WO2020251043A1 - Particules conductrices, matériau conducteur et structure de connexion - Google Patents

Particules conductrices, matériau conducteur et structure de connexion Download PDF

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Publication number
WO2020251043A1
WO2020251043A1 PCT/JP2020/023304 JP2020023304W WO2020251043A1 WO 2020251043 A1 WO2020251043 A1 WO 2020251043A1 JP 2020023304 W JP2020023304 W JP 2020023304W WO 2020251043 A1 WO2020251043 A1 WO 2020251043A1
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WO
WIPO (PCT)
Prior art keywords
conductive
particles
solder
conductive portion
particle
Prior art date
Application number
PCT/JP2020/023304
Other languages
English (en)
Japanese (ja)
Inventor
良 栗浦
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 CN202080042463.8A priority Critical patent/CN113950778A/zh
Priority to KR1020217040219A priority patent/KR20220016863A/ko
Priority to JP2020558067A priority patent/JPWO2020251043A1/ja
Publication of WO2020251043A1 publication Critical patent/WO2020251043A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
    • H01R12/70—Coupling devices
    • H01R12/71—Coupling devices for rigid printing circuits or like structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits

Definitions

  • the present invention relates to conductive particles in which a conductive portion is arranged on the surface of the base particles.
  • the present invention also relates to a conductive material and a connecting structure using the above conductive particles.
  • Patent Document 1 the other ends of a plurality of pins (20) whose one end is connected to the first member (10) are aligned by using the aligning member (50), and the second member (
  • the connection structure of the electronic component connected to 30) is disclosed.
  • the alignment member (50) is rotated with reference to the axial direction (A) after aligning the pins (20) at the outer peripheral portion in the axial direction (A). It separates from the pin (20) and is removed from the pin (20).
  • solder paste or the like may be used for electrical connection between the substrate and the electronic component.
  • solder paste agglomeration of solder particles may occur.
  • the base particles are provided with a base particle and a conductive portion arranged on the surface of the base particle, and the conductive portion contains or contains a component capable of metal diffusion at 400 ° C. or lower.
  • the conductive portion can be melt-deformed at 400 ° C. or lower, the conductive portion has a solder portion, and the area of the portion having the solder portion is 99% or less in 100% of the total surface area of the base material particles.
  • Conductive particles are provided.
  • the solder portion is a solder grain.
  • the material of the solder particles contains a tin-containing alloy, is pure tin, or is in a state different from the tin-containing alloy and different from pure tin. Contains tin in the state.
  • the material of the solder particles is pure tin.
  • the height of the solder particles is 10 nm or more and 10 ⁇ m or less.
  • the aspect ratio of the solder particles is 0.05 or more and 5 or less.
  • the conductive particles have a metal colloidal precipitate or a metal film on the outer surface of the solder particles.
  • the area of the metal colloidal precipitate or the portion where the metal film is present is 5% or more and 100% or less in the total surface area of the solder particles.
  • the metal species of the metal colloidal precipitate or the metal species of the metal film may be nickel, cobalt, lead, gold, zinc, palladium, copper, silver, bismuth, or It is indium.
  • the particle size is 0.5 ⁇ m or more and 500 ⁇ m or less.
  • a conductive material containing conductive particles and a binder, wherein the conductive particles are the above-mentioned conductive particles.
  • a first connection target member having a first electrode on the surface
  • a second connection target member having a second electrode on the surface
  • the first connection target member and the above. It is provided with a connecting portion connecting the second connection target member, and the connecting portion is formed of conductive particles or is formed of a conductive material containing the conductive particles and a binder.
  • the conductive particles are the above-mentioned conductive particles, and the first electrode and the second electrode are electrically connected by the conductive particles.
  • the conductive particles according to the present invention include base particles and conductive portions arranged on the surface of the base particles.
  • the conductive portion contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion is melt-deformable at 400 ° C. or lower.
  • the conductive portion has a solder portion.
  • the area of the portion where the solder portion is located is 99% or less of the total surface area of the base particles of 100%. Since the conductive particles according to the present invention have the above-mentioned configuration, it is possible to effectively suppress the occurrence of aggregation between the conductive particles.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing the conductive particles according to the third embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing conductive particles according to a fourth embodiment of the present invention.
  • FIG. 5 is a cross-sectional view showing the conductive particles according to the fifth embodiment of the present invention.
  • FIG. 6 is a cross-sectional view showing the conductive particles according to the sixth embodiment of the present invention.
  • FIG. 7 is a cross-sectional view showing the conductive particles according to the seventh embodiment of the present invention.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
  • FIG. 3 is
  • FIG. 8 is a cross-sectional view showing the conductive particles according to the eighth embodiment of the present invention.
  • FIG. 9 is a front sectional view schematically showing a connection structure using conductive particles according to a third embodiment of the present invention.
  • FIG. 10 is a front sectional view schematically showing an enlarged connection portion between the conductive particles and the electrodes in the connection structure shown in FIG.
  • the conductive particles according to the present invention include base particles and conductive portions arranged on the surface of the base particles.
  • the conductive portion contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion is melt-deformable at 400 ° C. or lower.
  • the conductive portion may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion may be melt-deformable at 400 ° C. or lower.
  • the conductive portion may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion may be melt-deformable at 400 ° C. or lower.
  • the conductive portion may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion may be melt-deformable at 400 ° C.
  • the conductive portion has a solder portion.
  • the area of the portion where the solder portion is located is 99% or less of the total surface area of the base particles of 100%.
  • metal diffusion means that metal atoms diffuse in a conductive portion or a connecting portion due to heat, pressure, deformation, or the like.
  • the melt deformation means a state in which a part or all of the components are melted and easily deformed by an external pressure.
  • the conductive particles according to the present invention have the above-mentioned configuration, it is possible to effectively suppress the occurrence of aggregation between the conductive particles.
  • solder paste or the like may be used for electrical connection between the substrate and the electronic component.
  • solder paste agglomeration of solder particles may occur.
  • the conductive portion contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion is melt-deformable at 400 ° C. or lower.
  • the conductive portion has a solder portion.
  • the solder portion is preferably solder grains.
  • the conductive portion can form a metal bond with a joint portion such as an electrode, and the solder portion (solder grain) can form a metal bond with a joint portion such as an electrode. Can be formed.
  • the conductive particles according to the present invention since the solder portion (solder particles) can form a metal bond with a joint portion such as an electrode, it is not necessary to melt the entire conductive portion at the time of joining. .. As a result, in the present invention, the reliability of conduction between the electrodes can be improved even when the thickness of the conductive portion is relatively thin. Further, in the present invention, since it is not necessary to increase the thickness of the conductive portion, it is possible to effectively suppress the aggregation of the conductive particles.
  • the temperature at which the components of the conductive portion can diffuse with metal and the melt deformation temperature of the conductive portion can be achieved by selecting the material of the conductive portion. For example, by forming the solder portion using solder or a solder alloy as the material of the conductive portion, the temperature at which the components of the conductive portion can diffuse the metal and the melt deformation temperature of the conductive portion are set to 400 ° C. or lower. Is easy.
  • the conductive portion has a solder portion.
  • the conductive portion may be a solder portion.
  • the metal diffusion state of the conductive portion is evaluated as follows.
  • a conductive paste is applied onto the transparent glass substrate to form a conductive paste layer.
  • the semiconductor chips are laminated on the conductive paste layer so that the electrodes face each other.
  • the pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 0.5 MPa is applied to cure the conductive paste layer at 250 ° C. To obtain a connection structure.
  • connection structure may be embedded in the resin and the connection structure embedded in the resin may be mechanically polished.
  • the contact portion between the conductive particles and the copper electrode and the gold electrode is subjected to line analysis or element mapping by an energy dispersive X-ray analyzer (EDX). Observe the diffusion state of the metal.
  • EDX energy dispersive X-ray analyzer
  • the contact ratio between the outer circumference of the conductive particles and the copper electrode and the gold electrode can be calculated, and the quantification can be performed by this.
  • the melt deformation temperature of the conductive part is evaluated as follows.
  • the melt deformation temperature of the conductive portion can be measured using a differential scanning calorimeter (“DSC-6300” manufactured by Yamato Scientific Co., Ltd.). In the above measurement, 15 g of conductive particles were used, and the temperature rise range was 30 ° C. to 500 ° C. , Nitrogen purge amount 5 ml / min. Perform under the measurement conditions of.
  • DSC-6300 differential scanning calorimeter
  • the conductive portion is melted at the melting temperature obtained by the above measurement.
  • the conductive portion may be melt-deformed by melting a part of the conductive portion such as the solder portion (solder grain).
  • the area of the portion where the solder portion is located is 99% or less of the total surface area of the base particle of 100%.
  • the area of the portion where the solder portion is located is preferably 95% or less, more preferably 90% or less, still more preferably 85% or less, particularly preferably. Is 70% or less.
  • the area of the portion where the solder portion is located is preferably 5% or more, more preferably 30% or more, and further preferably 60% or more in the total surface area of the base particles of 100%.
  • the coverage coverage of the solder portion
  • the covering ratio covering ratio of the solder portion
  • the area of the portion where the solder portion is located (coverage ratio of the solder portion) in the total surface area of the base particle is 100% by performing element mapping by SEM-EDX analysis of the cross section of the conductive particle and image analysis. Can be calculated.
  • the particle size of the conductive particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, particularly preferably 20 ⁇ m or less, most preferably. It is 10 ⁇ m or less.
  • the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrode can be sufficiently increased, and the conductive portion aggregated when the conductive portion is formed. It becomes difficult for the sex particles to be formed, and it becomes difficult for the conductive portion to peel off from the surface of the base particle.
  • the particle size of the conductive particles is preferably an average particle size, and preferably a number average particle size.
  • the average value of the particle size of each conductive particle is calculated, or a particle size distribution measuring device is used. Obtained using.
  • the particle size of each conductive particle is determined as the particle size in the equivalent circle diameter.
  • the average particle diameter of any 50 conductive particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent diameter of the sphere.
  • the particle size of each conductive particle is obtained as the particle size in the equivalent diameter of a sphere.
  • the average particle size of the conductive particles is preferably calculated using a particle size distribution measuring device.
  • the coefficient of variation (CV value) of the particle size of the conductive particles is preferably 10% or less, more preferably 5% or less.
  • the coefficient of variation of the particle size of the conductive particles is not more than the above upper limit, the contact area between the conductive particles and the electrode can be sufficiently increased.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle size of conductive particles Dn: Mean value of particle size of conductive particles
  • the shape of the conductive particles is not particularly limited.
  • the shape of the conductive particles may be spherical, non-spherical, flat or the like.
  • FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
  • the conductive particle 1 shown in FIG. 1 includes a base particle 2 and a conductive portion 3 arranged on the surface of the base particle 2.
  • the conductive portion 3 is in contact with the surface of the base particle 2.
  • the conductive particles 1 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 3.
  • the conductive portion 3 includes a first conductive portion 3A arranged on the surface of the base particle 2 and a second conductive portion (solder portion) 3B arranged on the surface of the first conductive portion 3A.
  • the first conductive portion 3A is arranged on the surface of the base particle 2.
  • the first conductive portion 3A is arranged between the base particle 2 and the second conductive portion (solder portion) 3B.
  • the first conductive portion 3A is in contact with the base particle 2.
  • the second conductive portion (solder portion) 3B is in contact with the first conductive portion 3A.
  • the first conductive portion 3A is arranged on the surface of the base particle 2, and the second conductive portion (solder portion) 3B is arranged on the surface of the first conductive portion 3A.
  • the base material particles may or may not be completely coated by the first conductive portion.
  • the base particle may have a portion not covered by the first conductive portion.
  • the first conductive portion and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the first conductive portion is arranged on the surface of the base material particles, and the solder particles are arranged on the surface of the first conductive portion.
