazole, carboxybenzotriazole, and the like.
　上記松脂はアビエチン酸を主成分とするロジン類である。上記ロジン類としては、例えば、アビエチン酸、アクリル変性ロジン等が挙げられる。フラックスはロジン類であることが好ましく、アビエチン酸であることがより好ましい。この好ましいフラックスの使用により、電極間の導通信頼性がより一層高くなる。 The above rosins are rosins whose main component is abietic acid. Examples of the rosins include abietic acid and acrylic modified rosin. The flux is preferably a rosin, and more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further enhanced.
　上記フラックスの融点（活性温度）は、好ましくは１０℃以上、より好ましくは５０℃以上、より好ましくは７０℃以上、さらに好ましくは８０℃以上であり、好ましくは２００℃以下、より好ましくは１９０℃以下、より一層好ましくは１６０℃以下、さらに好ましくは１５０℃以下、さらに一層好ましくは１４０℃以下である。上記フラックスの融点が、上記下限以上及び上記上限以下であると、フラックス効果がより一層効果的に発揮され、電極上に導電性粒子におけるはんだがより一層効率的に配置される。上記フラックスの融点（活性温度）は８０℃以上、１９０℃以下であることが好ましい。上記フラックスの融点（活性温度）は８０℃以上、１４０℃以下であることが特に好ましい。 The melting point (activation temperature) of the flux is preferably 10 ° C. or higher, more preferably 50 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, preferably 200 ° C. or lower, more preferably 190 ° C. Hereinafter, it is more preferably 160 ° C. or lower, further preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower. When the melting point of the flux is not less than the above lower limit and not more than the above upper limit, the flux effect is more effectively exhibited, and the solder in the conductive particles is more efficiently disposed on the electrode. The melting point (activation temperature) of the flux is preferably 80 ° C. or higher and 190 ° C. or lower. The melting point (activation temperature) of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
　フラックスの融点（活性温度）が８０℃以上、１９０℃以下である上記フラックスとしては、コハク酸（融点１８６℃）、グルタル酸（融点９６℃）、アジピン酸（融点１５２℃）、ピメリン酸（融点１０４℃）、スベリン酸（融点１４２℃）等のジカルボン酸、安息香酸（融点１２２℃）、リンゴ酸（融点１３０℃）等が挙げられる。 Examples of the flux having a melting point (activation temperature) 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.), dicarboxylic acids such as suberic acid (melting point 142 ° C.), benzoic acid (melting point 122 ° C.), malic acid (melting point 130 ° C.) and the like.
　また、上記フラックスの沸点は、２００℃以下であることが好ましい。 The boiling point of the flux is preferably 200 ° C. or lower.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記フラックスの融点は、上記導電性粒子におけるはんだの融点よりも、高いことが好ましく、５℃以上高いことがより好ましく、１０℃以上高いことがさらに好ましい。 From the viewpoint of more efficiently arranging the solder in the conductive particles on the electrode, the melting point of the flux is preferably higher than the melting point of the solder in the conductive particles, and more preferably 5 ° C. or higher. More preferably, it is 10 ° C. or higher.
　電極上に導電性粒子におけるはんだをより一層効率的に配置する観点からは、上記フラックスの融点は、上記熱硬化剤の反応開始温度よりも、高いことが好ましく、５℃以上高いことがより好ましく、１０℃以上高いことがさらに好ましい。 From the viewpoint of more efficiently disposing the solder in the conductive particles on the electrode, the melting point of the flux is preferably higher than the reaction start temperature of the thermosetting agent, and more preferably 5 ° C or higher. More preferably, it is 10 ° C. or higher.
　上記フラックスは、導電材料中に分散されていてもよく、導電性粒子の表面上に付着していてもよい。 The flux may be dispersed in the conductive material or may be adhered on the surface of the conductive particles.
　フラックスの融点が、導電性粒子におけるはんだの融点より高いことにより、電極部分に導電性粒子におけるはんだを効率的に凝集させることができる。これは、接合時に熱を付与した場合、接続対象部材上に形成された電極と、電極周辺の接続対象部材の部分とを比較すると、電極部分の熱伝導率が電極周辺の接続対象部材部分の熱伝導率よりも高いことにより、電極部分の昇温が速いことに起因する。導電性粒子におけるはんだの融点を超えた段階では、導電性粒子の内部は溶解するが、表面に形成された酸化被膜は、フラックスの融点（活性温度）に達していないので、除去されない。この状態で、電極部分の温度が先に、フラックスの融点（活性温度）に達するため、優先的に電極上に来た導電性粒子の表面の酸化被膜が除去され、導電性粒子におけるはんだが電極の表面上に濡れ拡がることができる。これにより、電極上に効率的に導電性粒子におけるはんだを凝集させることができる。 Since the melting point of the flux is higher than the melting point of the solder in the conductive particles, the solder in the conductive particles can be efficiently aggregated on the electrode portion. This is because, when heat is applied at the time of joining, when the electrode formed on the connection target member is compared with the portion of the connection target member around the electrode, the thermal conductivity of the electrode portion is that of the connection target member portion around the electrode. Due to the fact that it is higher than the thermal conductivity, the temperature rise of the electrode portion is fast. At the stage where the melting point of the solder exceeds the melting point of the conductive particles, the inside of the conductive particles dissolves, but the oxide film formed on the surface does not reach the melting point (activation temperature) of the flux and is not removed. In this state, since the temperature of the electrode portion first reaches the melting point (activation temperature) of the flux, the oxide film on the surface of the conductive particles that has come preferentially on the electrode is removed, and the solder in the conductive particles becomes the electrode. Can spread on the surface of the surface. Thereby, the solder in electroconductive particle can be efficiently aggregated on an electrode.
　上記導電材料１００重量％中、上記フラックスの含有量は、好ましくは０．５重量％以上であり、好ましくは３０重量％以下、より好ましくは２５重量％以下である。上記導電材料は、フラックスを含んでいなくてもよい。フラックスの含有量が、上記下限以上及び上記上限以下であると、導電性粒子及び電極の表面に酸化被膜がより一層形成され難くなり、さらに、導電性粒子及び電極の表面に形成された酸化被膜をより一層効果的に除去できる。 In 100% by weight of the conductive material, the content of the flux is preferably 0.5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less. The conductive material may not contain flux. When the content of the flux 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 surfaces of the conductive particles and the electrodes, and the oxide film formed on the surfaces of the conductive particles and the electrodes. Can be more effectively removed.
　（絶縁性粒子）
　導電材料の硬化物により接続される接続対象部材間の間隔を高精度に制御する観点、及びはんだ部により接続される接続対象部材間の間隔を高精度に制御する観点からは、上記導電材料は、絶縁性粒子を含むことが好ましい。上記導電材料において、上記絶縁性粒子は、上記はんだ粒子の表面に付着していなくてもよい。上記導電材料中で、上記絶縁性粒子は上記はんだ粒子と離れて存在することが好ましい。 (Insulating particles)
From the viewpoint of controlling the interval between the connection target members connected by the cured material of the conductive material with high accuracy, and from the viewpoint of controlling the interval between the connection target members connected by the solder portion with high accuracy, the conductive material is Insulating particles are preferably included. In the conductive material, the insulating particles may not be attached to the surface of the solder particles. In the conductive material, the insulating particles are preferably present apart from the solder particles.
　上記絶縁性粒子の粒子径は、好ましくは１０μｍ以上、より好ましくは２０μｍ以上、さらに好ましくは２５μｍ以上であり、好ましくは１００μｍ以下、より好ましくは７５μｍ以下、さらに好ましくは５０μｍ以下である。上記絶縁性粒子の粒子径が、上記下限以上及び上記上限以下であると、導電材料の硬化物により接続される接続対象部材間の間隔、及びはんだ部により接続される接続対象部材間の間隔がより一層適度になる。 The particle diameter of the insulating particles is preferably 10 μm or more, more preferably 20 μm or more, further preferably 25 μm or more, preferably 100 μm or less, more preferably 75 μm or less, and even more preferably 50 μm or less. When the particle diameter of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between the connection target members connected by the cured material of the conductive material and the interval between the connection target members connected by the solder portion are It becomes even more moderate.
　上記絶縁性粒子の材料としては、絶縁性の樹脂、及び絶縁性の無機物等が挙げられる。上記絶縁性の樹脂としては、ポリオレフィン化合物、（メタ）アクリレート重合体、（メタ）アクリレート共重合体、ブロックポリマー、熱可塑性樹脂、熱可塑性樹脂の架橋物、熱硬化性樹脂及び水溶性樹脂等が挙げられる。 The material for the insulating particles includes an insulating resin and an insulating inorganic substance. Examples of the insulating resin include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, cross-linked thermoplastic resins, thermosetting resins, and water-soluble resins. Can be mentioned.
　上記ポリオレフィン化合物としては、ポリエチレン、エチレン－酢酸ビニル共重合体及びエチレン－アクリル酸エステル共重合体等が挙げられる。上記（メタ）アクリレート重合体としては、ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート及びポリブチル（メタ）アクリレート等が挙げられる。上記ブロックポリマーとしては、ポリスチレン、スチレン－アクリル酸エステル共重合体、ＳＢ型スチレン－ブタジエンブロック共重合体、及びＳＢＳ型スチレン－ブタジエンブロック共重合体、並びにこれらの水素添加物等が挙げられる。上記熱可塑性樹脂としては、ビニル重合体及びビニル共重合体等が挙げられる。上記熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂及びメラミン樹脂等が挙げられる。上記水溶性樹脂としては、ポリビニルアルコール、ポリアクリル酸、ポリアクリルアミド、ポリビニルピロリドン、ポリエチレンオキシド及びメチルセルロース等が挙げられる。水溶性樹脂が好ましく、ポリビニルアルコールがより好ましい。 Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate. Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer, and hydrogenated products thereof. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. As said thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. A water-soluble resin is preferable, and polyvinyl alcohol is more preferable.
　上記絶縁性無機物としては、シリカ及び有機無機ハイブリッド粒子等が挙げられる。上記シリカにより形成された粒子としては特に限定されないが、例えば、加水分解性のアルコキシシリル基を２つ以上有するケイ素化合物を加水分解して架橋重合体粒子を形成した後に、必要に応じて焼成を行うことにより得られる粒子が挙げられる。上記有機無機ハイブリッド粒子としては、例えば、架橋したアルコキシシリルポリマーとアクリル樹脂とにより形成された有機無機ハイブリッド粒子等が挙げられる。 Examples of the insulating inorganic material include silica and organic-inorganic hybrid particles. The particles formed from the silica are not particularly limited. For example, after forming a crosslinked polymer particle by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups, firing may be performed as necessary. The particle | grains obtained by performing are mentioned. Examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
　上記導電材料１００重量％中、上記絶縁性粒子の含有量は、好ましくは０．１重量％以上、より好ましくは０．５重量％以上であり、好ましくは１０重量％以下、より好ましくは５重量％以下である。上記導電材料は、上記絶縁性粒子を含んでいなくてもよい。上記絶縁性粒子の含有量が、上記下限以上及び上記上限以下であると、導電材料の硬化物により接続される接続対象部材間の間隔、及びはんだ部により接続される接続対象部材間の間隔がより一層適度になる。 The content of the insulating particles in 100% by weight of the conductive material is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 10% by weight or less, more preferably 5% by weight. % Or less. The conductive material may not include the insulating particles. When the content of the insulating particles is not less than the above lower limit and not more than the above upper limit, the interval between connection target members connected by the cured material of the conductive material and the interval between connection target members connected by the solder portion are It becomes even more moderate.
　（他の成分）
　上記導電材料は、必要に応じて、例えば、カップリング剤、遮光剤、反応性希釈剤、消泡剤、レベリング剤、充填剤、増量剤、軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤及び難燃剤等の各種添加剤を含んでいてもよい。 (Other ingredients)
The conductive material may be, for example, a coupling agent, a light-shielding agent, a reactive diluent, an antifoaming agent, a leveling agent, a filler, an extender, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, or a coloring agent. Various additives such as an agent, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be included.