  • the conductive portion 3 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 3 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 3 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 3 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 3 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 3 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 3B (solder portion) is a component capable of metal diffusion at 400 ° C. or lower.
  • the second conductive portion 3B (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the first conductive portion may be a component capable of diffusing metal at 400 ° C. or lower, or the first conductive portion may be melt-deformable at 400 ° C. or lower.
  • the first conductive portion and the second conductive portion (solder portion) may be components capable of diffusing metal at 400 ° C. or lower, and the first conductive portion and the second conductive portion may be present.
  • the conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • FIG. 2 is a cross-sectional view showing the conductive particles according to the second embodiment of the present invention.
  • the conductive particle 11 shown in FIG. 2 includes a base particle 2 and a conductive portion 12 arranged on the surface of the base particle 2.
  • the conductive portion 12 is in contact with the surface of the base particle 2.
  • the conductive particles 11 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 12.
  • the conductive particle 11 is composed of the conductive portion 12A of the first a and the conductive portion 12B of the first b.
  • a first conductive portion having a two-layer structure is formed.
  • the conductive portion 12 is composed of a first conductive portion 12A arranged on the surface of the base particle 2, a first conductive portion 12B arranged on the surface of the first conductive portion 12A, and a first b. It has a second conductive portion (solder portion) 12C arranged on the surface of the conductive portion 12B.
  • the conductive portion 12A of the first a is arranged on the surface of the base particle 2.
  • the conductive portion 12B of the first b is arranged on the surface of the conductive portion 12A of the first a.
  • the conductive portion 12A of the first a and the conductive portion 12B of the first b are arranged between the base particle 2 and the second conductive portion (solder portion) 12C.
  • the conductive portion 12A of the first a is in contact with the base particle 2.
  • the second conductive portion (solder portion) 12C is in contact with the first conductive portion 12B. Therefore, the conductive portion 12A of the first a is arranged on the surface of the base particle 2, the conductive portion 12B of the first b is arranged on the surface of the conductive portion 12A of the first a, and the conductive portion 12B of the first b is arranged.
  • a second conductive portion (solder portion) 12C is arranged on the surface of the above.
  • the base material particles may or may not be completely covered by the conductive portion of the first a and the conductive portion of the first b.
  • the base material particles may have a portion not covered by the conductive portion of the first a and the conductive portion of the first b.
  • the conductive portion of the first a, the conductive portion of the first b, and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the conductive portion of the first 1a is arranged on the surface of the base material particles
  • the conductive portion of the first b is arranged on the surface of the conductive portion of the first a. It is preferable that the solder particles are arranged on the surface of the conductive portion of 1b.
  • the conductive portion 12 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 12 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 12 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 12 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 12 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 12 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 12C (solder portion) is a component capable of diffusing metal at 400 ° C. or lower.
  • the second conductive portion 12C (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the conductive portion of the first a or the conductive portion of the first b may be a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion of the first a or the conductive portion of the first b is 400. It may be melt-deformed at ° C or lower.
  • the conductive portion of the first a, the conductive portion of the first b, and the second conductive portion (solder portion) may be components capable of metal diffusion at 400 ° C. or lower, and the conductive particles of the first a.
  • the conductive portion, the conductive portion of the first b, and the second conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • FIG. 3 is a cross-sectional view showing the conductive particles according to the third embodiment of the present invention.
  • the conductive particle 21 shown in FIG. 3 includes a base particle 2 and a conductive portion 22 arranged on the surface of the base particle 2.
  • the conductive portion 22 is in contact with the surface of the base particle 2.
  • the conductive particles 21 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 22.
  • the conductive particles 1 and the conductive particles 21 differ only in the shape of the second conductive portion (solder portion). That is, in the conductive particle 1, the shape of the second conductive portion (solder portion) 3B is a part of a sphere, whereas in the conductive particle 21, the second conductive portion (solder portion) 22B The shape of is needle-shaped and is a rotating paraboloid.
  • the conductive portion 22 includes a first conductive portion 22A arranged on the surface of the base particle 2, and a second conductive portion (solder portion) 22B arranged on the surface of the first conductive portion 22A.
  • the first conductive portion 22A is arranged on the surface of the base particle 2.
  • the first conductive portion 22A is arranged between the base particle 2 and the second conductive portion (solder portion) 22B.
  • the first conductive portion 22A is in contact with the base particle 2.
  • the second conductive portion (solder portion) 22B is in contact with the first conductive portion 22A.
  • the first conductive portion 22A is arranged on the surface of the base particle 2, and the second conductive portion (solder portion) 22B is arranged on the surface of the first conductive portion 22A.
  • the base material particles may or may not be completely coated by the first conductive portion.
  • the base particle may have a portion not covered by the first conductive portion.
  • the first conductive portion and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the conductive portion 22 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 22 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 22 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 22 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 22 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 22 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 22B (solder portion) is a component capable of diffusing metal at 400 ° C. or lower.
  • the second conductive portion 22B (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the first conductive portion may be a component capable of diffusing metal at 400 ° C. or lower, or the first conductive portion may be melt-deformable at 400 ° C. or lower.
  • the first conductive portion and the second conductive portion (solder portion) may be components capable of diffusing metal at 400 ° C. or lower, and the first conductive portion and the second conductive portion may be present.
  • the conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • FIG. 4 is a cross-sectional view showing conductive particles according to a fourth embodiment of the present invention.
  • the conductive particle 31 shown in FIG. 4 includes a base particle 2 and a conductive portion 32 arranged on the surface of the base particle 2.
  • the conductive portion 32 is in contact with the surface of the base particle 2.
  • the conductive particles 31 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 32.
  • the conductive portion 22 is formed by the first conductive portion 22A and the second conductive portion (solder portion) 22B, whereas in the conductive particles 31, the conductive portion 32 is the second. It is formed by the conductive portion 32A of 1, the second conductive portion (solder portion) 32B, and the third conductive portion 32C.
  • the conductive portion 32 includes a first conductive portion 32A arranged on the surface of the base particle 2, and a second conductive portion (solder portion) 32B arranged on the surface of the first conductive portion 32A. It has a first conductive portion 32A and a third conductive portion 32C arranged on the surface of the second conductive portion (solder portion) 32B.
  • the first conductive portion 32A is arranged on the surface of the base particle 2.
  • the third conductive portion 32C is arranged on the surfaces of the first conductive portion 32A and the second conductive portion (solder portion) 32B.
  • a first conductive portion 32A and a second conductive portion (solder portion) 32B are arranged between the base particle 2 and the third conductive portion 32C.
  • the first conductive portion 32A is in contact with the base particle 2.
  • the second conductive portion (solder portion) 32B is in contact with the first conductive portion 32A.
  • the third conductive portion 32C is in contact with the first conductive portion 32A and the second conductive portion (solder portion) 32B. Therefore, the first conductive portion 32A is arranged on the surface of the base particle 2, and the second conductive portion (solder portion) 32B is arranged on the surface of the first conductive portion 32A.
  • a third conductive portion 32C is arranged on the surfaces of the conductive portion 32A and the second conductive portion (solder portion) 32B.
  • the base material particles may or may not be completely coated by the first conductive portion.
  • the base particle may have a portion not covered by the first conductive portion.
  • the base particles may or may not be completely coated by the third conductive portion.
  • the base material particles may have a portion not covered by the third conductive portion.
  • the first conductive portion, the second conductive portion (solder portion), and the third conductive portion may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the first conductive portion is arranged on the surface of the base material particles, the solder particles are arranged on the surface of the first conductive portion, and the first conductive portion is arranged. It is preferable that the third conductive portion is arranged on the surface of the portion and the solder particles.
  • the conductive portion 32 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 32 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 32 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 32 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 32 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 32 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 32B (solder portion) is a component capable of diffusing metal at 400 ° C. or lower.
  • the second conductive portion 32B (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the first conductive portion may be a component capable of diffusing metal at 400 ° C. or lower, or the first conductive portion may be melt-deformable at 400 ° C. or lower.
  • the third conductive portion may be a component capable of diffusing metal at 400 ° C. or lower, and the third conductive portion may be melt-deformable at 400 ° C. or lower.
  • the first conductive portion, the second conductive portion (solder portion), and the third conductive portion may be components capable of metal diffusion at 400 ° C. or lower, and the first conductive portion may be used.
  • the conductive portion, the second conductive portion (solder portion), and the third conductive portion may be melt-deformed at 400 ° C. or lower.
  • FIG. 5 is a cross-sectional view showing the conductive particles according to the fifth embodiment of the present invention.
  • the conductive particle 41 shown in FIG. 5 includes a base particle 2, a conductive portion 42 arranged on the surface of the base particle 2, and a metal colloidal precipitate 43 arranged on the surface of the conductive portion 42. ..
  • the conductive portion 42 is in contact with the surface of the base particle 2.
  • the conductive particles 41 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 42.
  • the conductive particles 1 and the conductive particles 41 differ only in the presence or absence of the metal colloidal precipitate 43. That is, in the conductive particle 1, the metal colloidal precipitate is not arranged on the surface of the conductive portion 3, whereas in the conductive particle 41, the metal colloidal precipitate 43 is arranged on the surface of the conductive portion 42. ing.
  • the conductive portion 42 includes a first conductive portion 42A arranged on the surface of the base particle 2 and a second conductive portion (solder portion) 42B arranged on the surface of the first conductive portion 42A.
  • the first conductive portion 42A is arranged on the surface of the base particle 2.
  • the first conductive portion 42A is arranged between the base particle 2 and the second conductive portion (solder portion) 42B.
  • the first conductive portion 42A is in contact with the base particle 2.
  • the second conductive portion (solder portion) 42B is in contact with the first conductive portion 42A.
  • the first conductive portion 42A is arranged on the surface of the base particle 2, and the second conductive portion (solder portion) 42B is arranged on the surface of the first conductive portion 42A.
  • the base material particles may or may not be completely coated by the first conductive portion.
  • the base particle may have a portion not covered by the first conductive portion.
  • the first conductive portion and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the first conductive portion is arranged on the surface of the base material particles, and the solder particles are arranged on the surface of the first conductive portion.
  • the metal colloidal precipitate 43 is arranged on the surface of the conductive portion 42.
  • the metal colloidal precipitate may be arranged only on the surface of the first conductive portion, may be arranged only on the surface of the second conductive portion (solder portion), and may be arranged only on the surface of the first conductive portion. It may be arranged on the surface of the conductive portion of the above and the second conductive portion (solder portion).
  • the metal colloidal precipitate is preferably arranged only on the surface of the second conductive portion (solder portion), and preferably is arranged only on the surface of the solder particles. In the conductive particles, the conductive portion may or may not be completely covered with the metal colloidal precipitate. The conductive portion may have a portion not covered with the metal colloidal precipitate.
  • the conductive portion 42 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 42 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 42 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 42 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 42 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 42 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 42B (solder portion) is a component capable of diffusing metal at 400 ° C. or lower.
  • the second conductive portion 42B (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the first conductive portion may be a component capable of diffusing metal at 400 ° C. or lower, or the first conductive portion may be melt-deformable at 400 ° C. or lower.
  • the first conductive portion and the second conductive portion (solder portion) may be components capable of diffusing metal at 400 ° C. or lower, and the first conductive portion and the second conductive portion may be present.
  • the conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • FIG. 6 is a cross-sectional view showing the conductive particles according to the sixth embodiment of the present invention.
  • the conductive particle 51 shown in FIG. 6 includes a base particle 2, a conductive portion 52 arranged on the surface of the base particle 2, and a metal colloidal precipitate 53 arranged on the surface of the conductive portion 52. .. In the sixth embodiment, the conductive portion 52 is in contact with the surface of the base particle 2.
  • the conductive particles 51 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 52.
  • the conductive particles 11 and the conductive particles 51 differ only in the presence or absence of the metal colloidal precipitate 53. That is, in the conductive particles 11, the metal colloidal precipitates are not arranged on the surface of the conductive portion 12, whereas in the conductive particles 51, the metal colloidal precipitates 53 are arranged on the surface of the conductive portion 52. ing.
  • the conductive portion 52 is a first conductive portion 52A arranged on the surface of the base particle 2, a first conductive portion 52B arranged on the surface of the first conductive portion 52A, and a first b. It has a second conductive portion (solder portion) 52C arranged on the surface of the conductive portion 52B.
  • the conductive portion 52A of the first a is arranged on the surface of the base particle 2.
  • the conductive portion 52B of the first b is arranged on the surface of the conductive portion 52A of the first a.
  • the first conductive portion 52A and the first conductive portion 52B are arranged between the base particle 2 and the second conductive portion (solder portion) 52C.
  • the conductive portion 52A of the first a is in contact with the base particle 2.
  • the second conductive portion (solder portion) 52C is in contact with the first conductive portion 52B. Therefore, the conductive portion 52A of the first a is arranged on the surface of the base particle 2, the conductive portion 52B of the first b is arranged on the surface of the conductive portion 52A of the first a, and the conductive portion 52B of the first b is arranged.
  • a second conductive portion (solder portion) 52C is arranged on the surface of the above.
  • the base material particles may or may not be completely covered by the conductive portion of the first a and the conductive portion of the first b.
  • the base material particles may have a portion not covered by the conductive portion of the first a and the conductive portion of the first b.
  • the conductive portion of the first a, the conductive portion of the first b, and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the conductive portion of the first 1a is arranged on the surface of the base material particles
  • the conductive portion of the first b is arranged on the surface of the conductive portion of the first a. It is preferable that the solder particles are arranged on the surface of the conductive portion of 1b.
  • a metal colloidal precipitate 53 is arranged on the surface of the conductive portion 52.
  • the metal colloidal precipitate may be arranged only on the surface of the conductive portion of the first b, or may be arranged only on the surface of the second conductive portion (solder portion), and may be arranged only on the surface of the conductive portion of the first b. It may be arranged on the surface of the conductive portion of the above and the second conductive portion (solder portion).
  • the metal colloidal precipitate is preferably arranged only on the surface of the second conductive portion (solder portion), and preferably is arranged only on the surface of the solder particles. In the conductive particles, the conductive portion may or may not be completely covered with the metal colloidal precipitate. The conductive portion may have a portion not covered with the metal colloidal precipitate.
  • the conductive portion 52 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 52 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 52 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 52 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 52 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 52 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 52C (solder portion) is a component capable of metal diffusion at 400 ° C. or lower.
  • the second conductive portion 52C (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the conductive portion of the first a or the conductive portion of the first b may be a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion of the first a or the conductive portion of the first b is 400. It may be melt-deformed at ° C or lower.
  • the conductive portion of the first a, the conductive portion of the first b, and the second conductive portion (solder portion) may be components capable of metal diffusion at 400 ° C. or lower, and the conductive particles of the first a.
  • the conductive portion, the conductive portion of the first b, and the second conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • FIG. 7 is a cross-sectional view showing the conductive particles according to the seventh embodiment of the present invention.
  • the conductive particle 61 shown in FIG. 7 includes a base particle 2, a conductive portion 62 arranged on the surface of the base particle 2, and a metal film 63 arranged on the surface of the conductive portion 62.
  • the conductive portion 62 is in contact with the surface of the base particle 2.
  • the conductive particles 61 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 62.
  • the conductive particles 1 and the conductive particles 61 differ only in the presence or absence of the metal film 63. That is, in the conductive particles 1, the metal film is not arranged on the surface of the conductive portion 3, whereas in the conductive particles 61, the metal film 63 is arranged on the surface of the conductive portion 62.
  • the conductive portion 62 includes a first conductive portion 62A arranged on the surface of the base particle 2 and a second conductive portion (solder portion) 62B arranged on the surface of the first conductive portion 62A.
  • the first conductive portion 62A is arranged on the surface of the base particle 2.
  • the first conductive portion 62A is arranged between the base particle 2 and the second conductive portion (solder portion) 62B.
  • the first conductive portion 62A is in contact with the base particle 2.
  • the second conductive portion (solder portion) 62B is in contact with the first conductive portion 62A.
  • the first conductive portion 62A is arranged on the surface of the base particle 2, and the second conductive portion (solder portion) 62B is arranged on the surface of the first conductive portion 62A.
  • the base material particles may or may not be completely coated by the first conductive portion.
  • the base particle may have a portion not covered by the first conductive portion.
  • the first conductive portion and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the first conductive portion is arranged on the surface of the base material particles, and the solder particles are arranged on the surface of the first conductive portion.
  • a metal film 63 is arranged on the surface of the conductive portion 62.
  • the metal film may be arranged only on the surface of the first conductive portion, may be arranged only on the surface of the second conductive portion (solder portion), and may be arranged only on the surface of the first conductive portion. It may be arranged on the surface of the portion and the second conductive portion (solder portion).
  • the metal film is preferably arranged only on the surface of the second conductive portion (solder portion), and is preferably arranged only on the surface of the solder grains.
  • the conductive portion may or may not be completely covered with the metal film.
  • the conductive portion may have a portion that is not covered with the metal film.
  • the conductive portion 62 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 62 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 62 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 62 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 62 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 62 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 62B (solder portion) is a component capable of diffusing metal at 400 ° C. or lower.
  • the second conductive portion 62B (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the first conductive portion may be a component capable of diffusing metal at 400 ° C. or lower, or the first conductive portion may be melt-deformable at 400 ° C. or lower.
  • the first conductive portion and the second conductive portion (solder portion) may be components capable of diffusing metal at 400 ° C. or lower, and the first conductive portion and the second conductive portion may be present.
  • the conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • FIG. 8 is a cross-sectional view showing the conductive particles according to the eighth embodiment of the present invention.
  • the conductive particle 71 shown in FIG. 8 includes a base particle 2, a conductive portion 72 arranged on the surface of the base particle 2, and a metal film 73 arranged on the surface of the conductive portion 72.
  • the conductive portion 72 is in contact with the surface of the base particle 2.
  • the conductive particles 71 are coated particles in which the surface of the base particle 2 is coated with the conductive portion 72.
  • the metal film 73 differs between the conductive particles 11 and the conductive particles 71. That is, in the conductive particles 11, the metal film is not arranged on the surface of the conductive portion 12, whereas in the conductive particles 71, the metal film 73 is arranged on the surface of the conductive portion 72.
  • the conductive portion 72 is a first conductive portion 72A arranged on the surface of the base particle 2, a first conductive portion 72B arranged on the surface of the first conductive portion 72A, and a first b. It has a second conductive portion (solder portion) 72C arranged on the surface of the conductive portion 72B.
  • the conductive portion 72A of the first a is arranged on the surface of the base particle 2.
  • the conductive portion 72B of the first b is arranged on the surface of the conductive portion 72A of the first a.
  • the conductive portion 72A of the first a and the conductive portion 72B of the first b are arranged between the base particle 2 and the second conductive portion (solder portion) 72C.
  • the conductive portion 72A of the first a is in contact with the base particle 2.
  • the second conductive portion (solder portion) 72C is in contact with the first conductive portion 72B. Therefore, the conductive portion 72A of the first a is arranged on the surface of the base particle 2, the conductive portion 72B of the first b is arranged on the surface of the conductive portion 72A of the first a, and the conductive portion 72B of the first b is arranged.
  • a second conductive portion (solder portion) 72C is arranged on the surface of the above.
  • the base material particles may or may not be completely covered by the conductive portion of the first a and the conductive portion of the first b.
  • the base material particles may have a portion not covered by the conductive portion of the first a and the conductive portion of the first b.
  • the conductive portion of the first a, the conductive portion of the first b, and the second conductive portion (solder portion) may be formed as different conductive portions or may be formed as the same conductive portion.
  • the second conductive portion (solder portion) is formed of solder.
  • the second conductive portion (solder portion) is preferably solder grains, which will be described later.
  • the conductive portion of the first 1a is arranged on the surface of the base material particles
  • the conductive portion of the first b is arranged on the surface of the conductive portion of the first a. It is preferable that the solder particles are arranged on the surface of the conductive portion of 1b.
  • a metal film 73 is arranged on the surface of the conductive portion 72.
  • the metal film may be arranged only on the surface of the conductive portion of the first b, may be arranged only on the surface of the second conductive portion (solder portion), or may be arranged only on the surface of the conductive portion of the first b. It may be arranged on the surface of the portion and the second conductive portion (solder portion).
  • the metal film is preferably arranged only on the surface of the second conductive portion (solder portion), and is preferably arranged only on the surface of the solder grains.
  • the conductive portion may or may not be completely covered with the metal film.
  • the conductive portion may have a portion that is not covered with the metal film.
  • the conductive portion 72 contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion 72 is melt-deformable at 400 ° C. or lower.
  • the conductive portion 72 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 72 may be melt-deformable at 400 ° C. or lower.
  • the conductive portion 72 may contain a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion 72 may be melt-deformable at 400 ° C. or lower.
  • the second conductive portion 72C (solder portion) is a component capable of diffusing metal at 400 ° C. or lower.
  • the second conductive portion 72C (solder portion) can be melt-deformed at 400 ° C. or lower.
  • the conductive portion of the first a or the conductive portion of the first b may be a component capable of diffusing metal at 400 ° C. or lower, and the conductive portion of the first a or the conductive portion of the first b is 400. It may be melt-deformed at ° C or lower.
  • the conductive portion of the first a, the conductive portion of the first b, and the second conductive portion (solder portion) may be components capable of metal diffusion at 400 ° C. or lower, and the conductive particles of the first a.
  • the conductive portion, the conductive portion of the first b, and the second conductive portion (solder portion) may be melt-deformed at 400 ° C. or lower.
  • (meth) acrylic means one or both of “acrylic” and “methacryl”
  • (meth) acryloxy means one or both of “acryloxy” and “methacryloxy”.
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”.
  • the material of the base particle is not particularly limited.
  • the material of the base particle may be an organic material or an inorganic material.
  • Examples of the base particle formed from the organic material alone include resin particles and the like.
  • Examples of the base particle formed only from the above-mentioned inorganic material include inorganic particles excluding metal.
  • Examples of the base particle formed by both the organic material and the inorganic material include organic-inorganic hybrid particles. From the viewpoint of further improving the compression characteristics of the base particles, the base particles are preferably resin particles or organic-inorganic hybrid particles, and more preferably resin particles.
  • organic material examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene; acrylic resins such as polymethylmethacrylate and polymethylacrylate; polycarbonate, polyamide, phenolformaldehyde resin and melamine.
  • polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene and polybutadiene
  • acrylic resins such as polymethylmethacrylate and polymethylacrylate
  • polycarbonate polyamide, phenolformaldehyde resin and melamine.
  • Formaldehyde resin benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, Examples thereof include polyester ether ketone, polyether sulfone, divinylbenzene polymer, and divinylbenzene copolymer.
  • the divinylbenzene copolymer and the like examples include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylic acid ester copolymer. Since the compression characteristics of the base material particles can be easily controlled within a suitable range, the material of the base material particles is a polymer obtained by polymerizing one or more kinds of polymerizable monomers having an ethylenically unsaturated group. Is preferable.
  • the base material particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group
  • the polymerizable monomer having an ethylenically unsaturated group is crosslinked with a non-crosslinkable monomer.
  • examples include sex monomers.
  • non-crosslinkable monomer examples include styrene monomers such as styrene, ⁇ -methylstyrene and chlorostyrene; vinyl ether compounds such as methylvinyl ether, ethylvinyl ether and propylvinyl ether; vinyl acetate, vinyl butyrate, etc.
  • Acid vinyl ester compounds such as vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; as (meth) acrylic compounds, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and other alkyl ( Meta) acrylate compound; oxygen atom-containing (meth) acrylate compound such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate; (meth)
  • Nitrile-containing monomer Halogen-containing (meth) acrylate compound such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate; olefins such as diisobutylene, isobutylene, linearene, ethylene and propylene as ⁇ -olefin compounds Compound;
  • Examples of the conjugated diene compound include isoprene and butadiene.