　（接続構造体及び接続構造体の製造方法）
　本発明に係る接続構造体は、少なくとも１つの第１の電極を表面に有する第１の接続対象部材と、少なくとも１つの第２の電極を表面に有する第２の接続対象部材と、上記第１の接続対象部材と、上記第２の接続対象部材とを接続している接続部とを備える。本発明に係る接続構造体では、上記接続部の材料が、上述した導電性粒子を含む。本発明に係る接続構造体では、上記接続部が、上述した導電性粒子であるか、又は上述した導電材料であることが好ましい。本発明に係る接続構造体では、上記接続部が、上述した導電性粒子により形成されているか、又は上述した導電材料により形成されていることが好ましい。本発明に係る接続構造体では、上記接続部が、上述した導電材料の硬化物であることが好ましい。本発明に係る接続構造体では、上記第１の電極と上記第２の電極とが、上記接続部中のはんだ部により電気的に接続されている。 (Connection structure and method of manufacturing connection structure)
A connection structure according to the present invention includes a first connection target member having at least one first electrode on the surface, a second connection target member having at least one second electrode on the surface, and the first The connection object member and the connection part which has connected the said 2nd connection object member are provided. In the connection structure according to the present invention, the material of the connection portion includes the conductive particles described above. In the connection structure according to the present invention, it is preferable that the connection portion is the above-described conductive particle or the above-described conductive material. In the connection structure according to the present invention, it is preferable that the connection portion is formed of the conductive particles described above or the conductive material described above. In the connection structure according to the present invention, the connection portion is preferably a cured product of the conductive material described above. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
　上記接続構造体の製造方法は、上述した導電性粒子又は上述した導電材料を用いて、少なくとも１つの第１の電極を表面に有する第１の接続対象部材の表面上に、上記導電性粒子又は上記導電材料を配置する工程を備える。上記接続構造体の製造方法は、上記導電性粒子又は上記導電材料の上記第１の接続対象部材側とは反対の表面上に、少なくとも１つの第２の電極を表面に有する第２の接続対象部材を、上記第１の電極と上記第２の電極とが対向するように配置する工程を備える。上記接続構造体の製造方法は、上記導電性粒子の融点以上に上記導電材料を加熱することで、上記第１の接続対象部材と上記第２の接続対象部材とを接続している接続部を、上記導電性粒子又は上記導電材料により形成し、かつ、上記第１の電極と上記第２の電極とを、上記接続部中のはんだ部により電気的に接続する工程を備える。好ましくは、上記熱硬化性化合物の硬化温度以上に上記導電材料を加熱する。 In the method for manufacturing the connection structure, the conductive particles or the conductive material described above is used to form the conductive particles or the conductive particles on the surface of the first connection target member having at least one first electrode on the surface. A step of disposing the conductive material. The manufacturing method of the connection structure includes a second connection target having at least one second electrode on the surface of the conductive particle or the conductive material opposite to the first connection target member side. A step of disposing the member such that the first electrode and the second electrode face each other; In the method for manufacturing the connection structure, the connection part connecting the first connection target member and the second connection target member is formed by heating the conductive material to a temperature equal to or higher than the melting point of the conductive particles. And a step of electrically connecting the first electrode and the second electrode with a solder portion in the connection portion, the conductive electrode or the conductive material. Preferably, the conductive material is heated above the curing temperature of the thermosetting compound.
　本発明に係る接続構造体及び接続構造体の製造方法では、特定の導電性粒子又は特定の導電材料を用いているので、導電性粒子が第１の電極と第２の電極との間に集まりやすく、導電性粒子を電極（ライン）上に効率的に配置することができる。また、導電性粒子の一部が、電極が形成されていない領域（スペース）に配置され難く、電極が形成されていない領域に配置される導電性粒子の量をかなり少なくすることができる。従って、第１の電極と第２の電極との間の導通信頼性を高めることができる。しかも、接続されてはならない横方向に隣接する電極間の電気的な接続を防ぐことができ、絶縁信頼性を高めることができる。 In the connection structure and the manufacturing method of the connection structure according to the present invention, the specific conductive particles or the specific conductive material is used. Therefore, the conductive particles gather between the first electrode and the second electrode. It is easy to efficiently arrange the conductive particles on the electrode (line). Moreover, it is difficult for some of the conductive particles to be disposed in a region (space) where no electrode is formed, and the amount of conductive 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.
　また、電極上に導電性粒子におけるはんだを効率的に配置し、かつ電極が形成されていない領域に配置されるはんだの量をかなり少なくするためには、上記導電材料は、導電フィルムではなく、導電ペーストを用いることが好ましい。 Further, in order to efficiently arrange the solder in the conductive particles on the electrode and to considerably reduce the amount of solder arranged in the region where the electrode is not formed, the conductive material is not a conductive film, It is preferable to use a conductive paste.
　電極間でのはんだ部の厚みは、好ましくは１０μｍ以上、より好ましくは２０μｍ以上であり、好ましくは１００μｍ以下、より好ましくは８０μｍ以下である。電極の表面上のはんだ濡れ面積（電極の露出した面積１００％中のはんだが接している面積）は、好ましくは５０％以上、より好ましくは７０％以上であり、好ましくは１００％以下である。 The thickness of the solder part between the electrodes is preferably 10 μm or more, more preferably 20 μm or more, preferably 100 μm or less, more preferably 80 μm or less. The solder wetted area on the surface of the electrode (area where the solder is in contact with 100% of the exposed area of the electrode) is preferably 50% or more, more preferably 70% or more, and preferably 100% or less.
　本発明に係る接続構造体の製造方法では、上記第２の接続対象部材を配置する工程及び上記接続部を形成する工程において、加圧を行わず、上記導電性粒子又は上記導電材料には、上記第２の接続対象部材の重量が加わることが好ましい。また、上記第２の接続対象部材を配置する工程及び上記接続部を形成する工程において、上記導電性粒子又は上記導電材料には、上記第２の接続対象部材の重量の力を超える加圧圧力は加わらないことが好ましい。これらの場合には、複数のはんだ部において、はんだ量の均一性をより一層高めることができる。さらに、はんだ部の厚みをより一層効果的に厚くすることができ、複数の導電性粒子が電極間に多く集まりやすくなり、複数の導電性粒子を電極（ライン）上により一層効率的に配置することができる。また、複数の導電性粒子の一部が、電極が形成されていない領域（スペース）に配置され難く、電極が形成されていない領域に配置される導電性粒子の量をより一層少なくすることができる。従って、電極間の導通信頼性をより一層高めることができる。しかも、接続されてはならない横方向に隣接する電極間の電気的な接続をより一層防ぐことができ、絶縁信頼性をより一層高めることができる。 In the manufacturing method of the connection structure according to the present invention, in the step of arranging the second connection target member and the step of forming the connection portion, the conductive particles or the conductive material is not pressurized, The weight of the second connection target member is preferably added. Further, in the step of disposing the second connection target member and the step of forming the connection portion, the conductive particles or the conductive material may include a pressurized pressure that exceeds the force of the weight of the second connection target member. Is preferably not added. In these cases, the uniformity of the amount of solder can be further enhanced in the plurality of solder portions. Furthermore, the thickness of the solder portion can be increased more effectively, and a plurality of conductive particles are likely to gather between the electrodes, and the plurality of conductive particles are arranged more efficiently on the electrodes (lines). be able to. Moreover, it is difficult for some of the plurality of conductive particles to be disposed in a region (space) where no electrode is formed, and the amount of conductive particles disposed in a region where no electrode is formed may be further reduced. it can. Therefore, the conduction reliability between the electrodes can be further enhanced. In addition, the electrical connection between the laterally adjacent electrodes that should not be connected can be further prevented, and the insulation reliability can be further improved.
　また、導電フィルムではなく、導電ペーストを用いれば、導電ペーストの塗布量によって、接続部及びはんだ部の厚みを調整することが容易になる。一方で、導電フィルムでは、接続部の厚みを変更したり、調整したりするためには、異なる厚みの導電フィルムを用意したり、所定の厚みの導電フィルムを用意したりしなければならないという問題がある。また、導電フィルムでは、導電ペーストと比べて、導電性粒子の溶融温度で、導電フィルムの溶融粘度を十分に下げることができず、導電性粒子におけるはんだの凝集が阻害されやすい傾向がある。 Also, if a conductive paste is used instead of a conductive film, it becomes easy to adjust the thicknesses of the connection part and the solder part depending on the amount of the conductive paste applied. On the other hand, in the conductive film, in order to change or adjust the thickness of the connection portion, it is necessary to prepare a conductive film having a different thickness or to prepare a conductive film having a predetermined thickness. There is. Moreover, in the conductive film, compared with the conductive paste, the melt viscosity of the conductive film cannot be sufficiently lowered at the melting temperature of the conductive particles, and the aggregation of the solder in the conductive particles tends to be hindered.
　以下、図面を参照しつつ、本発明の具体的な実施形態を説明する。 Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
　図１は、本発明の一実施形態に係る導電材料を用いて得られる接続構造体を模式的に示す断面図である。 FIG. 1 is a cross-sectional view schematically showing a connection structure obtained using a conductive material according to an embodiment of the present invention.
　図１に示す接続構造体１は、第１の接続対象部材２と、第２の接続対象部材３と、第１の接続対象部材２と第２の接続対象部材３とを接続している接続部４とを備える。接続部４は、上述した導電材料により形成されている。本実施形態では、上記導電材料は、熱硬化性化合物と、熱硬化剤と、導電性粒子とを含む。本実施形態では、導電材料として、導電ペーストが用いられている。 The connection structure 1 shown in FIG. 1 is a connection that connects a first connection target member 2, a second connection target member 3, and the first connection target member 2 and the second connection target member 3. Part 4. The connection part 4 is formed of the conductive material described above. In the present embodiment, the conductive material includes a thermosetting compound, a thermosetting agent, and conductive particles. In the present embodiment, a conductive paste is used as the conductive material.
　接続部４は、複数の導電性粒子が集まり互いに接合したはんだ部４Ａと、熱硬化性化合物が熱硬化された硬化物部４Ｂとを有する。 The connection part 4 has a solder part 4A in which a plurality of conductive particles gather and are joined to each other, and a cured part 4B in which a thermosetting compound is thermally cured.
　第１の接続対象部材２は表面（上面）に、複数の第１の電極２ａを有する。第２の接続対象部材３は表面（下面）に、複数の第２の電極３ａを有する。第１の電極２ａと第２の電極３ａとが、はんだ部４Ａにより電気的に接続されている。従って、第１の接続対象部材２と第２の接続対象部材３とが、はんだ部４Ａにより電気的に接続されている。なお、接続部４において、第１の電極２ａと第２の電極３ａとの間に集まったはんだ部４Ａとは異なる領域（硬化物部４Ｂ部分）では、導電性粒子は存在しない。はんだ部４Ａとは異なる領域（硬化物部４Ｂ部分）では、はんだ部４Ａと離れた導電性粒子は存在しない。なお、少量であれば、第１の電極２ａと第２の電極３ａとの間に集まったはんだ部４Ａとは異なる領域（硬化物部４Ｂ部分）に、導電性粒子が存在していてもよい。 The first connection object member 2 has a plurality of first electrodes 2a on the surface (upper surface). The second connection target member 3 has a plurality of second electrodes 3a on the surface (lower surface). The first electrode 2a and the second electrode 3a are electrically connected by the solder portion 4A. Therefore, the first connection target member 2 and the second connection target member 3 are electrically connected by the solder portion 4A. In addition, in the connection part 4, in the area | region (hardened | cured material part 4B part) different from the solder part 4A gathered between the 1st electrode 2a and the 2nd electrode 3a, electroconductive particle does not exist. In a region (cured product portion 4B portion) different from the solder portion 4A, there are no conductive particles separated from the solder portion 4A. If the amount is small, conductive particles may be present in a region (cured product portion 4B portion) different from the solder portion 4A gathered between the first electrode 2a and the second electrode 3a. .