  • crosslinkable monomer examples include vinyl monomers such as divinylbenzene, 1,4-dibinyloxybutane, and divinylsulfone as vinyl compounds; and tetramethylolmethanetetra (meth) acrylate as (meth) acrylic compounds.
  • examples of the inorganic material include silica, alumina, barium titanate, zirconia, carbon black, silicate glass, borosilicate glass, lead glass, soda-lime glass and alumina silicate glass.
  • the base particle may be an organic-inorganic hybrid particle.
  • the base material particles may be core-shell particles.
  • examples of the inorganic material as the material of the base material particles include silica, alumina, barium titanate, zirconia, and carbon black. It is preferable that the inorganic substance is not a metal.
  • the base particles formed of the above silica are not particularly limited, but after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, firing is performed if necessary. Examples thereof include substrate particles obtained by carrying out the process.
  • Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
  • the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell arranged on the surface of the core. It is preferable that the core is an organic core. It is preferable that the shell is an inorganic shell.
  • the base material particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell arranged on the surface of the organic core.
  • Examples of the organic core material include the above-mentioned organic material and the like.
  • the material for the inorganic shell examples include the above-mentioned inorganic substances as the material for the base particle.
  • the material of the inorganic shell is preferably silica.
  • the inorganic shell is preferably formed by forming a metal alkoxide into a shell-like material by a sol-gel method on the surface of the core and then firing the shell-like material.
  • the metal alkoxide is preferably a silane alkoxide.
  • the inorganic shell is preferably formed of silane alkoxide.
  • the particle size of the base particles is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, particularly preferably 20 ⁇ m or less, most preferably. It is 10 ⁇ m or less.
  • the particle size of the base material particles is not less than the above lower limit and not more than the above upper limit, it can be more preferably used to obtain conductive particles.
  • the contact area between the conductive particles and the electrode can be sufficiently increased, and the conductive portion aggregated when the conductive portion is formed. It becomes difficult for the sex particles to be formed, and it becomes difficult for the conductive portion to peel off from the surface of the base particle.
  • the particle size of the base particle is 1 ⁇ m or more and 50 ⁇ m or less.
  • the particle size of the base material particles is within the range of 1 ⁇ m or more and 50 ⁇ m or less, it becomes difficult to agglomerate when forming a conductive portion on the surface of the base material particles, and it becomes difficult to form agglomerated conductive particles.
  • the particle size of the base material particles is within the range of 1 ⁇ m or more and 50 ⁇ m or less, it can be more preferably used to obtain conductive particles.
  • the particle diameter of the base material particles indicates the diameter when the base material particles are spherical, and when the base material particles are not spherical, the diameter when it is assumed to be a true sphere corresponding to the volume thereof. means.
  • the particle size of the base particle indicates a number average particle size.
  • 50 arbitrary base particles are observed with an electron microscope or an optical microscope, the average value of the particle size of each base particle is calculated, or a particle size distribution measuring device is used. Desired.
  • the particle size of each base particle is determined as the particle size in the equivalent circle diameter.
  • the average particle diameter of any 50 base particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent diameter of the sphere.
  • the particle size of each base particle is determined as the particle size in the equivalent sphere diameter.
  • the average particle size of the base particles is preferably calculated using a particle size distribution measuring device. When measuring the particle size of the base material particles in the conductive particles, for example, the measurement can be performed as follows.
  • the conductive particles according to the present invention include base particles and conductive portions arranged on the surface of the base particles.
  • the conductive portion preferably contains a metal.
  • the conductive portion contains a component capable of diffusing metal at 400 ° C. or lower, or the conductive portion is melt-deformable at 400 ° C. or lower.
  • the temperature at which the metal can diffuse is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, further preferably 250 ° C. or lower, and particularly preferably 200 ° C. or lower.
  • the temperature at which the metal can diffuse can be controlled by the type of metal.
  • the conductive portion can be melt-deformed at 400 ° C. or lower.
  • the conductive portion is preferably melt-deformable at 350 ° C. or lower, more preferably melt-deformable at 300 ° C. or lower, further preferably melt-deformable at 250 ° C. or lower, and 200 ° C. or lower. It is particularly preferable that it can be melt-deformed.
  • the melt deformation temperature of the conductive portion is within the above preferable range, the melt deformation temperature can be lowered, the energy consumption during heating can be suppressed, and the thermal deterioration of the member to be connected or the like can be suppressed. be able to.
  • the melt deformation temperature of the conductive portion can be controlled by the type of metal of the conductive portion.
  • the conductive portion may have a portion exceeding 200 ° C., may have a portion exceeding 250 ° C., may have a portion exceeding 300 ° C., and may have a portion exceeding 350 ° C. It may have a portion exceeding 400 ° C.
  • the metal constituting the conductive portion is not particularly limited.
  • Metals constituting the conductive portion include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, tarium, germanium, cadmium, etc. Examples thereof include silicon, tungsten, molybdenum and alloys thereof. Examples of the metal constituting the conductive portion include tin-doped indium oxide (ITO) and solder. Only one kind of metal constituting the conductive portion may be used, or two or more kinds may be used in combination.
  • ITO tin-doped indium oxide
  • the metal constituting the conductive portion is selected so that the conductive portion contains a component capable of diffusing the metal at 400 ° C. or lower, and the conductive portion can be melt-deformed at 400 ° C. or lower.
  • the conductive portion preferably contains solder, and preferably has a solder portion.
  • the solder portion is formed of solder.
  • the conductive portion preferably has a solder portion formed of solder.
  • the conductive portion preferably contains an alloy containing nickel, gold, palladium, silver, copper, tin or tin, and nickel, gold, palladium, tin or tin. It is more preferable to contain an alloy containing.
  • the silver content in 100% by weight of the conductive portion containing silver is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 100% by weight or less, and more preferably 90% by weight or less. is there.
  • the silver content may be 80% by weight or less, 60% by weight or less, 40% by weight or less, 20% by weight or less, or 10% by weight. It may be as follows. When the silver content is at least the above lower limit and at least the above upper limit, the occurrence of aggregation of the conductive particles can be suppressed more effectively.
  • the copper content in 100% by weight of the conductive portion containing copper is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 100% by weight or less, and more preferably 90% by weight or less. is there.
  • the copper content may be 80% by weight or less, 60% by weight or less, 40% by weight or less, 20% by weight or less, or 10% by weight. It may be as follows. When the copper content is at least the above lower limit and at least the above upper limit, the occurrence of aggregation of the conductive particles can be suppressed more effectively.
  • the content of tin or an alloy containing tin is preferably 20% by weight or more, more preferably 50% by weight or more, and particularly preferably 90% by weight or more in 100% by weight of the conductive portion containing tin or an alloy containing tin. ..
  • the content of the tin or the alloy containing the tin is at least the above lower limit, the occurrence of agglomeration of the conductive particles can be suppressed more effectively.
  • the solder is preferably a metal having a melting point of 450 ° C. or lower (low melting point metal).
  • the low melting point metal refers to a metal having a melting point of 450 ° C. or lower.
  • the melting point of the low melting point metal is preferably 300 ° C. or lower, more preferably 160 ° C. or lower.
  • the solder contains tin.
  • the tin content in 100% by weight of the metal contained in the solder is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. When the tin content in the solder is at least the above lower limit, the continuity reliability becomes even higher.
  • the contents of the nickel, copper, and tin are determined by a high-frequency inductively coupled plasma emission spectroscopic analyzer (“ICP-AES” manufactured by Horiba, Ltd.) or a fluorescent X-ray analyzer (“EDX-” manufactured by Shimadzu Corporation). It can be measured using 800HS ”) or the like.
  • ICP-AES high-frequency inductively coupled plasma emission spectroscopic analyzer
  • EDX- fluorescent X-ray analyzer
  • the solder melts and joins to the electrodes, and the solder conducts between the electrodes.
  • the solder and the electrode are likely to make surface contact rather than point contact, so that the connection resistance is low.
  • peeling between the solder and the electrode is more difficult to occur, and the conduction reliability is further improved.
  • the low melting point metal constituting the above solder is not particularly limited.
  • the low melting point metal is preferably tin or an alloy containing tin.
  • the alloy include tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, tin-bismuth alloy, tin-zinc alloy, tin-indium alloy and the like.
  • the low melting point metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy, tin-indium alloy, and tin-bismuth alloy or tin, because it has excellent wettability to the electrode.
  • -It is more preferable that it is an indium alloy.
  • the solder is preferably a filler material having a liquidus line of 450 ° C. or lower based on JIS Z3001: welding terminology.
  • the composition of the solder include a metal composition containing zinc, gold, silver, lead, copper, tin, bismuth, indium and the like.
  • the solder is preferably a tin-indium type (117 ° C. eutectic) or a tin-bismuth type (139 ° C. eutectic), which has a low melting point and is lead-free. That is, the solder preferably does not contain lead, and preferably contains tin and indium, or tin and bismuth.
  • the above solder uses metals such as nickel, copper, antimony, aluminum, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, chromium, molybdenum and palladium. It may be included. Further, from the viewpoint of further increasing the bonding strength, the solder preferably contains nickel, copper, antimony, aluminum or zinc. From the viewpoint of further increasing the bonding strength, the content of these metals for increasing the bonding strength is preferably 0.0001% by weight or more, preferably 1% by weight or less, based on 100% by weight of the solder.
  • the conductive portion may be formed by one layer.
  • the conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers. From the viewpoint of further effectively enhancing the conduction reliability, the conductive portion preferably has a laminated structure of two or more layers.
  • the method of forming the conductive portion on the surface of the base material particles is not particularly limited.
  • Examples of the method for forming the conductive portion include the following methods. Method by electroless plating. Electroplating method. Method by physical collision. Method by mechanochemical reaction. Method by physical vapor deposition or physical adsorption. A method of coating the surface of base particles with a metal powder or a paste containing a metal powder and a binder.
  • the method for forming the conductive portion is preferably a method by electroless plating, electroplating or physical collision.
  • Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering. Further, as the method by the above physical collision, a sheeter composer (manufactured by Tokuju Kosakusho Co., Ltd.) or the like is used.
  • the thickness of the conductive portion is preferably 10 nm or more, more preferably 500 nm or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, still more preferably 1 ⁇ m or less, and particularly preferably 800 nm or less.
  • the thickness of the conductive portion means the thickness of the entire conductive portion when the conductive portion has a laminated structure of two or more layers.
  • the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, the occurrence of aggregation of the conductive particles can be suppressed more effectively. Further, when the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained and it is possible to prevent the conductive particles from becoming hard.
  • the thickness of the conductive portion of the outermost layer is preferably 10 nm or more, more preferably 500 nm or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further. It is preferably 1 ⁇ m or less, particularly preferably 800 nm or less.
  • the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, it is possible to more effectively suppress the occurrence of aggregation of the conductive particles.
  • the thickness of the conductive portion can be measured by observing the cross section of the conductive particles, for example, using a transmission electron microscope (TEM).
  • the thickness of the conductive portion is preferably the thickness of the portion where the thickness of the conductive portion is maximized in any conductive particles.
  • the thickness of the conductive portion is preferably obtained by calculating the average value of the thickness of the conductive portion of each conductive particle for 10 arbitrary conductive particles.
  • solder grain In the conductive particles, the conductive portion has a solder portion.
  • the conductive portion has a solder portion formed of solder.
  • the solder portion is preferably solder particles.
  • the conductive portion it is preferable that the conductive portion has solder particles.
  • the second conductive portion (solder portion) 32B inside is preferably solder grains.
  • the second conductive portion (solder portion) 42B in FIG. 5 the second conductive portion (solder portion) 52C in FIG. 6, the second conductive portion (solder portion) 62B in FIG. 7, and FIG.