　図１に示すように、接続構造体１では、第１の電極２ａと第２の電極３ａとの間に、複数の導電性粒子が集まり、複数の導電性粒子が溶融した後、導電性粒子の溶融物が電極の表面を濡れ拡がった後に固化して、はんだ部４Ａが形成されている。このため、はんだ部４Ａと第１の電極２ａ、並びにはんだ部４Ａと第２の電極３ａとの接続面積が大きくなる。このことによっても、接続構造体１における導通信頼性及び接続信頼性が高くなる。なお、導電材料にフラックスが含まれる場合に、フラックスは、一般に、加熱により次第に失活する。 As shown in FIG. 1, in the connection structure 1, after a plurality of conductive particles gather between the first electrode 2a and the second electrode 3a and the plurality of conductive particles melt, the conductive particles The melted material solidifies after the surface of the electrode wets and spreads to form the solder portion 4A. For this reason, the connection area of 4 A of solder parts and the 1st electrode 2a, and 4 A of solder parts, and the 2nd electrode 3a becomes large. This also increases the conduction reliability and connection reliability in the connection structure 1. In addition, when a flux is contained in the conductive material, the flux is generally gradually deactivated by heating.
　なお、図１に示す接続構造体１では、はんだ部４Ａの全てが、第１，第２の電極２ａ，３ａ間の対向している領域に位置している。図３に示す変形例の接続構造体１Ｘは、接続部４Ｘのみが、図１に示す接続構造体１と異なる。接続部４Ｘは、はんだ部４ＸＡと硬化物部４ＸＢとを有する。接続構造体１Ｘのように、はんだ部４ＸＡの多くが、第１，第２の電極２ａ，３ａの対向している領域に位置しており、はんだ部４ＸＡの一部が第１，第２の電極２ａ，３ａの対向している領域から側方にはみ出していてもよい。第１，第２の電極２ａ，３ａの対向している領域から側方にはみ出しているはんだ部４ＸＡは、はんだ部４ＸＡの一部であり、はんだ部４ＸＡから離れた導電性粒子ではない。なお、本実施形態では、はんだ部から離れた導電性粒子の量を少なくすることができるが、はんだ部から離れた導電性粒子が硬化物部中に存在していてもよい。 In addition, in the connection structure 1 shown in FIG. 1, all of the solder portions 4A are located in the facing region between the first and second electrodes 2a and 3a. The connection structure 1X of the modification shown in FIG. 3 is different from the connection structure 1 shown in FIG. 1 only in the connection portion 4X. The connection part 4X has the solder part 4XA and the hardened | cured material part 4XB. As in the connection structure 1X, most of the solder portions 4XA are located in regions where the first and second electrodes 2a and 3a are opposed to each other, and a part of the solder portion 4XA is first and second. You may protrude to the side from the area | region which electrode 2a, 3a has opposed. The solder part 4XA protruding laterally from the region where the first and second electrodes 2a, 3a are opposed is a part of the solder part 4XA and is not a conductive particle separated from the solder part 4XA. In this embodiment, the amount of conductive particles separated from the solder portion can be reduced, but the conductive particles separated from the solder portion may exist in the cured product portion.
　導電性粒子の使用量を少なくすれば、接続構造体１を得ることが容易になる。導電性粒子の使用量を多くすれば、接続構造体１Ｘを得ることが容易になる。 If the use amount of the conductive particles is reduced, it becomes easy to obtain the connection structure 1. If the usage-amount of electroconductive particle is increased, it will become easy to obtain the connection structure 1X.
　接続構造体１，１Ｘでは、第１の電極２ａと接続部４，４Ｘと第２の電極３ａとの積層方向に第１の電極２ａと第２の電極３ａとの対向し合う部分をみたときに、第１の電極２ａと第２の電極３ａとの対向し合う部分の面積１００％中の５０％以上に、接続部４，４Ｘ中のはんだ部４Ａ，４ＸＡが配置されていることが好ましい。接続部４，４Ｘ中のはんだ部４Ａ，４ＸＡが、上記の好ましい態様を満足することで、導通信頼性をより一層高めることができる。 In connection structure 1, 1X, when the part which 1st electrode 2a and 2nd electrode 3a oppose in the lamination direction of 1st electrode 2a, connection part 4, 4X, and 2nd electrode 3a is seen In addition, it is preferable that the solder portions 4A and 4XA in the connection portions 4 and 4X are arranged in 50% or more of the area of 100% of the facing portion between the first electrode 2a and the second electrode 3a. . When the solder portions 4A and 4XA in the connection portions 4 and 4X satisfy the above-described preferable mode, the conduction reliability can be further improved.
　上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の５０％以上に、上記接続部中のはんだ部が配置されていることが好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の６０％以上に、上記接続部中のはんだ部が配置されていることがより好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の７０％以上に、上記接続部中のはんだ部が配置されていることがさらに好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の８０％以上に、上記接続部中のはんだ部が配置されていることが特に好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分の面積１００％中の９０％以上に、上記接続部中のはんだ部が配置されていることが最も好ましい。上記接続部中のはんだ部が、上記の好ましい態様を満足することで、導通信頼性をより一層高めることができる。 When 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, the first electrode and the second electrode It is preferable that the solder portion in the connecting portion is arranged in 50% or more of the area of 100% of the portion facing the two electrodes. When 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, the first electrode and the second electrode It is more preferable that the solder portion in the connection portion is disposed in 60% or more of 100% of the area of the portion facing the two electrodes. When 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, the first electrode and the second electrode More preferably, the solder portion in the connecting portion is arranged in 70% or more of the area of 100% of the portion facing the two electrodes. When 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, the first electrode and the second electrode It is particularly preferable that the solder portion in the connecting portion is disposed in 80% or more of 100% of the area facing the two electrodes. When 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, the first electrode and the second electrode It is most preferable that the solder portion in the connection portion is disposed in 90% or more of the area of 100% of the portion facing the two electrodes. When the solder part in the connection part satisfies the above-described preferable aspect, the conduction reliability can be further improved.
　上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の６０％以上が配置されていることが好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の７０％以上が配置されていることがより好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の９０％以上が配置されていることがさらに好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の９５％以上が配置されていることが特に好ましい。上記第１の電極と上記接続部と上記第２の電極との積層方向と直交する方向に上記第１の電極と上記第２の電極との対向し合う部分をみたときに、上記第１の電極と上記第２の電極との対向し合う部分に、上記接続部中のはんだ部の９９％以上が配置されていることが最も好ましい。上記接続部中のはんだ部が、上記の好ましい態様を満足することで、導通信頼性をより一層高めることができる。 When the 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, It is preferable that 60% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other. 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, More preferably, 70% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other. 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, More preferably, 90% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other. 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, It is particularly preferable that 95% or more of the solder portion in the connection portion is disposed at a portion where the electrode and the second electrode face each other. 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, It is most preferable that 99% or more of the solder portion in the connection portion is disposed in a portion where the electrode and the second electrode face each other. When the solder part in the connection part satisfies the above-described preferable aspect, the conduction reliability can be further improved.
　次に、本発明の一実施形態に係る導電材料を用いて、接続構造体１を製造する方法の一例を説明する。 Next, an example of a method for manufacturing the connection structure 1 using the conductive material according to the embodiment of the present invention will be described.
　先ず、第１の電極２ａを表面（上面）に有する第１の接続対象部材２を用意する。次に、図２（ａ）に示すように、第１の接続対象部材２の表面上に、熱硬化性成分１１Ｂと、複数の導電性粒子１１Ａとを含む導電材料１１を配置する（第１の工程）。用いた導電材料１１は、熱硬化性成分１１Ｂとして、熱硬化性化合物と熱硬化剤とを含む。 First, the first connection target member 2 having the first electrode 2a on the surface (upper surface) is prepared. Next, as shown in FIG. 2A, a conductive material 11 including a thermosetting component 11B and a plurality of conductive particles 11A is disposed on the surface of the first connection target member 2 (first Process). The used conductive material 11 contains a thermosetting compound and a thermosetting agent as the thermosetting component 11B.
　第１の接続対象部材２の第１の電極２ａが設けられた表面上に、導電材料１１を配置する。導電材料１１の配置の後に、導電性粒子１１Ａは、第１の電極２ａ（ライン）上と、第１の電極２ａが形成されていない領域（スペース）上との双方に配置されている。 The conductive material 11 is disposed on the surface of the first connection target member 2 on which the first electrode 2a is provided. After the arrangement of the conductive material 11, the conductive particles 11A are arranged both on the first electrode 2a (line) and on a region (space) where the first electrode 2a is not formed.
　導電材料１１の配置方法としては、特に限定されないが、ディスペンサーによる塗布、スクリーン印刷、及びインクジェット装置による吐出等が挙げられる。 The arrangement method of the conductive material 11 is not particularly limited, and examples thereof include application by a dispenser, screen printing, and discharge by an inkjet device.
　また、第２の電極３ａを表面（下面）に有する第２の接続対象部材３を用意する。次に、図２（ｂ）に示すように、第１の接続対象部材２の表面上の導電材料１１において、導電材料１１の第１の接続対象部材２側とは反対側の表面上に、第２の接続対象部材３を配置する（第２の工程）。導電材料１１の表面上に、第２の電極３ａ側から、第２の接続対象部材３を配置する。このとき、第１の電極２ａと第２の電極３ａとを対向させる。 Moreover, the 2nd connection object member 3 which has the 2nd electrode 3a on the surface (lower surface) is prepared. Next, as shown in FIG. 2B, in the conductive material 11 on the surface of the first connection target member 2, on the surface opposite to the first connection target member 2 side of the conductive material 11, The 2nd connection object member 3 is arrange | positioned (2nd process). On the surface of the conductive material 11, the second connection target member 3 is disposed from the second electrode 3a side. At this time, the first electrode 2a and the second electrode 3a are opposed to each other.
　次に、導電性粒子１１Ａの融点以上に導電材料１１を加熱する（第３の工程）。好ましくは、熱硬化性成分１１Ｂ（熱硬化性化合物）の硬化温度以上に導電材料１１を加熱する。この加熱時には、電極が形成されていない領域に存在していた導電性粒子１１Ａは、第１の電極２ａと第２の電極３ａとの間に集まる（自己凝集効果）。導電フィルムではなく、導電ペーストを用いた場合には、導電性粒子１１Ａが、第１の電極２ａと第２の電極３ａとの間により一層効果的に集まる。また、導電性粒子１１Ａは溶融し、互いに接合する。また、熱硬化性成分１１Ｂは熱硬化する。この結果、図２（ｃ）に示すように、第１の接続対象部材２と第２の接続対象部材３とを接続している接続部４が、導電材料１１により形成される。導電材料１１により接続部４が形成され、複数の導電性粒子１１Ａが接合することによってはんだ部４Ａが形成され、熱硬化性成分１１Ｂが熱硬化することによって硬化物部４Ｂが形成される。導電性粒子１１Ａが十分に移動すれば、第１の電極２ａと第２の電極３ａとの間に位置していない導電性粒子１１Ａの移動が開始してから、第１の電極２ａと第２の電極３ａとの間に導電性粒子１１Ａの移動が完了するまでに、温度を一定に保持しなくてもよい。 Next, the conductive material 11 is heated above the melting point of the conductive particles 11A (third step). Preferably, the conductive material 11 is heated above the curing temperature of the thermosetting component 11B (thermosetting compound). At the time of this heating, the conductive particles 11A that existed in the region where no electrode is formed gather between the first electrode 2a and the second electrode 3a (self-aggregation effect). When the conductive paste is used instead of the conductive film, the conductive particles 11A are more effectively collected between the first electrode 2a and the second electrode 3a. In addition, the conductive particles 11A are melted and joined to each other. Further, the thermosetting component 11B is thermoset. As a result, as shown in FIG. 2C, the connection portion 4 that connects the first connection target member 2 and the second connection target member 3 is formed of the conductive material 11. The connection part 4 is formed of the conductive material 11, the solder part 4A is formed by joining the plurality of conductive particles 11A, and the cured part 4B is formed by thermosetting the thermosetting component 11B. If the conductive particles 11A are sufficiently moved, the first electrode 2a and the second electrode 2a are moved after the movement of the conductive particles 11A that are not positioned between the first electrode 2a and the second electrode 3a starts. The temperature does not have to be kept constant until the movement of the conductive particles 11A between the electrodes 3a is completed.
　本実施形態では、上記第１の工程及び上記第２の工程においては、導電性粒子１１Ａにおけるはんだ粒子のはんだと、導電性粒子１１Ａの被覆部に含まれる銀とは合金化していない。このため、上記第３の工程において導電材料１１を加熱する際には、はんだ粒子の融点以上に加熱すればよく、導電性粒子１１Ａは比較的低温で溶融させることができ、比較的低温ではんだ部４Ａを形成することができる。また、本実施形態では、複数の導電性粒子１１Ａが接合して形成されたはんだ部４Ａにおいては、導電性粒子１１Ａにおけるはんだ粒子のはんだと、導電性粒子１１Ａの被覆部に含まれる銀とが合金化している。このため、はんだ部４Ａの融点を、はんだ粒子の融点よりも高くすることができ、はんだ部４Ａの耐衝撃性を効果的に高めることができる。 In the present embodiment, in the first step and the second step, the solder of the solder particles in the conductive particles 11A and the silver contained in the covering portion of the conductive particles 11A are not alloyed. For this reason, when the conductive material 11 is heated in the third step, the conductive material 11 may be heated to a temperature higher than the melting point of the solder particles, and the conductive particles 11A can be melted at a relatively low temperature. The portion 4A can be formed. Moreover, in this embodiment, in the solder part 4A formed by joining a plurality of conductive particles 11A, the solder of the solder particles in the conductive particles 11A and the silver contained in the covering part of the conductive particles 11A. Alloyed. For this reason, melting | fusing point of 4 A of solder parts can be made higher than melting | fusing point of a solder particle, and the impact resistance of 4 A of solder parts can be improved effectively.
　本実施形態では、上記第２の工程及び上記第３の工程において、加圧を行わない方が好ましい。この場合には、導電材料１１には、第２の接続対象部材３の重量が加わる。このため、接続部４の形成時に、導電性粒子１１Ａが、第１の電極２ａと第２の電極３ａとの間により一層効果的に集まる。なお、上記第２の工程及び上記第３の工程の内の少なくとも一方において、加圧を行えば、導電性粒子１１Ａが第１の電極２ａと第２の電極３ａとの間に集まろうとする作用が阻害される傾向が高くなる。 In this embodiment, it is preferable that no pressure is applied in the second step and the third step. In this case, the weight of the second connection target member 3 is added to the conductive material 11. For this reason, the conductive particles 11A are more effectively collected between the first electrode 2a and the second electrode 3a when the connection portion 4 is formed. In addition, if pressurization is performed in at least one of the second step and the third step, the conductive particles 11A try to gather between the first electrode 2a and the second electrode 3a. The tendency for the action to be inhibited increases.
　また、本実施形態では、加圧を行っていないため、導電材料を塗布した第１の接続対象部材に、第２の接続対象部材を重ね合わせた際に、第１の電極と第２の電極とのアライメントがずれた状態でも、そのずれを補正して、第１の電極と第２の電極とを接続させることができる（セルフアライメント効果）。これは、第１の電極と第２の電極との間に自己凝集している溶融したはんだが、第１の電極と第２の電極との間のはんだと導電材料のその他の成分とが接する面積が最小となる方がエネルギー的に安定になるため、その最小の面積となる接続構造であるアライメントのあった接続構造にする力が働くためである。この際、導電材料が硬化していないこと、及び、その温度、時間にて、導電材料の導電性粒子以外の成分の粘度が十分低いことが望ましい。 In the present embodiment, since no pressure is applied, when the second connection target member is superimposed on the first connection target member coated with the conductive material, the first electrode and the second electrode are overlapped. Even in a state where the alignment is shifted, the shift can be corrected and the first electrode and the second electrode can be connected (self-alignment effect). This is because the molten solder self-aggregating between the first electrode and the second electrode is in contact with the solder between the first electrode and the second electrode and the other components of the conductive material. This is because the area having the smallest area is more stable in terms of energy, and therefore the force to make the connection structure with alignment, which is the connection structure having the smallest area, works. At this time, it is desirable that the conductive material is not cured, and that the viscosity of components other than the conductive particles of the conductive material is sufficiently low at that temperature and time.
　このようにして、図１に示す接続構造体１が得られる。なお、上記第２の工程と上記第３の工程とは連続して行われてもよい。また、上記第２の工程を行った後に、得られる第１の接続対象部材２と導電材料１１と第２の接続対象部材３との積層体を、加熱部に移動させて、上記第３の工程を行ってもよい。上記加熱を行うために、加熱部材上に上記積層体を配置してもよく、加熱された空間内に上記積層体を配置してもよい。 In this way, the connection structure 1 shown in FIG. 1 is obtained. The second step and the third step may be performed continuously. Moreover, after performing the said 2nd process, the laminated body of the 1st connection object member 2, the electrically-conductive material 11, and the 2nd connection object member 3 which are obtained is moved to a heating part, and the said 3rd connection object is carried out. You may perform a process. In order to perform the heating, the laminate may be disposed on a heating member, or the laminate may be disposed in a heated space.
　上記第３の工程における上記加熱温度は、好ましくは１４０℃以上、より好ましくは１６０℃以上であり、好ましくは４５０℃以下、より好ましくは２５０℃以下、さらに好ましくは２００℃以下である。 The heating temperature in the third step is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, preferably 450 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 200 ° C. or lower.
　上記第３の工程における加熱方法としては、導電性粒子の融点以上及び熱硬化性化合物の硬化温度以上に、接続構造体全体を、リフロー炉を用いて又はオーブンを用いて加熱する方法や、接続構造体の接続部のみを局所的に加熱する方法が挙げられる。 As the heating method in the third step, a method of heating the entire connection structure using a reflow furnace or an oven above the melting point of the conductive particles and the curing temperature of the thermosetting compound, or connecting The method of heating only the connection part of a structure locally is mentioned.
　局所的に加熱する方法に用いる器具としては、ホットプレート、熱風を付与するヒートガン、はんだゴテ、及び赤外線ヒーター等が挙げられる。 Examples of instruments used in the method of locally heating include a hot plate, a heat gun that applies hot air, a soldering iron, and an infrared heater.
　また、ホットプレートにて局所的に加熱する際、接続部直下は、熱伝導性の高い金属にて、その他の加熱することが好ましくない個所は、フッ素樹脂等の熱伝導性の低い材質にて、ホットプレート上面を形成することが好ましい。 In addition, when heating locally with a hot plate, the metal directly under the connection is made of a metal with high thermal conductivity, and other places where heating is not preferred are made of a material with low thermal conductivity such as a fluororesin. The upper surface of the hot plate is preferably formed.
　上記第１，第２の接続対象部材は、特に限定されない。上記第１，第２の接続対象部材としては、具体的には、半導体チップ、半導体パッケージ、ＬＥＤチップ、ＬＥＤパッケージ、コンデンサ及びダイオード等の電子部品、並びに樹脂フィルム、プリント基板、フレキシブルプリント基板、フレキシブルフラットケーブル、リジッドフレキシブル基板、ガラスエポキシ基板及びガラス基板等の回路基板等の電子部品等が挙げられる。上記第１，第２の接続対象部材は、電子部品であることが好ましい。 The first and second connection target members are not particularly limited. Specifically as said 1st, 2nd connection object member, electronic components, such as a semiconductor chip, a semiconductor package, LED chip, LED package, a capacitor | condenser, a diode, and a resin film, a printed circuit board, a flexible printed circuit board, flexible Examples thereof include electronic components such as circuit boards such as flat cables, rigid flexible boards, glass epoxy boards, and glass boards. The first and second connection target members are preferably electronic components.
　上記第１の接続対象部材及び上記第２の接続対象部材の内の少なくとも一方が、樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板であることが好ましい。上記第２の接続対象部材が、樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板であることが好ましい。樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル及びリジッドフレキシブル基板は、柔軟性が高く、比較的軽量であるという性質を有する。このような接続対象部材の接続に導電フィルムを用いた場合には、導電性粒子におけるはんだが電極上に集まりにくい傾向がある。これに対して、導電ペーストを用いることで、樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板を用いたとしても、導電性粒子におけるはんだを電極上に効率的に集めることで、電極間の導通信頼性を十分に高めることができる。樹脂フィルム、フレキシブルプリント基板、フレキシブルフラットケーブル又はリジッドフレキシブル基板を用いる場合に、半導体チップ等の他の接続対象部材を用いた場合と比べて、加圧を行わないことによる電極間の導通信頼性の向上効果がより一層効果的に得られる。 It is preferable that at least one of the first connection target member and the second connection target member is a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board. 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 the connection of such connection target members, the solder in the conductive particles tends not to collect on the electrodes. On the other hand, by using a conductive paste, even if a resin film, a flexible printed board, a flexible flat cable, or a rigid flexible board is used, the solder in the conductive particles can be efficiently collected on the electrodes, The conduction reliability can be sufficiently increased. When using a resin film, a flexible printed circuit board, a flexible flat cable, or a rigid flexible circuit board, compared to the case of using other connection target members such as a semiconductor chip, the conduction reliability between the electrodes by not applying pressure is improved. The improvement effect can be obtained more effectively.
　上記接続対象部材に設けられている電極としては、金電極、ニッケル電極、スズ電極、アルミニウム電極、銅電極、モリブデン電極、銀電極、ＳＵＳ電極、及びタングステン電極等の金属電極が挙げられる。上記接続対象部材がフレキシブルプリント基板である場合には、上記電極は金電極、ニッケル電極、スズ電極、銀電極又は銅電極であることが好ましい。上記接続対象部材がガラス基板である場合には、上記電極はアルミニウム電極、銅電極、モリブデン電極、銀電極又はタングステン電極であることが好ましい。なお、上記電極がアルミニウム電極である場合には、アルミニウムのみで形成された電極であってもよく、金属酸化物層の表面にアルミニウム層が積層された電極であってもよい。上記金属酸化物層の材料としては、３価の金属元素がドープされた酸化インジウム及び３価の金属元素がドープされた酸化亜鉛等が挙げられる。上記３価の金属元素としては、Ｓｎ、Ａｌ及びＧａ等が挙げられる。 Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, a SUS electrode, and a tungsten electrode. When the connection target member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. In addition, when the said electrode is an aluminum electrode, the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated | stacked on the surface of the metal oxide layer may be sufficient. Examples of the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.