  • the second conductive portion (solder portion) 72C inside is preferably solder grains.
  • the above solder grains are different from the protrusions described later.
  • the solder grains can form a metal bond with a joint portion such as an electrode.
  • the solder grains are used for joining with electrodes and the like. Since the conductive portion has the solder particles, the solder particles can easily form a metal bond with the joint portion such as an electrode, so that it is not necessary to melt the entire conductive portion at the time of joining. As a result, the reliability of conduction between the electrodes can be improved even when the thickness of the conductive portion is relatively thin. Further, since it is not necessary to increase the thickness of the conductive portion, it is possible to effectively suppress the aggregation of the conductive particles.
  • the solder particles are relatively small, the outer surface of the solder particles is relatively difficult to be oxidized, and the influence of the oxide film can be suppressed. Therefore, the solder particles can more easily form a metal bond with a joint portion such as an electrode.
  • the conductive particles have a solder layer coated with solder instead of the solder particles, the outer surface of the solder layer is relatively easily oxidized, and it is difficult to suppress the influence of the oxide film. .. For this reason, the solder layer cannot easily form a metal bond with a joint portion such as an electrode, and measures such as thickening the solder layer are required to suppress the occurrence of agglomeration of conductive particles. Becomes difficult.
  • the shape of the solder grains is not particularly limited.
  • the shape of the solder grains is preferably a needle shape or a part of a sphere.
  • the needle-like shape is preferably a pyramid, a cone, or a rotating paraboloid, more preferably a cone or a rotating paraboloid, and even more preferably a cone.
  • the shape of the solder grains may be a pyramid shape, a conical shape, or a rotating paraboloid shape.
  • the material of the above solder grains is not particularly limited.
  • the solder grains are preferably made of metal.
  • the material of the solder grains preferably contains tin in an alloy containing tin, is pure tin, or contains tin in a state different from the alloy containing tin and in a state different from pure tin.
  • the material of the solder grains may contain an alloy containing tin or may be pure tin.
  • the material of the solder grains may be an alloy containing tin or pure tin.
  • the material of the solder particles may contain tin in a state different from that of the alloy containing tin and in a state different from that of pure tin.
  • the material of the solder particles is more preferably pure tin.
  • the fact that the material of the solder particles is pure tin means that the tin content is 90% by weight or more in 100% by weight of the material of the solder particles.
  • the tin content in 100% by weight of the solder grain material may be less than 90% by weight, 80% by weight or less, 75% by weight or less, 70% by weight or less. It may be.
  • the tin content in 100% by weight of the solder grains containing tin is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 90% by weight or more, and preferably 99.5% by weight or less. More preferably, it is 99% by weight or less.
  • the tin content is at least the above lower limit and at least the above upper limit, it is possible to more effectively suppress the occurrence of aggregation of the conductive particles.
  • the solder particles can more easily form a metal bond with a joint portion such as an electrode.
  • the height of the solder grains is preferably 10 nm or more, more preferably 250 nm or more, further preferably 350 nm or more, particularly preferably 500 nm or more, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the height of the solder particles is not less than the above lower limit and not more than the above upper limit, it is possible to more effectively suppress the occurrence of aggregation of the conductive particles.
  • the height of the solder particles is equal to or higher than the lower limit and lower than the upper limit, the solder grains can more easily form a metal bond with a joint portion such as an electrode, which is superior to physical contact. The conduction characteristics can be obtained, and the bonding strength can be further increased.
  • the height of the solder particles is based on the assumption that there are no solder particles (solder portion) on the line (broken line L1 shown in FIG. 1) connecting the center of the conductive particles and the tip of the solder particles (solder portion).
  • the distance from the outer surface of the first conductive portion to the tip of the solder grain (solder portion) is shown. That is, in FIG. 1, the distance from the intersection L2 between the broken line L1 and the outer surface of the first conductive portion to the tip of the solder grain (solder portion) is shown.
  • the height of the solder particles is preferably the average of the heights of the solder particles in one conductive particle.
  • the height of the solder particles is preferably an average value of the heights of the solder particles at five locations in the conductive particles.
  • the height of the solder grains can be measured as follows, for example.
  • the aspect ratio of the solder grains is preferably 0.05 or more, more preferably 0.47 or more, still more preferably 0.5 or more, preferably 5 or less, and more preferably 3 or less.
  • the aspect ratio of the solder particles is not less than the above lower limit and not more than the above upper limit, the occurrence of aggregation of the conductive particles can be suppressed more effectively.
  • the aspect ratio of the solder grains is equal to or higher than the lower limit and lower than the upper limit, the solder grains can more easily form a metal bond with a joint portion such as an electrode, and the solder grains and the electrode or the like can be formed. A sufficient area with the joint can be secured.
  • the aspect ratio of the solder grains is the ratio of the height of the solder grains to the width of the solder grains (height of the solder grains / width of the solder grains), and is calculated from the height of the solder grains and the width of the solder grains. ..
  • the height of the solder particles is such that there is no solder particles (solder portion) on the line (broken line L1 shown in FIG. 1) connecting the center of the conductive particles and the tip of the solder particles (solder portion). The distance from the outer surface of the first conductive portion to the tip of the solder particles (solder portion) in the assumed case is shown.
  • the width of the solder particles is the distance obtained by connecting two points on the outer circumference of the solder particles (solder portion) with a straight line in a direction orthogonal to the line connecting the center of the conductive particles and the tip of the solder particles (solder portion). Indicates the maximum value.
  • the width of the solder particles is preferably the average of the widths of the solder particles in one conductive particle.
  • the width of the solder particles is preferably an average value of the widths of the solder particles at five locations in the conductive particles.
  • the width of the solder grains can be measured as follows, for example.
  • the width of the solder grains is preferably 250 nm or more, more preferably 500 nm or more, further preferably 650 nm or more, preferably 3000 nm or less, more preferably 1700 nm or less, still more preferably 1500 nm or less.
  • the width of the solder particles is not less than the above lower limit and not more than the above upper limit, the occurrence of aggregation of the conductive particles can be suppressed more effectively.
  • the width of the solder grains is equal to or more than the lower limit and equal to or lower than the upper limit, the solder grains can more easily form a metal bond with a joint portion such as an electrode, which is superior to physical contact. Conductivity characteristics can be obtained, and the bonding strength can be further increased.
  • the method for forming the above solder grains is not particularly limited.
  • Examples of the method for forming the solder particles include a method by electroless plating and a method by electroplating.
  • the shape formed is not only film-like but also granular as plating.
  • the conductive particles preferably have a metal colloidal precipitate or a metal film on the outer surface of the solder particles.
  • the conductive particles may have a metal colloidal precipitate on the outer surface of the solder particles, or may have a metal film.
  • the melting points or metal diffusion temperatures of the solder particles (the solder portion) and the conductive portion can be changed to a temperature more suitable for the joint portion such as an electrode. be able to. As a result, the solder particles can more easily form a metal bond with a joint portion such as an electrode.
  • the area of the metal colloidal precipitate or the portion where the metal film is present is preferably 5% or more, more preferably 40% or more in the total area of 100% of the solder grains. It is preferably 100% or less, more preferably 95% or less.
  • coverage coverage of metal colloidal precipitate or metal film
  • the melting point or metal diffusion temperature of the solder particles (solder portion) and the conductive portion is changed. It is possible to make the temperature more suitable for the joint portion such as an electrode. As a result, the solder particles can more easily form a metal bond with a joint portion such as an electrode.
  • the area of the metal colloidal precipitate or the portion where the metal film is present (the coverage of the metal colloidal precipitate or the metal film) in 100% of the total surface area of the solder grains is the cross section of the solder grains in the conductive particles SEM-EDX. It can be calculated by analyzing, performing element mapping, and performing image analysis.
  • the metal species of the metal colloid precipitate or the metal film of the metal film is preferably nickel, cobalt, lead, gold, zinc, palladium, copper, silver, bismuth, or indium, and is preferably copper, silver, bismuth, or It is more preferably indium.
  • the melting points or metal diffusion temperatures of the solder grains (the solder portion) and the conductive portion can be changed. The temperature can be made more suitable for the joint portion such as an electrode. As a result, the solder particles can more easily form a metal bond with a joint portion such as an electrode.
  • the metal colloid for obtaining the metal colloid deposit is preferably nickel colloid, cobalt colloid, lead colloid, gold colloid, zinc colloid, palladium colloid, copper colloid, silver colloid, bismuth colloid, or indium colloid.
  • the metal colloid for obtaining the metal colloidal precipitate is more preferably a copper colloid, a silver colloid, a bismuth colloid, or an indium colloid.
  • the metal film is preferably a nickel thin film, a cobalt thin film, a lead thin film, a gold thin film, a zinc thin film, a palladium thin film, a copper thin film, a silver thin film, a bismuth thin film, or an indium thin film.
  • the metal film is more preferably a copper thin film, a silver thin film, a bismuth thin film, or an indium thin film.
  • the melting point or the metal diffusion temperature of the solder grains (the solder portion) and the conductive portion can be changed, and the joint portion such as an electrode can be used. It can be a suitable temperature. As a result, the solder particles can more easily form a metal bond with a joint portion such as an electrode.
  • the metal colloidal precipitate is preferably metal fine particles.
  • the particle size of the metal fine particles is preferably 1 nm or more, more preferably 10 nm or more, preferably 1 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • the thickness of the metal film is preferably 1 nm or more, more preferably 10 nm or more, preferably 1 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • the particle size of the metal colloidal precipitate or the thickness of the metal film can be measured, for example, as follows.
  • the method of arranging the metal colloidal precipitate or the metal film on the outer surface of the solder particles is not particularly limited.
  • a method of arranging the metal colloidal precipitate or the metal film on the outer surface of the solder grains a method by electroless plating, a method by electroplating, a method by physical collision, and a method by physical vapor deposition or physical adsorption And so on.
  • the conductive particles preferably have protrusions on the outer surface of the conductive portion.
  • the conductive particles preferably have protrusions on the conductive surface. It is preferable that the number of the protrusions is plurality.
  • An oxide film is often formed on the surface of the electrode that comes into contact with the conductive particles. When conductive particles having protrusions on the surface of the conductive portion are used, the oxide film can be effectively removed by the protrusions by crimping the conductive particles and the electrode. Therefore, the electrode and the conductive portion are more reliably contacted with each other, the contact area between the conductive particles and the electrode can be sufficiently increased, and the connection resistance can be further effectively lowered.
  • the protrusions of the conductive particles can more effectively remove the binder between the conductive particles and the electrode. Therefore, the contact area between the conductive particles and the electrodes can be sufficiently increased, and the connection resistance can be lowered even more effectively.
  • the protrusions are different from the solder particles described above.
  • the protrusions are used to remove conductive particles and an oxide film existing on the surface of the electrode, and to remove a binder between the conductive particles and the electrode.
  • a method of forming a conductive portion by electroless plating after adhering a core substance to the surface of the base material particles As a method of forming the above-mentioned protrusions, a method of forming a conductive portion by electroless plating after adhering a core substance to the surface of the base material particles, and a method of forming a conductive portion by electroless plating on the surface of the base material particles. After that, a method of adhering a core substance and further forming a conductive portion by electroless plating can be mentioned. Further, the core material may not be used to form the protrusions.
  • a method of adding a core substance in the middle of forming a conductive portion on the surface of the base material particles can be mentioned. Further, in order to form protrusions, a conductive portion is formed on the substrate particles by electroless plating without using the above-mentioned core substance, and then plating is deposited in a protrusion shape on the surface of the conductive portion, and further electroless plating is performed. You may use the method of forming the conductive part by
  • the core substance is added to the dispersion liquid of the base particle, and the core substance is accumulated and adhered to the surface of the base particle by van der Waals force.
  • Examples thereof include a method in which a core substance is added to a container containing the base material particles, and the core substance is attached to the surface of the base material particles by a mechanical action such as rotation of the container.
  • the method of adhering the core substance to the surface of the base material particles is a method of accumulating and adhering the core substance to the surface of the base material particles in the dispersion liquid. preferable.
  • Examples of the substance constituting the core substance include a conductive substance and a non-conductive substance.
  • Examples of the conductive substance include metals, metal oxides, conductive non-metals such as graphite, and conductive polymers.
  • Examples of the conductive polymer include polyacetylene and the like.
  • Examples of the non-conductive substance include silica, alumina and zirconia. From the viewpoint of more effectively removing the oxide film, the core material is preferably hard. From the viewpoint of further effectively lowering the connection resistance between the electrodes, the core material is preferably a metal.
  • the above metals are not particularly limited.
  • the metals include metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead alloys.
  • examples thereof include alloys composed of two or more kinds of metals such as tin-copper alloy, tin-silver alloy, tin-lead-silver alloy and tungsten carbide.
  • the metal is preferably nickel, copper, silver or gold.
  • the metal may be the same as or different from the metal constituting the conductive portion (conductive layer).
  • the shape of the core substance is not particularly limited.
  • the shape of the core material is preferably lumpy.
  • Examples of the core material include particulate lumps, agglomerates in which a plurality of fine particles are agglomerated, and amorphous lumps.
  • the particle size of the core substance is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, and more preferably 0.2 ⁇ m or less.
  • the particle size of the core substance is not less than the above lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced.
  • the particle size of the core material is preferably an average particle size, and more preferably a number average particle size.
  • the particle size of the core material can be obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope, calculating the average value of the particle size of each core material, or using a particle size distribution measuring device. In observation with an electron microscope or an optical microscope, the particle size of each core substance is determined as the particle size in the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 core materials in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent diameter of the sphere. In the particle size distribution measuring device, the particle size of each core substance is obtained as the particle size in the equivalent diameter of a sphere.
  • the average particle size of the core material is preferably calculated using a particle size distribution measuring device.
  • the number of the protrusions per the conductive particles is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of protrusions is not particularly limited.
  • the upper limit of the number of protrusions can be appropriately selected in consideration of the particle size of the conductive particles and the like. When the number of the protrusions is at least the above lower limit, the connection resistance between the electrodes can be further effectively reduced.
  • the number of protrusions can be calculated by observing arbitrary conductive particles with an electron microscope or an optical microscope.
  • the number of protrusions is preferably determined by observing 50 arbitrary conductive particles with an electron microscope or an optical microscope and calculating the average value of the number of protrusions in each conductive particle.
  • the height of the protrusion is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, and more preferably 0.2 ⁇ m or less.
  • the connection resistance between the electrodes can be further effectively reduced.
  • the height of the protrusions can be calculated by observing the protrusions on any conductive particle with an electron microscope or an optical microscope.
  • the height of the protrusions is preferably calculated by calculating the average value of the heights of all the protrusions per conductive particle as the height of the protrusions of one conductive particle.
  • the height of the protrusions is preferably obtained by calculating the average value of the heights of the protrusions of each of the conductive particles for 50 arbitrary conductive particles.
  • the conductive particles preferably include an insulating substance arranged on the outer surface of the conductive portion.
  • an insulating substance exists between the plurality of electrodes, so that it is possible to prevent a short circuit between the electrodes adjacent to each other in the lateral direction rather than between the upper and lower electrodes.
  • the insulating substance is preferably insulating particles because the insulating substance can be more easily removed during crimping between the electrodes.
  • Examples of the material of the insulating substance include the above-mentioned organic material, the above-mentioned inorganic material, and the above-mentioned inorganic substance as the material of the base particle.
  • the material of the insulating substance is preferably the organic material described above.
  • insulating substance examples include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, crosslinked products of thermoplastic resins, thermosetting resins and water-soluble materials. Examples include resin.
  • As the material of the insulating substance only one kind may be used, or two or more kinds may be used in combination.
  • Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and the like.
  • Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polydodecyl (meth) acrylate, and polystearyl (meth) acrylate.
  • Examples of the block polymer include polystyrene, styrene-acrylic acid ester 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 examples include epoxy resin, phenol resin, melamine resin and the like.
  • crosslinked product of the thermoplastic resin examples include the introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate and the like.
  • water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methyl cellulose and the like.
  • a chain transfer agent may be used to adjust the degree of polymerization. Examples of the chain transfer agent include thiols and carbon tetrachloride.
  • Examples of the method of arranging the insulating substance on the surface of the conductive portion include a chemical method and a physical or mechanical method.
  • Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
  • Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion method, spraying method, dipping and vacuum deposition method. From the viewpoint of further effectively enhancing the insulation reliability and the conduction reliability when the electrodes are electrically connected, the method of arranging the insulating substance on the surface of the conductive portion is a physical method. It is preferable to have.
  • the outer surface of the conductive portion and the outer surface of the insulating substance may each be coated with a compound having a reactive functional group.
  • the outer surface of the conductive portion and the outer surface of the insulating substance may not be directly chemically bonded, or may be indirectly chemically bonded by a compound having a reactive functional group.
  • the carboxyl group may be chemically bonded to a functional group on the outer surface of the insulating substance via a polymer electrolyte such as polyethyleneimine.
  • the particle size of the insulating particle can be appropriately selected depending on the particle size of the conductive particle, the application of the conductive particle, and the like.
  • the particle size of the insulating particles is preferably 10 nm or more, more preferably 100 nm or more, further preferably 300 nm or more, particularly preferably 500 nm or more, preferably 4000 nm or less, more preferably 2000 nm or less, still more preferably 1500 nm or less. , Especially preferably 1000 nm or less.
  • the particle size of the insulating particles is at least the above lower limit, it becomes difficult for the conductive portions of the plurality of conductive particles to come into contact with each other when the conductive particles are dispersed in the binder.
  • the particle size of the insulating particles is not more than the above upper limit, it is not necessary to increase the pressure too much in order to eliminate the insulating particles between the electrodes and the conductive particles when connecting the electrodes, and the temperature is high. There is no need to heat it.
  • the particle size of the insulating particles is preferably an average particle size, and preferably a number average particle size.
  • the particle size of the insulating particles can be obtained by observing 50 arbitrary insulating particles with an electron microscope or an optical microscope, calculating the average value of the particle size of each insulating particle, or using a particle size distribution measuring device. Be done. In observation with an electron microscope or an optical microscope, the particle size of each insulating particle is determined as the particle size in the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 insulating particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent diameter of the sphere.
  • the particle size of each insulating particle is obtained as the particle size in the equivalent diameter of a sphere.
  • the average particle size of the insulating particles is preferably calculated using a particle size distribution measuring device.
  • it can be measured as follows.
  • Conductive particles are added to "Technobit 4000” manufactured by Kulzer so as to have a content of 30% by weight and dispersed to prepare an embedded resin body for conducting conductive particle inspection.
  • a cross section of the conductive particles is cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the dispersed conductive particles in the embedded resin body for inspection.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • FE-SEM field emission scanning electron microscope
  • 50 conductive particles are randomly selected, and the insulating particles of each conductive particle are observed.
  • the particle size of the insulating particles in each conductive particle is measured, and they are arithmetically averaged to obtain the particle size of the insulating particles.
  • the conductive material according to the present invention includes conductive particles and a binder.
  • the conductive particles are the conductive particles described above.
  • the conductive particles are preferably dispersed in a binder and used, and preferably dispersed in a binder and used as a conductive material.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is preferably used for electrical connection between electrodes.
  • the conductive material is preferably a conductive material for circuit connection. Since the above-mentioned conductive particles are used in the above-mentioned conductive material, the connection resistance between the electrodes can be further effectively lowered, and the occurrence of aggregation between the conductive particles can be further effectively suppressed. be able to. Since the above-mentioned conductive particles are used in the above-mentioned conductive material, the conduction reliability can be further effectively enhanced when the electrodes are electrically connected, and the insulation reliability can be further enhanced. Can be effectively enhanced.
  • the above binder is not particularly limited.
  • a known insulating resin or solvent can be used.
  • the binder preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component.
  • the curable component include a photocurable component and a thermosetting component.
  • the photocurable component preferably contains a photocurable compound and a photopolymerization initiator.
  • the thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
  • binder examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, elastomers, solvents and the like. Only one kind of the binder may be used, or two or more kinds may be used in combination.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, styrene resin and the like.
  • examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins.
  • examples of the curable resin include epoxy resin, urethane resin, polyimide resin, and unsaturated polyester resin.
  • the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
  • the curable resin may be used in combination with a curing agent.
  • thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated additive of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene-styrene.
  • examples include a hydrogenated additive of a block copolymer.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • Examples of the solvent include water and organic solvents.
  • Organic solvents are preferred because they can be easily removed.
  • Examples of the organic solvent include alcohol compounds such as ethanol, ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbon compounds such as toluene, xylene and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol and methylcarbitol.
  • Butyl carbitol propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ether compounds, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol.
  • Ester compounds such as acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate, aliphatic hydrocarbon compounds such as octane and decane, and petroleum solvents such as petroleum ether and naphtha. Can be mentioned.
  • the conductive material includes, for example, a filler, a bulking agent, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • a filler for example, a filler, a bulking agent, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
  • UV absorbers, lubricants, antistatic agents, flame retardants and other various additives may be included.
  • the method for dispersing the conductive particles in the binder can be a conventionally known dispersion method and is not particularly limited.
  • Examples of the method for dispersing the conductive particles in the binder include the following methods. A method in which the conductive particles are added to the binder and then kneaded and dispersed with a planetary mixer or the like. A method in which the conductive particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, added to the binder, and kneaded and dispersed by a planetary mixer or the like. A method in which the binder is diluted with water or an organic solvent, the conductive particles are added, and the particles are kneaded and dispersed with a planetary mixer or the like.
  • the viscosity ( ⁇ 25) of the conductive material at 25 ° C. is preferably 30 Pa ⁇ s or more, more preferably 50 Pa ⁇ s or more, preferably 400 Pa ⁇ s or less, and more preferably 300 Pa ⁇ s or less.
  • the viscosity ( ⁇ 25) can be appropriately adjusted depending on the type and amount of the compounding components.
  • the viscosity ( ⁇ 25) can be measured at 25 ° C. and 5 rpm using, for example, an E-type viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.).
  • the conductive material according to the present invention can be used as a conductive paste, a conductive film, or the like.
  • the conductive material according to the present invention is a conductive film
  • a film containing no conductive particles may be laminated on the conductive film containing the conductive particles.
  • the conductive paste is preferably an anisotropic conductive paste.
  • the conductive film is preferably an anisotropic conductive film.
  • the content of the binder in 100% by weight of the conductive material is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, and preferably 70% by weight or more. It is 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the binder is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be further effectively lowered, and the connection reliability between the electrodes can be further effectively enhanced. be able to.
  • the content of the conductive particles in 100% by weight of the conductive material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 80% by weight or less, more preferably 60% by weight. % Or less, more preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% 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 connection resistance between the electrodes can be further effectively lowered, and the connection reliability between the electrodes is further effective. Can be enhanced to.
  • the conductive material may contain a flux. By using the flux, the continuity reliability can be further effectively improved when the electrodes are electrically connected.
  • the above flux is not particularly limited.
  • As the flux a flux generally used for solder bonding or the like can be used.
  • the flux includes 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, a hydrazine, an amine compound, an organic acid and the like.
  • Examples include pine fat. Only one type of the above flux may be used, or two or more types may be used in combination.
  • Examples of the molten salt include ammonium chloride and the like.
  • Examples of the organic acid include lactic acid, citric acid, stearic acid, glutamic acid and glutaric acid.
  • Examples of the above-mentioned pine resin include activated pine resin and non-activated pine resin.
  • the flux is preferably an organic acid having two or more carboxyl groups or pine resin.