　本発明に係る接続構造体では、上記第１の電極及び上記第２の電極は、エリアアレイ又はペリフェラルにて配置されていることが好ましい。上記第１の電極及び上記第２の電極が、エリアアレイ又はペリフェラルにて配置されている場合において、本発明の効果がより一層効果的に発揮される。上記エリアアレイとは、接続対象部材の電極が配置されている面にて、格子状に電極が配置されている構造のことである。上記ペリフェラルとは、接続対象部材の外周部に電極が配置されている構造のことである。電極が櫛型に並んでいる構造の場合は、櫛に垂直な方向に沿って導電性粒子におけるはんだが凝集すればよいのに対して、上記エリアアレイ又はペリフェラル構造では電極が配置されている面において、全面にて均一に導電性粒子におけるはんだが凝集する必要がある。このため、従来の方法では、はんだ量が不均一になりやすいのに対して、本発明の方法では、電極上に導電性粒子におけるはんだをより一層効率的に配置することができ、全面にて均一に導電性粒子におけるはんだを凝集させることができる。 In the connection structure according to the present invention, it is preferable that the first electrode and the second electrode are arranged in an area array or a peripheral. In the case where the first electrode and the second electrode are arranged in an area array or a peripheral, the effect of the present invention is more effectively exhibited. The area array is a structure in which electrodes are arranged in a grid pattern on the surface on which the electrodes of the connection target members are arranged. The peripheral is a structure in which electrodes are arranged on the outer periphery of a connection target member. In the case of a structure in which the electrodes are arranged in a comb shape, the solder in the conductive particles may be aggregated along the direction perpendicular to the comb, whereas in the area array or peripheral structure, the surface on which the electrodes are arranged In this case, it is necessary that the solder in the conductive particles uniformly aggregate on the entire surface. For this reason, in the conventional method, the amount of solder tends to be non-uniform, whereas in the method of the present invention, the solder in the conductive particles can be arranged more efficiently on the electrode, The solder in the conductive particles can be uniformly aggregated.
　以下、実施例及び比較例を挙げて、本発明を具体的に説明する。本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited only to the following examples.
　熱硬化性化合物：
　熱硬化性化合物１：レゾルシノール型エポキシ化合物、共栄社化学社製「エポライトＴＤＣ－ＬＣ」、エポキシ当量１２０ｇ／ｅｑ
　熱硬化性化合物２：エポキシ化合物、ＡＤＥＫＡ社製「ＥＰ－３３００」、エポキシ当量１６０ｇ／ｅｑ Thermosetting compound:
Thermosetting compound 1: Resorcinol type epoxy compound, “Epolite TDC-LC” manufactured by Kyoeisha Chemical Co., epoxy equivalent 120 g / eq
Thermosetting compound 2: Epoxy compound, “EP-3300” manufactured by ADEKA, epoxy equivalent 160 g / eq
　熱硬化剤：
　潜在性エポキシ熱硬化剤１：Ｔ＆Ｋ　ＴＯＫＡ社製「フジキュア７０００」
　潜在性エポキシ熱硬化剤２：旭化成イーマテリアルズ社製「ＨＸＡ－３９２２ＨＰ」 Thermosetting agent:
Latent epoxy thermosetting agent 1: “Fujicure 7000” manufactured by T & K TOKA
Latent epoxy thermosetting agent 2: “HXA-3922HP” manufactured by Asahi Kasei E-Materials
　フラックス：
　フラックス１：和光純薬工業社製「グルタル酸」 flux:
Flux 1: “Glutaric acid” manufactured by Wako Pure Chemical Industries, Ltd.
　導電性粒子：
　導電性粒子１（ＳｎＢｉはんだ粒子、融点１３９℃、三井金属社製「Ｓｎ４２Ｂｉ５８」を選別したはんだ粒子を用い、無電解メッキにより被覆部が形成された導電性粒子、粒子径：３１μｍ、被覆部の厚み：０．５μｍ） Conductive particles:
Conductive particles 1 (SnBi solder particles, melting point 139 ° C., using the solder particles selected from Mitsui Kinzoku “Sn42Bi58”, conductive particles having a coating portion formed by electroless plating, particle diameter: 31 μm, (Thickness: 0.5 μm)
　（導電性粒子１の作製方法）
　無電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、１重量％のクエン酸溶液５００ｇに入れて、はんだ粒子の表面の酸化膜を除去した。硝酸銀５ｇとイオン交換水１０００ｇとを含む溶液を調製し、該溶液に酸化膜を除去したはんだ粒子５０ｇを入れて混合し、懸濁液を得た。得られた懸濁液に、チオリンゴ酸３０ｇと、Ｎ－アセチルイミダゾール８０ｇと、次亜リン酸ナトリウム１０ｇとを入れて混合し、メッキ液を得た。得られたメッキ液のｐＨが９となるように、１０重量％のアンモニア溶液を用いて調整し、２５℃で２０分間無電解メッキを実施することによって、無電解メッキにより被覆部が形成された導電性粒子を得た。 (Method for producing conductive particles 1)
Conductive particles with a coating formed by electroless plating:
50 g of solder particles having a particle size of 30 μm were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate and 1000 g of ion-exchanged water was prepared, and 50 g of solder particles from which the oxide film had been removed was added and mixed to obtain a suspension. To the obtained suspension, 30 g of thiomalic acid, 80 g of N-acetylimidazole and 10 g of sodium hypophosphite were added and mixed to obtain a plating solution. A coating portion was formed by electroless plating by adjusting the pH of the obtained plating solution to 9 using an ammonia solution of 10% by weight and performing electroless plating at 25 ° C. for 20 minutes. Conductive particles were obtained.
　導電性粒子２（ＳｎＢｉはんだ粒子、融点１３９℃、三井金属社製「Ｓｎ４２Ｂｉ５８」を選別したはんだ粒子を用い、無電解メッキにより金属部及び被覆部が形成された導電性粒子、粒子径：３３μｍ、金属部の厚み：１μｍ、被覆部の厚み：０．５μｍ） Conductive particles 2 (SnBi solder particles, melting point 139 ° C., using the solder particles selected from Mitsui Kinzoku “Sn42Bi58”, conductive particles having a metal part and a covering part formed by electroless plating, particle diameter: 33 μm, (Metal part thickness: 1 μm, coating part thickness: 0.5 μm)
　（導電性粒子２の作製方法）
　無電解メッキにより金属部及び被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、１重量％のクエン酸溶液５００ｇに入れて、はんだ粒子の表面の酸化膜を除去した。酸化膜を除去したはんだ粒子５０ｇを用いて、二液活性化法によりパラジウムを付着させ、表面にパラジウムが付着したはんだ粒子を得た。硫酸ニッケル２０ｇとイオン交換水１０００ｇとを含む溶液を調製し、該溶液に表面にパラジウムが付着したはんだ粒子３０ｇを入れて混合し、第１の懸濁液を得た。得られた第１の懸濁液に、クエン酸３０ｇと、次亜リン酸ナトリウム８０ｇと、酢酸１０ｇとを入れて混合し、第１のメッキ液を得た。得られた第１のメッキ液のｐＨが１０となるように、１０重量％のアンモニア溶液を用いて調整し、６０℃で２０分間無電解メッキを実施することによって、無電解メッキにより金属部が形成された導電性粒子を得た。 (Method for producing conductive particles 2)
Conductive particles having a metal part and a covering part formed by electroless plating:
50 g of solder particles having a particle size of 30 μm were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. Using 50 g of solder particles from which the oxide film had been removed, palladium was attached by a two-component activation method to obtain solder particles with palladium attached to the surface. A solution containing 20 g of nickel sulfate and 1000 g of ion-exchanged water was prepared, and 30 g of solder particles with palladium attached to the surface were mixed and mixed to obtain a first suspension. To the obtained first suspension, 30 g of citric acid, 80 g of sodium hypophosphite, and 10 g of acetic acid were added and mixed to obtain a first plating solution. The pH of the obtained first plating solution is adjusted to 10 with an ammonia solution of 10% by weight, and electroless plating is performed at 60 ° C. for 20 minutes. The formed conductive particles were obtained.
　次に、硝酸銀５ｇとイオン交換水１０００ｇとを含む溶液を調製し、該溶液に金属部が形成された導電性粒子５０ｇを入れて混合し、第２の懸濁液を得た。得られた第２の懸濁液に、コハク酸イミド３０ｇと、Ｎ－アセチルイミダゾール８０ｇと、グリオキシル酸５ｇとを入れて混合し、第２のメッキ液を得た。得られた第２のメッキ液のｐＨが９となるように、１０重量％のアンモニア溶液を用いて調整し、２０℃で２０分間無電解メッキを実施することによって、無電解メッキにより金属部及び被覆部が形成された導電性粒子を得た。 Next, a solution containing 5 g of silver nitrate and 1000 g of ion-exchanged water was prepared, and 50 g of conductive particles having a metal part formed therein were mixed and mixed to obtain a second suspension. The resulting second suspension was mixed with 30 g of succinimide, 80 g of N-acetylimidazole and 5 g of glyoxylic acid to obtain a second plating solution. By adjusting the pH of the obtained second plating solution to 9 using an ammonia solution of 10% by weight and performing electroless plating at 20 ° C. for 20 minutes, the metal part and The electroconductive particle in which the coating part was formed was obtained.
　導電性粒子３（ＳｎＢｉはんだ粒子、融点１３９℃、三井金属社製「Ｓｎ４２Ｂｉ５８」を選別したはんだ粒子を用い、電解メッキにより被覆部が形成された導電性粒子、粒子径：３２μｍ、被覆部の厚み：１μｍ） Conductive particles 3 (SnBi solder particles, melting point 139 ° C., solder particles selected from Mitsui Kinzoku Co., Ltd. “Sn42Bi58”, conductive particles having a coating part formed by electrolytic plating, particle diameter: 32 μm, coating part thickness : 1μm)
　（導電性粒子３の作製方法）
　電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、１重量％のクエン酸溶液５００ｇに入れて、はんだ粒子の表面の酸化膜を除去した。硝酸銀５ｇと、イオン交換水１０００ｇと、１，３－ジブロモ－５，５－ジメチルヒダントイン５ｇと、チオリンゴ酸３ｇとを含む溶液を調製し、該溶液に酸化膜を除去したはんだ粒子５０ｇを入れて混合し、懸濁液を得た。得られた懸濁液を用いて、アノード：白金、カソード：含リン銅、電流密度：１Ａ／ｄｍ２の条件で、電解めっきを実施することによって、電解メッキにより被覆部が形成された導電性粒子を得た。 (Method for producing conductive particles 3)
Conductive particles having a coating formed by electrolytic plating:
50 g of solder particles having a particle size of 30 μm were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate, 1000 g of ion-exchanged water, 5 g of 1,3-dibromo-5,5-dimethylhydantoin, and 3 g of thiomalic acid was prepared, and 50 g of solder particles from which the oxide film had been removed were put in the solution. Mix to obtain a suspension. Conductivity in which a coating portion was formed by electrolytic plating by performing electrolytic plating under the conditions of anode: platinum, cathode: phosphorous copper, current density: 1 A / dm 2 using the obtained suspension. Particles were obtained.
　導電性粒子４（ＳＡＣ粒子、融点２１８℃、千住金属社製「Ｍ７０５」、粒子径：３０μｍ） Conductive particles 4 (SAC particles, melting point 218 ° C., “M705” manufactured by Senju Metal Co., Ltd., particle diameter: 30 μm)
　導電性粒子５（ＳｎＢｉはんだ粒子、融点１３９℃、三井金属社製「Ｓｎ４２Ｂｉ５８」を選別したはんだ粒子を用い、電解メッキにより被覆部が形成された導電性粒子、粒子径：３５μｍ、被覆部の厚み：２．５μｍ） Conductive particles 5 (SnBi solder particles, melting point 139 ° C., solder particles selected from Mitsui Kinzoku Co., Ltd. “Sn42Bi58”, conductive particles having a coating portion formed by electrolytic plating, particle diameter: 35 μm, thickness of the coating portion : 2.5μm)
　（導電性粒子５の作製方法）
　電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、１重量％のクエン酸溶液５００ｇに入れて、はんだ粒子の表面の酸化膜を除去した。硝酸銀５ｇと、イオン交換水１０００ｇと、１，３－ジブロモ－５，５－ジメチルヒダントイン５ｇと、チオリンゴ酸３ｇとを含む溶液を調製し、該溶液に酸化膜を除去したはんだ粒子５０ｇを入れて混合し、懸濁液を得た。得られた懸濁液を用いて、アノード：白金、カソード：含リン銅、電流密度：３Ａ／ｄｍ２の条件で、電解めっきを実施することによって、電解メッキにより被覆部が形成された導電性粒子を得た。 (Method for producing conductive particles 5)
Conductive particles having a coating formed by electrolytic plating:
50 g of solder particles having a particle size of 30 μm were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate, 1000 g of ion-exchanged water, 5 g of 1,3-dibromo-5,5-dimethylhydantoin, and 3 g of thiomalic acid was prepared, and 50 g of solder particles from which the oxide film had been removed were put in the solution. Mix to obtain a suspension. Conductivity in which a coating portion was formed by electrolytic plating by performing electrolytic plating under the conditions of anode: platinum, cathode: phosphorous copper, current density: 3 A / dm 2 using the obtained suspension. Particles were obtained.