  • the flux may be an organic acid having two or more carboxyl groups, or may be pine resin. By using an organic acid or pine resin having two or more carboxyl groups, the conduction reliability between the electrodes is further improved.
  • 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.
  • Examples of the amine compound include cyclohexylamine, dicyclohexylamine, benzylamine, benzhydrylamine, imidazole, benzimidazole, phenylimidazole, carboxybenzoimidazole, benzotriazole, and carboxybenzotriazole.
  • the above pine resin is a rosin containing abietic acid as the main component.
  • the rosins include abietic acid and acrylic-modified rosins.
  • the flux is preferably rosins, more preferably abietic acid. By using this preferable flux, the conduction reliability between the electrodes is further increased.
  • the active temperature (melting point) of the flux is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, preferably 200 ° C. or lower, more preferably 190 ° C. or lower, still more preferably 160 ° C. or higher. ° C. or lower, more preferably 150 ° C. or lower, even more preferably 140 ° C. or lower.
  • the active temperature (melting point) of the flux is preferably 80 ° C. or higher and 190 ° C. or lower.
  • the active temperature (melting point) of the flux is particularly preferably 80 ° C. or higher and 140 ° C. or lower.
  • the active temperature (melting point) of the flux is 80 ° C. or higher and 190 ° C. or lower.
  • the flux include succinic acid (melting point 186 ° C.), glutaric acid (melting point 96 ° C.), adipic acid (melting point 152 ° C.), and pimeric acid (melting point 104 ° C.).
  • °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 flux may be dispersed in the conductive material or may be adhered to the surface of the conductive particles. From the viewpoint of further effectively enhancing the conduction reliability when the electrodes are electrically connected, the flux is preferably adhered to the surface of the conductive particles.
  • the flux is preferably a salt of an acid compound and a base compound.
  • the acid compound is preferably an organic compound having a carboxyl group.
  • the acid compound include malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, citric acid, malic acid and cyclic aliphatic carboxylic acid, which are aliphatic carboxylic acids.
  • examples thereof include cyclohexylcarboxylic acid, 1,4-cyclohexyldicarboxylic acid, isophthalic acid which is an aromatic carboxylic acid, terephthalic acid, trimellitic acid, ethylenediamine tetraacetic acid and the like.
  • the acid compound is preferably glutaric acid, cyclohexylcarboxylic acid, or adipic acid.
  • the above basic compound is preferably an organic compound having an amino group.
  • the basic compound include diethanolamine, triethanolamine, methyldiethanolamine, ethyldiethanolamine, cyclohexylamine, dicyclohexylamine, benzylamine, benzhydrylamine, 2-methylbenzylamine, 3-methylbenzylamine, and 4-tert-butylbenzylamine. , N-Methylbenzylamine, N-ethylbenzylamine, N-phenylbenzylamine, N-tert-butylbenzylamine, N-isopropylbenzylamine, N, N-dimethylbenzylamine, imidazole compounds, and triazole compounds. .. From the viewpoint of further effectively enhancing the conduction reliability, the basic compound is preferably benzylamine.
  • the content of the flux in 100% by weight of the conductive material is preferably 0.5% by weight or more, preferably 30% by weight or less, and more preferably 25% by weight or less.
  • the content of the flux is at least the above lower limit and at least the above upper limit, it becomes more difficult to form an oxide film on the surface of the electrode, and further, the oxide film formed on the surface of the electrode is removed more effectively. it can.
  • connection structure includes a first connection target member having a first electrode on the surface, a second connection target member having a second electrode on the surface, the first connection target member, and the above. It includes a connecting portion that connects to the second connection target member.
  • the connection portion is formed of conductive particles or is formed of a conductive material containing the conductive particles and a binder.
  • the conductive particles are the above-mentioned conductive particles.
  • the first electrode and the second electrode are electrically connected by the conductive particles.
  • FIG. 9 is a front sectional view schematically showing a connection structure using conductive particles according to a fourth embodiment of the present invention.
  • connection structure 81 shown in FIG. 9 connects the first connection target member 82, the second connection target member 83, and the first connection target member 82 and the second connection target member 83.
  • a unit 84 is provided.
  • the connecting portion 84 is formed of a conductive material containing the conductive particles 21. In FIG. 9, the conductive particles 21 are shown schematicly for convenience of illustration.
  • the first connection target member 82 has a plurality of first electrodes 82a on the surface (upper surface).
  • the second connection target member 83 has a plurality of second electrodes 83a on the surface (lower surface).
  • the first electrode 82a and the second electrode 83a are electrically connected by one or more conductive particles 21. Therefore, the first connection target member 82 and the second connection target member 83 are electrically connected by the conductive particles 21.
  • the method for manufacturing the connection structure is not particularly limited.
  • the conductive material is arranged between the first connection target member and the second connection target member, and after obtaining a laminate, the laminate is heated. And a method of pressurizing and the like.
  • the conductive portion (solder portion) of the conductive particles 21 is melted, and the electrodes are electrically connected by the conductive particles 21.
  • the binder contains a thermosetting compound
  • the thermosetting compound is thermosetting
  • the thermosetting cured product connects the first connection target member and the second connection target member.
  • a connection is formed.
  • the pressurizing pressure is 9.8 ⁇ 10 4 Pa to 4.9 ⁇ 10 6 Pa.
  • the heating temperature is 120 ° C to 220 ° C.
  • FIG. 10 is a front sectional view schematically showing an enlarged connection portion between the conductive particles and the electrodes in the connection structure shown in FIG.
  • the second conductive portion (solder portion) 22B of the conductive particles 21 is melted by heating and pressurizing the laminated body, and then the second conductive portion is melted.
  • the portion (solder portion) portion 22Ba is in sufficient contact with the first electrode 82a and the second electrode 83a. That is, by using the conductive particles 21 whose surface layer is the solder portion, the conductive particles 21 are compared with the case where the surface layer of the conductive layer is a metal such as nickel, gold or copper.
  • the contact area between the first electrode 82a and the second electrode 83a is increased. Therefore, the continuity reliability of the connection structure 81 is increased.
  • the first connection target member and the second connection target member are not particularly limited.
  • Specific examples of the first connection target member and the second connection target member include electronic components such as semiconductor chips, semiconductor packages, LED chips, LED packages, capacitors and diodes, resin films, printed circuit boards, and flexible devices. Examples thereof include electronic components such as printed circuit boards, flexible flat cables, rigid flexible boards, glass epoxy boards, and circuit boards such as glass boards.
  • the first connection target member and the second connection target member are preferably electronic components.
  • the electrodes provided on the connection target member include metal electrodes such as gold electrodes, nickel electrodes, tin electrodes, aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes, SUS electrodes, and tungsten electrodes.
  • the electrodes are preferably gold electrodes, nickel electrodes, tin electrodes, silver electrodes or copper electrodes.
  • the electrodes are preferably aluminum electrodes, copper electrodes, molybdenum electrodes, silver electrodes or tungsten electrodes.
  • the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer.
  • the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al and Ga.
  • Example 1 Preparation of Conductive Particle 1: Divinylbenzene copolymer resin particles (“Micropearl SP-220, particle diameter 20 ⁇ m” manufactured by Sekisui Chemical Co., Ltd.) were prepared as the base particles (S1).
  • Divinylbenzene copolymer resin particles (“Micropearl SP-220, particle diameter 20 ⁇ m” manufactured by Sekisui Chemical Co., Ltd.) were prepared as the base particles (S1).
  • the base material particles (S1) 10 parts by weight of the base material particles (S1) are dispersed in 100 parts by weight of an alkaline solution containing 5% by weight of the palladium catalyst solution by an ultrasonic disperser, and then the base material particles (S1) are taken out by filtering the solution. It was. Next, the base particle (S1) was added to 100 parts by weight of a 1 wt% dimethylamine borane solution to activate the surface of the substrate particle (S1). The surface-activated substrate particles (S1) were thoroughly washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension (A1).
  • the suspension (A1) was placed in a solution containing 25 g / L of nickel sulfate, 15 ppm of thallium nitrate and 10 ppm of bismuth nitrate to obtain a particle mixture (B1).
  • a nickel plating solution (C1) (pH 5.5) containing 100 g / L of nickel sulfate, 40 g / L of sodium hypophosphite, 15 g / L of sodium citrate, 25 ppm of thallium nitrate, and 10 ppm of bismuth nitrate was prepared.
  • an electroless tin plating solution for forming solder grains a mixed solution containing 15 g / L of tin sulfate, 45 g / L of ethylenediaminetetraacetic acid, and 1.5 g / L of phosphinic acid was adjusted to pH 8.5 with sodium hydroxide.
  • a tin plating solution (D1) was prepared.
  • a reducing solution (E1) in which a solution containing 5 g / L of sodium borohydride was adjusted to pH 10.0 with sodium hydroxide was prepared.
  • the nickel plating solution (C1) was gradually added dropwise to the particle mixture (B1) at 50 ° C. in which the particles were dispersed, and electroless nickel plating was performed. Electroless nickel plating was performed with a dropping rate of the nickel plating solution (C1) of 12.5 mL / min and a dropping time of 30 minutes (Ni plating step). In this way, a particle mixed solution (F1) containing particles having a nickel-phosphorus alloy conductive portion as a first conductive portion on the surface of the base particle S1 was obtained.
  • the particles were taken out by filtering the particle mixture (F1) and washed with water to obtain particles in which the nickel-phosphorus alloy conductive portion was arranged on the surface of the base particle S1. After thoroughly washing the particles with water, the particles were added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (G1).
  • the tin plating solution (D1) was gradually added to the particle mixture (G1) at 60 ° C. in which the particles were dispersed.
  • the reducing liquid (E1) was added dropwise to perform electroless tin plating.
  • the dropping rate of the reducing solution (E1) was 0.5 mL / min, the dropping time was 40 minutes, and then stirring was performed for 10 minutes to perform electroless tin plating.
  • the particles are taken out by filtration, washed with water, and dried to obtain a nickel-phosphorus alloy conductive portion and a tin conductive portion (solder particles) (the entire conductive portion in a portion without solder particles) on the surface of the base particle S1.
  • the conductive particles 1 having a thickness of 0.1 ⁇ m and a height of solder grains: 0.6 ⁇ m) were obtained.
  • Example 2 Preparation of conductive particles 2: The suspension (A1) of Example 1 was prepared.
  • the suspension (A1) is placed in a solution containing 2 g / L of potassium gold cyanide, 10 g / L of sodium citrate, 0.5 g / L of ethylenediaminetetraacetic acid, and 5 g / L of sodium hydroxide. (B2) was obtained.
  • the electroless gold plating solution includes potassium gold cyanide 10 g / L, sodium citrate 20 g / L, tallium nitrate 5 ppm, ethylenediamine tetraacetic acid 3.0 g / L, sodium hydroxide 20 g / L, and dimethylamine borane 10 g / L.
  • a gold plating solution (C2) (pH 8.0) containing L was prepared.
  • the tin solution for forming solder grains the tin plating solution (D1) and the reducing solution (E1) of Example 1 were prepared.
  • the gold plating solution (C2) was gradually added dropwise to the particle mixture (B2) at 60 ° C. in which the particles were dispersed, and electroless gold plating was performed. Electroless gold plating was performed with a dropping rate of the gold plating solution (C2) of 2 mL / min and a dropping time of 45 minutes. In this way, a particle mixed solution (D2) containing particles in which a gold metal portion is arranged as a first conductive portion on the surface of the base particle S1 was obtained.
  • the particles were taken out by filtering the particle mixture (D2) and washed with water to obtain particles in which the gold conductive portion was arranged on the surface of the base particle S1. After thoroughly washing the particles with water, the particles were added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (E2).
  • the tin plating solution (D1) and the reducing solution (E1) are used in the same manner as in Example 1 to form solder particles, and a particle mixture containing the particles in which the solder particles are formed on the gold conductive portion. (F2) was obtained.