　導電性粒子６（ＳｎＢｉはんだ粒子、融点１３９℃、三井金属社製「Ｓｎ４２Ｂｉ５８」を選別したはんだ粒子を用い、電解メッキにより被覆部が形成された導電性粒子、粒子径：３３μｍ、被覆部の厚み：１．５μｍ） Conductive particles 6 (SnBi solder particles, melting point 139 ° C., using solder particles selected from Mitsui Kinzoku “Sn42Bi58”, conductive particles having a coating portion formed by electrolytic plating, particle diameter: 33 μm, thickness of the coating portion : 1.5μm)
　（導電性粒子６の作製方法）
　電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、１重量％のクエン酸溶液５００ｇに入れて、はんだ粒子の表面の酸化膜を除去した。硝酸銀５ｇと、イオン交換水１０００ｇと、１，３－ジブロモ－５，５－ジメチルヒダントイン５ｇと、チオリンゴ酸３ｇとを含む溶液を調製した。該溶液に酸化膜を除去したはんだ粒子５０ｇを入れて混合し、懸濁液を得た。得られた懸濁液を用いて、アノード：白金、カソード：含リン銅、電流密度：２Ａ／ｄｍ２の条件で、電解めっきを実施することによって、電解メッキにより被覆部が形成された導電性粒子を得た。 (Method for producing conductive particles 6)
Conductive particles having a coating formed by electrolytic plating:
50 g of solder particles having a particle size of 30 μm were put in 500 g of a 1 wt% citric acid solution, and the oxide film on the surface of the solder particles was removed. A solution containing 5 g of silver nitrate, 1000 g of ion-exchanged water, 5 g of 1,3-dibromo-5,5-dimethylhydantoin, and 3 g of thiomalic acid was prepared. 50 g of solder particles from which the oxide film has been removed were added to the solution and mixed to obtain a suspension. Conductivity in which a coating portion was formed by electrolytic plating by performing electrolytic plating under the conditions of anode: platinum, cathode: phosphorous copper, current density: 2 A / dm 2 using the obtained suspension. Particles were obtained.
　導電性粒子７（ＳｎＢｉはんだ粒子、融点１３９℃、千住金属社製「Ｌ２０-３００５０」を選別したはんだ粒子を用い、無電解メッキにより被覆部が形成された導電性粒子、粒子径：３１μｍ、被覆部の厚み：０．０８μｍ） Conductive particles 7 (SnBi solder particles, melting point 139 ° C., using the solder particles selected from “L20-30050” manufactured by Senju Metal Co., Ltd., conductive particles having a coating portion formed by electroless plating, particle diameter: 31 μm, coating Part thickness: 0.08 μm)
　（導電性粒子７の作製方法）
　無電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、ニトリロ三酢酸１gと、１０重量％水酸化ナトリウム５０ｇとを含む溶液に入れ、５０℃で５分間撹拌し、水洗することではんだ表面の酸化膜を除去した。硫酸パラジウム２ｇと、イオン交換水１００ｇとを含む溶液に、酸化膜を除去したはんだ粒子５０ｇを入れ、はんだ粒子の表面にパラジウムを付着させた。 (Method for producing conductive particles 7)
Conductive particles with a coating formed by electroless plating:
50 g of solder particles having a particle size of 30 μm were placed in a solution containing 1 g of nitrilotriacetic acid and 50 g of 10 wt% sodium hydroxide, stirred at 50 ° C. for 5 minutes, and washed with water to remove the oxide film on the solder surface. . In a solution containing 2 g of palladium sulfate and 100 g of ion-exchanged water, 50 g of solder particles from which the oxide film had been removed was put, and palladium was adhered to the surface of the solder particles.
　イオン交換水１０００ｇと、エチレンジアミン四酢酸１０ｇと、ニトリロ三酢酸１０ｇと、リン酸水素ナトリウム３０ｇと、水酸化ナトリウム３０ｇと、硝酸銀３ｇと、ポリエチレングリコール（ポリエチレングリコール１０００）１ｇとを入れて混合し、メッキ液を得た。得られたメッキ液のｐＨが８となるように、１０重量％のアンモニア溶液を用いて調整した。パラジウムを付着させたはんだ粒子を５０ｇと、水素化ホウ素ナトリウムを６ｇとをメッキ液に入れて、２５℃で２０分間無電解メッキを実施することによって、無電解メッキにより被覆部が形成された導電性粒子を得た。 1000 g of ion exchange water, 10 g of ethylenediaminetetraacetic acid, 10 g of nitrilotriacetic acid, 30 g of sodium hydrogen phosphate, 30 g of sodium hydroxide, 3 g of silver nitrate, and 1 g of polyethylene glycol (polyethylene glycol 1000) are mixed. A plating solution was obtained. The resulting plating solution was adjusted to have a pH of 8 using a 10 wt% ammonia solution. 50 g of solder particles to which palladium is attached and 6 g of sodium borohydride are placed in a plating solution, and electroless plating is performed at 25 ° C. for 20 minutes. Sex particles were obtained.
　導電性粒子８（ＳｎＢｉはんだ粒子、融点１３９℃、千住金属社製「Ｌ２０-３００５０」を選別したはんだ粒子を用い、無電解メッキにより被覆部が形成された導電性粒子、粒子径：３１μｍ、被覆部の厚み：０．１２μｍ） Conductive particles 8 (SnBi solder particles, melting point 139 ° C., solder particles selected from Senju Metal Co., Ltd. “L20-30050”, conductive particles having a coating formed by electroless plating, particle diameter: 31 μm, coating Part thickness: 0.12 μm)
　（導電性粒子８の作製方法）
　無電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、ニトリロ三酢酸１gと、１０重量％水酸化ナトリウム５０ｇとを含む溶液に入れ、５０℃で５分間撹拌し、水洗することではんだ表面の酸化膜を除去した。硫酸パラジウム２ｇと、イオン交換水１００ｇとを含む溶液に、酸化膜を除去したはんだ粒子５０ｇを入れ、はんだ粒子の表面にパラジウムを付着させた。 (Method for producing conductive particles 8)
Conductive particles with a coating formed by electroless plating:
50 g of solder particles having a particle size of 30 μm were placed in a solution containing 1 g of nitrilotriacetic acid and 50 g of 10 wt% sodium hydroxide, stirred at 50 ° C. for 5 minutes, and washed with water to remove the oxide film on the solder surface. . In a solution containing 2 g of palladium sulfate and 100 g of ion-exchanged water, 50 g of solder particles from which the oxide film had been removed was put, and palladium was adhered to the surface of the solder particles.
　イオン交換水１０００ｇと、エチレンジアミン四酢酸四ナトリウム１０ｇと、ニトリロ三酢酸ニナトリウム１０ｇと、リン酸水素ナトリウム３０ｇと、水酸化ナトリウム３０ｇと、メタンスルホン酸銀７ｇと、ポリエチレングリコール（ポリエチレングリコール１０００）１ｇとを入れて混合し、メッキ液を得た。得られたメッキ液のｐＨが３となるように、１０重量％の硫酸溶液を用いて調整した。パラジウムを付着させたはんだ粒子を５０ｇと、シュウ酸６ｇとをメッキ液に入れて、２５℃で２０分間無電解メッキを実施することによって、無電解メッキにより被覆部が形成された導電性粒子を得た。 1000 g of ion-exchanged water, 10 g of tetrasodium ethylenediaminetetraacetate, 10 g of disodium nitrilotriacetate, 30 g of sodium hydrogen phosphate, 30 g of sodium hydroxide, 7 g of silver methanesulfonate, and 1 g of polyethylene glycol (polyethylene glycol 1000) And mixed to obtain a plating solution. The obtained plating solution was adjusted using a 10 wt% sulfuric acid solution so that the pH was 3. 50 g of solder particles to which palladium is attached and 6 g of oxalic acid are placed in a plating solution, and electroless plating is performed at 25 ° C. for 20 minutes, whereby conductive particles having a coating portion formed by electroless plating are obtained. Obtained.
　導電性粒子９（ＳｎＢｉはんだ粒子、融点１３９℃、千住金属社製「Ｌ２０-３００５０」を選別したはんだ粒子を用い、無電解メッキにより被覆部が形成された導電性粒子、粒子径：３１μｍ、被覆部の厚み：０．１５μｍ） Conductive particles 9 (SnBi solder particles, melting point 139 ° C., using the solder particles selected from Senju Metal Co., Ltd. “L20-30050”, conductive particles with covering portions formed by electroless plating, particle diameter: 31 μm, covering Part thickness: 0.15 μm)
　（導電性粒子９の作製方法）
　無電解メッキにより被覆部が形成された導電性粒子：
　粒子径が３０μｍのはんだ粒子５０ｇを、ニトリロ三酢酸１gと、１０重量％水酸化ナトリウム５０ｇとを含む溶液に入れ、５０℃で５分間撹拌し、水洗することではんだ表面の酸化膜を除去した。硫酸パラジウム２ｇと、イオン交換水１００ｇとを含む溶液に、酸化膜を除去したはんだ粒子５０ｇを入れ、はんだ粒子の表面にパラジウムを付着させた。 (Method for producing conductive particles 9)
Conductive particles with a coating formed by electroless plating:
50 g of solder particles having a particle size of 30 μm were placed in a solution containing 1 g of nitrilotriacetic acid and 50 g of 10 wt% sodium hydroxide, stirred at 50 ° C. for 5 minutes, and washed with water to remove the oxide film on the solder surface. . In a solution containing 2 g of palladium sulfate and 100 g of ion-exchanged water, 50 g of solder particles from which the oxide film had been removed was put, and palladium was adhered to the surface of the solder particles.
　イオン交換水１０００ｇと、エチレンジアミン四酢酸四ナトリウム１０ｇと、ニトリロ三酢酸ニナトリウム１０ｇと、リン酸水素ナトリウム３０ｇと、水酸化ナトリウム３０ｇと、メタンスルホン酸銀７ｇと、ポリエチレングリコール（ポリエチレングリコール１０００）１ｇと入れて混合し、メッキ液を得た。得られたメッキ液のｐＨが７となるように、１０重量％の水酸化ナトリウム溶液を用いて調整した。パラジウムを付着させたはんだ粒子を５０ｇと、ギ酸６ｇとをメッキ液に入れて、４０℃で２０分間無電解メッキを実施することによって、無電解メッキにより被覆部が形成された導電性粒子を得た。 1000 g of ion-exchanged water, 10 g of tetrasodium ethylenediaminetetraacetate, 10 g of disodium nitrilotriacetate, 30 g of sodium hydrogen phosphate, 30 g of sodium hydroxide, 7 g of silver methanesulfonate, and 1 g of polyethylene glycol (polyethylene glycol 1000) And mixed to obtain a plating solution. The obtained plating solution was adjusted to have a pH of 7 using a 10 wt% sodium hydroxide solution. 50 g of solder particles to which palladium is attached and 6 g of formic acid are put in a plating solution and electroless plating is performed at 40 ° C. for 20 minutes to obtain conductive particles having a coating portion formed by electroless plating. It was.
　金属部の厚み及び被覆部の厚み：
　金属部の厚み及び被覆部の厚みを、上述した方法により測定した。 Metal part thickness and coating part thickness:
The thickness of the metal part and the thickness of the covering part were measured by the method described above.
　（実施例１～８及び比較例１）
　（１）導電材料の作製
　下記の表１に示す成分を下記の表１に示す配合量で配合して、遊星式撹拌装置で混合及び脱泡することにより導電材料（異方性導電ペースト）を得た。 (Examples 1 to 8 and Comparative Example 1)
(1) Production of conductive material The components shown in Table 1 below are blended in the blending amounts shown in Table 1 below, and the conductive material (anisotropic conductive paste) is mixed and defoamed with a planetary stirrer. Obtained.
　（２）接続構造体（エリアアレイ基板）の作製
　（２－１）条件Ａでの接続構造体の具体的な作製方法：
　第２の接続対象部材として、半導体チップ本体（サイズ５×５ｍｍ、厚み０．４ｍｍ）の表面に、４００μｍピッチで２５０μｍの銅電極が、エリアアレイにて配置されており、最表面にパッシベーション膜（ポリイミド、厚み５μｍ、電極部の開口径２００μｍ）が形成されている半導体チップを準備した。銅電極の数は、半導体チップ１個当たり、１０個×１０個の合計１００個である。 (2) Production of connection structure (area array substrate) (2-1) Specific production method of connection structure under condition A:
As a second connection target member, a copper electrode of 250 μm at a pitch of 400 μm is arranged in an area array on the surface of a semiconductor chip body (size 5 × 5 mm, thickness 0.4 mm), and a passivation film ( A semiconductor chip on which polyimide, a thickness of 5 μm, and an opening diameter of the electrode portion of 200 μm were formed was prepared. The number of copper electrodes is 10 × 10 in total per 100 semiconductor chips.
　第１の接続対象部材として、ガラスエポキシ基板本体（サイズ２０×２０ｍｍ、厚み１．２ｍｍ、材質ＦＲ－４）の表面に、第２の接続対象部材の電極に対して、同じパターンとなるように、銅電極が配置されており、銅電極が配置されていない領域にソルダーレジスト膜が形成されているガラスエポキシ基板を準備した。銅電極の表面とソルダーレジスト膜の表面との段差は、１５μｍであり、ソルダーレジスト膜は銅電極よりも突出している。 As the first connection target member, the same pattern is formed on the surface of the glass epoxy substrate body (size 20 × 20 mm, thickness 1.2 mm, material FR-4) with respect to the electrode of the second connection target member. The glass epoxy board | substrate with which the copper resist is arrange | positioned and the soldering resist film is formed in the area | region where the copper electrode is not arrange | positioned was prepared. The level difference between the surface of the copper electrode and the surface of the solder resist film is 15 μm, and the solder resist film protrudes from the copper electrode.
　上記ガラスエポキシ基板の上面に、作製直後の導電材料（異方性導電ペースト）を厚さ１００μｍとなるように塗工し、異方性導電ペースト層を形成した。次に、異方性導電ペースト層の上面に半導体チップを電極同士が対向するように積層した。異方性導電ペースト層には、上記半導体チップの重量は加わる。その状態から、異方性導電ペースト層の温度が、昇温開始から５秒後に１３９℃（はんだの融点）となるように加熱した。さらに、昇温開始から１５秒後に、異方性導電ペースト層の温度が１６０℃となるように加熱し、異方性導電ペースト層を硬化させ、接続構造体を得た。加熱時には、加圧を行わなかった。 The conductive material (anisotropic conductive paste) immediately after fabrication was applied to the upper surface of the glass epoxy substrate so as to have a thickness of 100 μm, thereby forming an anisotropic conductive paste layer. Next, a semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other. The weight of the semiconductor chip is added to the anisotropic conductive paste layer. From this state, the anisotropic conductive paste layer was heated so that the temperature became 139 ° C. (melting point of solder) after 5 seconds from the start of temperature increase. Further, 15 seconds after the start of temperature increase, the anisotropic conductive paste layer was heated to 160 ° C. to cure the anisotropic conductive paste layer, thereby obtaining a connection structure. No pressure was applied during heating.
　（２－２）条件Ｂでの接続構造体の具体的な作製方法：
　以下の変更をしたこと以外は、条件Ａと同様にして、接続構造体（エリアアレイ基板）を作製した。 (2-2) Specific manufacturing method of connection structure under condition B:
A connection structure (area array substrate) was produced in the same manner as in Condition A except that the following changes were made.
　条件Ａから条件Ｂへの変更点：
　上記ガラスエポキシ基板の上面に、作製直後の導電材料（異方性導電ペースト）を厚さ１００μｍとなるように塗工し、異方性導電ペースト層を形成した後、２５℃及び湿度５０％の環境下に６時間放置した。放置後、異方性導電ペースト層の上面に半導体チップを電極同士が対向するように積層した。 Changes from Condition A to Condition B:
On the upper surface of the glass epoxy substrate, a conductive material (anisotropic conductive paste) immediately after fabrication was applied to a thickness of 100 μm to form an anisotropic conductive paste layer. It was left in the environment for 6 hours. After leaving, a semiconductor chip was laminated on the upper surface of the anisotropic conductive paste layer so that the electrodes face each other.
　（評価）
　（１）２５℃における導電材料（異方性導電ペースト）の粘度（η２５）
　作製直後の導電材料（異方性導電ペースト）の２５℃での粘度（η２５）を、Ｅ型粘度計（東機産業社製「ＴＶＥ２２Ｌ」）を用いて、２５℃及び５ｒｐｍの条件で測定した。η２５を以下の基準で判定した。 (Evaluation)
(1) Viscosity of conductive material (anisotropic conductive paste) at 25 ° C. (η25)
The viscosity (η25) at 25 ° C. of the conductive material (anisotropic conductive paste) immediately after production was measured using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and 5 rpm. . η25 was determined according to the following criteria.
　［η２５の判定基準］
　△：η２５が２０Ｐａ・ｓ未満
　〇：η２５が２０Ｐａ・ｓ以上、６００Ｐａ・ｓ以下
　×：η２５が６００Ｐａ・ｓを超える [Criteria for η25]
Δ: η25 is less than 20 Pa · s ◯: η25 is 20 Pa · s or more and 600 Pa · s or less ×: η25 exceeds 600 Pa · s
　（２）導電性粒子の融点における導電材料（異方性導電ペースト）の粘度（ηｍｐ）　作製直後の導電材料（異方性導電ペースト）を、ＳＴＲＥＳＳＴＥＣＨ（ＲＥＯＬＯＧＩＣＡ社製）を用いて、歪制御１ｒａｄ、周波数１Ｈｚ、昇温速度２０℃／分、測定温度範囲４０℃～導電性粒子の融点の条件で測定した。この測定において、導電性粒子の融点での粘度を読み取り、導電性粒子の融点における導電材料（異方性導電ペースト）の粘度（ηｍｐ）とした。ηｍｐを以下の基準で判定した。 (2) Viscosity (ηmp) of conductive material (anisotropic conductive paste) at melting point of conductive particles Strain control 1 rad using STRESSTECH (manufactured by REOLOGICA) as the conductive material (anisotropic conductive paste) immediately after production. The measurement was performed under the conditions of a frequency of 1 Hz, a heating rate of 20 ° C./min, and a measurement temperature range of 40 ° C. to the melting point of the conductive particles. In this measurement, the viscosity at the melting point of the conductive particles was read and used as the viscosity (ηmp) of the conductive material (anisotropic conductive paste) at the melting point of the conductive particles. ηmp was determined according to the following criteria.
　［ηｍｐの判定基準］
　△：ηｍｐが０．１Ｐａ・ｓ未満
　〇：ηｍｐが０．１Ｐａ・ｓ以上、５Ｐａ・ｓ以下
　×：ηｍｐが５Ｐａ・ｓを超える [Criteria for ηmp]
Δ: ηmp is less than 0.1 Pa · s ◯: ηmp is 0.1 Pa · s or more and 5 Pa · s or less ×: ηmp is more than 5 Pa · s
　（３）貯蔵安定性
　作製直後の導電材料（異方性導電ペースト）の２５℃での粘度（η１）を、Ｅ型粘度計（東機産業社製「ＴＶＥ２２Ｌ」）を用いて、２５℃及び５ｒｐｍの条件で測定した。また、２５℃及び湿度５０％で３日間静置した後の導電材料（異方性導電ペースト）の２５℃での粘度（η２）をη１と同様にして測定した。貯蔵安定性を以下の基準で判定した。 (3) Storage stability The viscosity (η1) of a conductive material (anisotropic conductive paste) immediately after production at 25 ° C. was measured at 25 ° C. using an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.) The measurement was performed at 5 rpm. Further, the viscosity (η2) at 25 ° C. of the conductive material (anisotropic conductive paste) after standing at 25 ° C. and 50% humidity for 3 days was measured in the same manner as η1. Storage stability was determined according to the following criteria.
　［貯蔵安定性の判定基準］
　○：η２／η１が２未満
　△：η２／η１が２以上、３未満
　×：η２／η１が３以上 [Criteria for storage stability]
○: η2 / η1 is less than 2 Δ: η2 / η1 is 2 or more and less than 3 ×: η2 / η1 is 3 or more
　（４）はんだの濡れ性
　上記（３）の評価で用いた２５℃及び湿度５０％で３日間静置した後の導電材料（異方性導電ペースト）を準備した。これらの導電材料（異方性導電ペースト）を用いて、はんだの濡れ性を評価した。はんだの濡れ性は、下記のようにして評価した。はんだの濡れ性を以下の基準で判定した。 (4) Solder wettability A conductive material (anisotropic conductive paste) was prepared after standing for 3 days at 25 ° C. and 50% humidity used in the evaluation of (3) above. Using these conductive materials (anisotropic conductive paste), the wettability of the solder was evaluated. Solder wettability was evaluated as follows. Solder wettability was determined according to the following criteria.
　はんだの濡れ性の評価方法：
　金電極８ｍｍ２上に２ｍｍφのマスクで導電材料（異方性導電ペースト）を２ｍｇ塗布し、１７０℃で１０分間ホットプレートで加熱した。その後、画像解析にて金電極に対するはんだの濡れ面積（金電極の表面におけるはんだが接触している面積）の割合を算出した。 Method for evaluating solder wettability:
2 mg of a conductive material (anisotropic conductive paste) was applied onto a gold electrode 8 mm 2 with a 2 mmφ mask and heated on a hot plate at 170 ° C. for 10 minutes. Thereafter, the ratio of the wetted area of the solder to the gold electrode (area where the solder is in contact with the surface of the gold electrode) was calculated by image analysis.
　［はんだの濡れ性の判定基準］
　○：金電極に対するはんだの濡れ面積の割合が７０％以上
　△：金電極に対するはんだの濡れ面積の割合が４０％以上、７０％未満
　×：金電極に対するはんだの濡れ面積の割合が４０％未満 [Criteria for solder wettability]
○: The ratio of the solder wet area to the gold electrode is 70% or more. Δ: The ratio of the solder wet area to the gold electrode is 40% or more and less than 70%. X: The ratio of the solder wet area to the gold electrode is less than 40%.
　（５）電極上のはんだの配置精度
　条件Ａ及び条件Ｂにて得られた接続構造体において、第１の電極と接続部と第２の電極との積層方向に第１の電極と第２の電極との対向し合う部分をみたときに、第１の電極と第２の電極との対向し合う部分の面積１００％中の、接続部中のはんだ部が配置されている面積の割合Ｘを評価した。電極上のはんだの配置精度を以下の基準で判定した。 (5) Solder placement accuracy on the electrode In the connection structure obtained under the conditions A and B, the first electrode and the second electrode in the stacking direction of the first electrode, the connection portion, and the second electrode. When the portion facing the electrode is viewed, the ratio X of the area where the solder portion in the connecting portion is arranged in the area of 100% of the portion facing the first electrode and the second electrode is evaluated. The placement accuracy of the solder on the electrode was determined according to the following criteria.
　［電極上のはんだの配置精度の判定基準］
　○○：割合Ｘが７０％以上
　○：割合Ｘが６０％以上、７０％未満
　△：割合Ｘが５０％以上、６０％未満
　×：割合Ｘが５０％未満 [Criteria for solder placement accuracy on electrodes]
○○: Ratio X is 70% or more ○: Ratio X is 60% or more and less than 70% Δ: Ratio X is 50% or more and less than 60% X: Ratio X is less than 50%
　（６）上下の電極間の導通信頼性
　条件Ａ及び条件Ｂにて得られた接続構造体（ｎ＝１５個）において、上下の電極間の１接続箇所当たりの接続抵抗をそれぞれ、４端子法により測定した。接続抵抗の平均値を算出した。なお、電圧＝電流×抵抗の関係から、一定の電流を流した時の電圧を測定することにより接続抵抗を求めることができる。導通信頼性を以下の基準で判定した。 (6) Conduction reliability between upper and lower electrodes In the connection structure (n = 15) obtained in condition A and condition B, the connection resistance per connection point between the upper and lower electrodes is respectively determined by the four-terminal method. It was measured by. The average value of connection resistance was calculated. Note that the connection resistance can be obtained by measuring the voltage when a constant current is passed from the relationship of voltage = current × resistance. The conduction reliability was determined according to the following criteria.
　［導通信頼性の判定基準］
　○○：接続抵抗の平均値が５０ｍΩ以下
　○：接続抵抗の平均値が５０ｍΩを超え、７０ｍΩ以下
　△：接続抵抗の平均値が７０ｍΩを超え、１００ｍΩ以下
　×：接続抵抗の平均値が１００ｍΩを超える、又は接続不良が生じている [Judgment criteria for conduction reliability]
◯: Average connection resistance is 50 mΩ or less ○: Average connection resistance exceeds 50 mΩ, 70 mΩ or less △: Average connection resistance exceeds 70 mΩ, 100 mΩ or less ×: Average connection resistance exceeds 100 mΩ Or there is a bad connection
　（７）隣接する電極間の絶縁信頼性
　条件Ａ及び条件Ｂにて得られた接続構造体（ｎ＝１５個）において、８５℃及び湿度８５％の雰囲気中に１００時間放置後、隣接する電極間に、５Ｖを印加し、抵抗値を２５箇所で測定した。絶縁信頼性を以下の基準で判定した。 (7) Insulation reliability between adjacent electrodes In the connection structure (n = 15 pieces) obtained under the conditions A and B, the adjacent electrodes are left in an atmosphere of 85 ° C. and 85% humidity for 100 hours, and then adjacent electrodes. In the meantime, 5V was applied and the resistance value was measured at 25 locations. Insulation reliability was judged according to the following criteria.
　［絶縁信頼性の判定基準］
　○○：接続抵抗の平均値が１０７Ω以上
　○：接続抵抗の平均値が１０６Ω以上、１０７Ω未満
　△：接続抵抗の平均値が１０５Ω以上、１０６Ω未満
　×：接続抵抗の平均値が１０５Ω未満 [Criteria for insulation reliability]
◯: Average value of connection resistance is 10 7 Ω or more ○: Average value of connection resistance is 10 6 Ω or more, less than 10 7 Ω △: Average value of connection resistance is 10 5 Ω or more, less than 10 6 Ω ×: Connection The average resistance is less than 10 5 Ω
　（８）耐衝撃性
　上記（６）の評価に用いた接続構造体を準備した。これらの接続構造体を高さ７０ｃｍの位置から落下させて、上記（６）の評価と同様にして、導通信頼性を確認することにより耐衝撃性の評価を行った。上記（６）の評価で得られた接続抵抗の平均値からの抵抗値の上昇率により耐衝撃性を以下の基準で判定した。 (8) Impact resistance The connection structure used for the evaluation of (6) above was prepared. These connection structures were dropped from a position having a height of 70 cm, and the impact resistance was evaluated by confirming the conduction reliability in the same manner as in the evaluation of (6) above. Impact resistance was determined according to the following criteria based on the rate of increase in resistance value from the average value of connection resistance obtained in the evaluation of (6) above.
　［耐衝撃性の判定基準］
　○○：接続抵抗の平均値からの抵抗値の上昇率が２０％以下
　○：接続抵抗の平均値からの抵抗値の上昇率が２０％を超え、３５％以下
　△：接続抵抗の平均値からの抵抗値の上昇率が３５％を超え、５０％以下
　×：接続抵抗の平均値からの抵抗値の上昇率が５０％を超える [Evaluation criteria for impact resistance]
○○: The increase rate of resistance value from the average value of connection resistance is 20% or less ○: The increase rate of resistance value from the average value of connection resistance exceeds 20%, 35% or less △: From the average value of connection resistance The rate of increase in resistance value exceeds 35% and 50% or less. X: The rate of increase in resistance value from the average value of connection resistance exceeds 50%
　（９）被覆率
　得られた導電性粒子について、はんだ粒子の表面積全体１００％中、上記はんだ粒子の表面の被覆部により覆われている表面積（被覆率）を算出した。上記被覆率は、得られた導電性粒子をＳＥＭ－ＥＤＸ分析することで、Ａｇマッピングを行い、画像解析することで算出した。被覆率を以下の基準で判定した。 (9) Coverage About the obtained electroconductive particle, the surface area (coverage) covered with the coating | coated part of the surface of the said solder particle was calculated in 100% of the whole surface area of a solder particle. The coverage was calculated by performing SEM-EDX analysis on the obtained conductive particles, performing Ag mapping, and analyzing the image. The coverage was determined according to the following criteria.
　［被覆率の判定基準］
　○○：被覆率が９５％を超える
　○：被覆率が９０％を超え、９５％以下
　△：被覆率が８０％を超え、９０％以下
　×：被覆率が８０％以下 [Criteria for coverage rate]
◯: Coverage exceeds 95% ○: Coverage exceeds 90%, 95% or less △: Coverage exceeds 80%, 90% or less ×: Coverage is 80% or less
　結果を下記の表１に示す。 The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　フレキシブルプリント基板、樹脂フィルム、フレキシブルフラットケーブル及びリジッドフレキシブル基板を用いた場合でも、同様の傾向が見られた。 The same tendency was observed when using a flexible printed circuit board, a resin film, a flexible flat cable, and a rigid flexible circuit board.
　１，１Ｘ…接続構造体
　２…第１の接続対象部材
　２ａ…第１の電極
　３…第２の接続対象部材
　３ａ…第２の電極
　４，４Ｘ…接続部
　４Ａ，４ＸＡ…はんだ部
　４Ｂ，４ＸＢ…硬化物部
　１１…導電材料
　１１Ａ…導電性粒子
　１１Ｂ…熱硬化性成分
　２１，３１…導電性粒子
　２２…はんだ粒子
　２３…被覆部
　３２…金属部 DESCRIPTION OF SYMBOLS 1,1X ... Connection structure 2 ... 1st connection object member 2a ... 1st electrode 3 ... 2nd connection object member 3a ... 2nd electrode 4, 4X ... Connection part 4A, 4XA ... Solder part 4B, 4XB ... cured material part 11 ... conductive material 11A ... conductive particle 11B ... thermosetting component 21,31 ... conductive particle 22 ... solder particle 23 ... covering part 32 ... metal part

Claims (14)

  1. 　融点が２００℃未満のはんだ粒子と、
    　前記はんだ粒子の表面上に配置された被覆部とを備え、
    　前記被覆部が、銀を含む、導電性粒子。     Solder particles having a melting point of less than 200 ° C .;
    A coating portion disposed on the surface of the solder particles,
    The electroconductive particle in which the said coating | coated part contains silver.
  2. 　前記はんだ粒子が、スズ及びビスマスを含む、請求項１に記載の導電性粒子。 The conductive particles according to claim 1, wherein the solder particles include tin and bismuth.
  3. 　導電性粒子１００重量％中、前記銀の含有量が、１重量％以上、２０重量％以下である、請求項１又は２に記載の導電性粒子。 The conductive particles according to claim 1 or 2, wherein the content of the silver is 1 wt% or more and 20 wt% or less in 100 wt% of the conductive particles.
  4. 　前記はんだ粒子の表面積全体１００％中、前記はんだ粒子の表面の前記被覆部により覆われている表面積が、８０％以上である、請求項１～３のいずれか１項に記載の導電性粒子。 The conductive particles according to any one of claims 1 to 3, wherein a surface area of the surface of the solder particles covered by the covering portion is 100% or more out of 100% of the entire surface area of the solder particles.
  5. 　前記被覆部の厚みが、０．１μｍ以上、５μｍ以下である、請求項１～４のいずれか１項に記載の導電性粒子。 The conductive particles according to any one of claims 1 to 4, wherein the covering portion has a thickness of 0.1 µm or more and 5 µm or less.
  6. 　前記はんだ粒子の外表面と前記被覆部との間に、ニッケルを含む金属部を備える、請求項１～５のいずれか１項に記載の導電性粒子。 The conductive particle according to any one of claims 1 to 5, further comprising a metal part containing nickel between an outer surface of the solder particle and the covering part.
  7. 　請求項１～６のいずれか１項に記載の導電性粒子と、熱硬化性化合物とを含む、導電材料。 A conductive material comprising the conductive particles according to any one of claims 1 to 6 and a thermosetting compound.
  8. 　導電材料１００重量％中、前記導電性粒子の含有量が、５０重量％を超える、請求項７に記載の導電材料。 The conductive material according to claim 7, wherein a content of the conductive particles exceeds 50% by weight in 100% by weight of the conductive material.
  9. 　前記熱硬化性化合物が、ポリエーテル骨格を有する熱硬化性化合物を含む、請求項７又は８に記載の導電材料。 The conductive material according to claim 7 or 8, wherein the thermosetting compound includes a thermosetting compound having a polyether skeleton.
  10. 　融点が５０℃以上、１４０℃以下であるフラックスを含む、請求項７～９のいずれか１項に記載の導電材料。 10. The conductive material according to claim 7, comprising a flux having a melting point of 50 ° C. or higher and 140 ° C. or lower.
  11. 　２５℃での粘度が、２０Ｐａ・ｓ以上、６００Ｐａ・ｓ以下である、請求項７～１０のいずれか１項に記載の導電材料。 The conductive material according to any one of claims 7 to 10, wherein a viscosity at 25 ° C is 20 Pa · s or more and 600 Pa · s or less.
  12. 　導電ペーストである、請求項７～１１のいずれか１項に記載の導電材料。 The conductive material according to any one of claims 7 to 11, which is a conductive paste.
  13. 　少なくとも１つの第１の電極を表面に有する第１の接続対象部材と、
    　少なくとも１つの第２の電極を表面に有する第２の接続対象部材と、
    　前記第１の接続対象部材と、前記第２の接続対象部材とを接続している接続部とを備え、
    　前記接続部の材料が、請求項１～６のいずれか１項に記載の導電性粒子を含み、
    　前記第１の電極と前記第２の電極とが、前記接続部中のはんだ部により電気的に接続されている、接続構造体。     A first connection target member having at least one first electrode on its surface;
    A second connection target member having at least one second electrode on its surface;
    A connecting portion connecting the first connection target member and the second connection target member;
    The material of the connecting portion includes the conductive particles according to any one of claims 1 to 6,
    A connection structure in which the first electrode and the second electrode are electrically connected by a solder portion in the connection portion.
  14. 　前記第１の電極と前記接続部と前記第２の電極との積層方向に前記第１の電極と前記第２の電極との対向し合う部分をみたときに、前記第１の電極と前記第２の電極との対向し合う部分の面積１００％中の５０％以上に、前記接続部中のはんだ部が配置されている、請求項１３に記載の接続構造体。 When 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, the first electrode and the second electrode 14. The connection structure according to claim 13, wherein the solder portion in the connection portion is arranged in 50% or more of 100% of the area facing the two electrodes.
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