  • the particles were taken out by filtering the particle mixture (F2) and washed with water to obtain particles in which the gold conductive portion was arranged on the surface of the base particle S1 and the solder particles were formed. .. After thoroughly washing the particles with water, the particles were added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (G2).
  • the gold plating solution (C2) was gradually added dropwise to the particle mixture (G2) at 60 ° C. in which the particles were dispersed, and electroless gold plating was performed. Electroless gold plating was performed with a dropping rate of the gold plating solution (C2) of 1 mL / min and a dropping time of 1 minute. Then, the particles are taken out by filtration, washed with water, and dried to form a gold conductive portion (thickness of the entire conductive portion: 0.1 ⁇ m) and solder particles (height of solder particles: height: 0.1 ⁇ m) on the surface of the base particle S1. Conductive particles 2 having a gold thin film (thickness of metal film: 0.01 ⁇ m) on top of 0.6 ⁇ m) were obtained.
  • Example 3 Preparation of Conductive Particles 3: In the same manner as in Example 1, conductive particles having a nickel-phosphorus alloy conductive portion and solder particles as base particles were obtained. The obtained conductive particles were added to 500 parts by weight of distilled water and dispersed to obtain a suspension (A3).
  • a silver plating solution (B3) prepared by adjusting a mixed solution of silver nitrate 30 g / L, succinate imide 100 g / L, and formaldehyde 20 g / L to pH 8.0 with aqueous ammonia was prepared. ..
  • suspension (A3) at 60 ° C. was mixed with the silver plating solution (B3) and dispersed to obtain a particle mixture (C3).
  • the silver plating solution (B3) was gradually added dropwise to the particle mixture (C3) at 60 ° C. in which the particles were dispersed, and electroless silver plating was performed. Electroless plating was performed with a dropping rate of the silver plating solution (B3) of 10 mL / min and a dropping time of 10 minutes. Then, the particles are taken out by filtration, washed with water, and dried to form a nickel-phosphorus alloy conductive portion (thickness of the entire conductive portion: 0.1 ⁇ m) and solder particles (solder particles of the solder particles) on the surface of the base material particles S1. Conductive particles 3 having a silver thin film (thickness of metal film: 0.01 ⁇ m) on top of (height: 0.6 ⁇ m) were obtained.
  • Example 4 Preparation of Conductive Particles 4: The suspension (A3) of Example 3 was prepared.
  • a silver solution (B4) was prepared in which a mixed solution containing 1 g / L of silver nitrate, 30 g / L of ethylenediaminetetraacetic acid, and 20 ppm of polyethylene glycol (molecular weight 6000) was adjusted to pH 11 with sodium hydroxide as a silver solution.
  • a solution containing 10 g / L of sodium borohydride and 40 g / L of sodium hydroxide was prepared as a reducing solution (D4) for forming a metal colloidal precipitate.
  • suspension (A3) was mixed with the silver solution (B4) and dispersed to obtain a particle mixture (C4).
  • Example 5 Preparation of Conductive Particles 5: The suspension (A3) of Example 3 was prepared.
  • an indium solution (B5) was prepared in which a mixed solution containing 5 g / L of indium chloride, 40 g / L of ethylenediaminetetraacetic acid, and 0.01 g / L of polyvinylpyrrolidone was adjusted to pH 10 with sodium hydroxide.
  • the reducing liquid (D4) for forming a colloidal precipitate of Example 4 was prepared.
  • the suspension (A3) was mixed with the indium solution (B5) and dispersed to obtain a particle mixture (C5).
  • Example 6 Preparation of Conductive Particles 6: The suspension (A3) of Example 3 was prepared.
  • the reducing liquid (D4) for forming a metal colloidal precipitate of Example 4 was prepared.
  • the suspension (A3) was mixed with the copper solution (B6) and dispersed to obtain a particle mixture (C6).
  • Example 7 Preparation of Conductive Particles 7: As a non-electrolytic tin plating solution for forming solder grains, a mixed solution containing 15 g / L of tin sulfate, 45 g / L of ethylenediamine tetraacetic acid, 1.5 g / L of phosphinic acid, and 10 g / L of trehalose dihydrate was added to sodium hydroxide. A tin plating solution (B7) adjusted to pH 9.0 was prepared.
  • Conductive particles 7 were obtained in the same manner as in Example 1 except that the electroless tin plating solution for forming solder grains (D1) was changed to the electroless tin plating solution for forming solder grains (B7). Thickness of the entire conductive part in the portion without solder grains: 0.2 ⁇ m, height of solder grains: 0.9 ⁇ m).
  • Preparation of conductive particles 8 (1) Preparation of Silicone Oligomer 1 part by weight of 1,3-divinyltetramethyldisiloxane and 20 parts by weight of 0.5% by weight p-toluenesulfonic acid aqueous solution were placed in a 100 ml separable flask placed in a warm bath. I put it in. After stirring at 40 ° C. for 1 hour, 0.05 parts by weight of sodium hydrogen carbonate was added.
  • aqueous solution B was prepared by mixing with 80 parts by weight of a 5% by weight aqueous solution of "Gosenol GH-20" manufactured by Synthetic Chemical Co., Ltd. The solution A was placed in a separable flask placed in a warm bath, and then the aqueous solution B was added.
  • emulsification was carried out by using a Shirasu Porous Glass (SPG) membrane (pore average diameter of about 1 ⁇ m). Then, the temperature was raised to 85 ° C., and polymerization was carried out for 9 hours. The entire amount of the polymerized particles was washed with water by centrifugation and freeze-dried. After drying, the particles are pulverized with a ball mill until the agglomerates of the particles have the desired ratio (average secondary particle diameter / average primary particle diameter) to obtain silicone particles (base particle S2) having a particle diameter of 3.0 ⁇ m. Obtained.
  • SPG Shirasu Porous Glass
  • Conductive particles 8 were obtained in the same manner as in Example 1 except that the base particle S1 was changed to the base particle S2.
  • Example 9 Preparation of Conductive Particles 9: Silicone particles with a particle size of 3.0 ⁇ m (group) in the same manner as in Example 8 except that acrylic silicone oil at both ends (“X-22-2445” manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicone oligomer. Material particles S3) were obtained.
  • Conductive particles 9 were obtained in the same manner as in Example 1 except that the base particle S1 was changed to the base particle S3.
  • Example 10 Preparation of Conductive Particles 10: A base particle S4 having a particle diameter of 3.0 ⁇ m, which differs from the base particle S1 only in particle diameter, was prepared.
  • Conductive particles 10 were obtained in the same manner as in Example 1 except that the base particle S1 was changed to the base particle S4.
  • Conductive particles 11 were obtained in the same manner as in Example 1 except that the base particle S1 was changed to the base particle S5.
  • Conductive particles 12 were obtained in the same manner as in Example 1 except that the base particle S1 was changed to the base particle S6.
  • Example 13 Preparation of Conductive Particles 13: The suspension (A1) of Example 1 was prepared.
  • a nickel plating solution (C1) electroless nickel plating was performed in the same manner as in Example 1, and a nickel-phosphorus alloy was used as a first conductive portion on the surface of the base particle containing the metallic nickel core material.
  • a particle mixture (F13) containing particles having a conductive portion was obtained.
  • the particles are taken out by filtering the particle mixed solution (F13) and washed with water, so that the nickel-phosphorus alloy conductive portion containing the metallic nickel core substance is arranged on the surface of the base particle S1.
  • the particles were added to 500 parts by weight of distilled water and dispersed to obtain a particle mixture (G13).
  • Example 2 the tin plating solution (D1) and the reducing solution (E1) were used to form solder particles, and the solder particles were formed on the nickel-phosphorus alloy conductive portion. A particle mixture (H13) containing the above was obtained.
  • the particles are taken out by filtration, washed with water, and dried to obtain a nickel-phosphorus alloy conductive portion containing a core substance on the surface of the base particle S1 (thickness of the entire conductive portion in the portion without the core substance: 0).
  • Conductive particles 13 having .1 ⁇ m) and solder particles (solder particle height: 0.6 ⁇ m) were obtained.
  • Conductive particles 14 were obtained in the same manner as in Example 13 except that the metallic nickel particle slurry was changed to the titanium oxide particle slurry.
  • Example 15 Preparation of Conductive Particles 15: An alumina particle slurry (average particle diameter 150 nm) was prepared.
  • Conductive particles 15 were obtained in the same manner as in Example 13 except that the metal nickel particle slurry was changed to the alumina particle slurry.
  • Example 16 Preparation of Conductive Particles 16: A 1000 mL separable flask equipped with a 4-port separable cover, a stirring blade, a three-way cock, a cooling tube and a temperature probe was prepared. In the separable flask, 100 mmol of methyl methacrylate, 1 mmol of N, N, N-trimethyl-N-2-methacryloyloxyethylammonium chloride, and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride are placed. The monomer composition containing the mixture was weighed in ion-exchanged water so that the solid content was 5% by weight.
  • the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, the reaction was freeze-dried to obtain insulating particles having an ammonium group on the surface, having an average particle diameter of 220 nm and a CV value of 10%.
  • Insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10% by weight aqueous dispersion of insulating particles.
  • Example 2 10 g of the conductive particles obtained in Example 1 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtering with a mesh filter of 30 ⁇ m, the mixture was further washed with methanol and dried to obtain conductive particles 16 to which insulating particles were attached.
  • Example 17 Preparation of Conductive Particles 17: In the same manner as in Example 1 except that the dropping time of the reducing liquid (E1) was changed to 20 minutes, the nickel-phosphorus alloy conductive portion and the tin conductive portion (solder particles) (solder) were placed on the surface of the base particle S1. Conductive particles 17 having the thickness of the entire conductive portion in the portion without particles: 0.1 ⁇ m and the height of the solder particles: 0.3 ⁇ m) were obtained.
  • the electroless tin plating solution includes tin chloride 20 g / L, nitrilotriacetic acid 50 g / L, thiourea 2 g / L, thioalic acid 1 g / L, ethylenediaminetetraacetic acid 7.5 g / L, and titanium trichloride 15 g / L.
  • a tin plating solution (d1) was prepared by adjusting the pH of the mixed solution containing the above to 7.0 with sulfuric acid.
  • the tin plating solution (d1) was gradually added dropwise to the particle mixture (G1) at 70 ° C. in which the particles were dispersed, and electroless tin plating was performed. Electroless tin plating was performed with a dropping rate of the tin plating solution (d1) of 30 mL / min and a dropping time of 20 minutes. Then, the particles are taken out by filtration, washed with water, and dried to provide a nickel-phosphorus alloy conductive portion and a tin conductive portion (thickness of the entire conductive portion: 0.3 ⁇ m) on the surface of the base particle S1. Sex particles A were obtained.
  • Electroless tin plating was performed in the same manner as in Comparative Example 1, and a nickel-phosphorus alloy conductive portion and a tin conductive portion containing a core material on the surface of the base particle S1 (thickness of the entire conductive portion in the portion without the core material: 0). Conductive particles B having a thickness of .3 ⁇ m) were obtained.
  • a transparent glass substrate having a copper electrode pattern having an L / S of 200 ⁇ m / 200 ⁇ m on the upper surface was prepared. Further, a semiconductor chip having a gold electrode pattern having an L / S of 200 ⁇ m / 200 ⁇ m on the lower surface was prepared.
  • An anisotropic conductive paste immediately after production was applied onto the transparent glass substrate so as to have a thickness of 30 ⁇ m to form an anisotropic conductive paste layer.
  • the semiconductor chips were laminated on the anisotropic conductive paste layer so that the electrodes face each other.
  • the pressure heating head is placed on the upper surface of the semiconductor chip, and a pressure of 0.5 MPa is applied to the anisotropic conductive paste.
  • the layer was cured at 250 ° C. to give a connection structure.
  • connection structure the metal diffusion state of the conductive part was determined by observing the cross section of the connection structure.
  • EDX energy dispersive X-ray analyzer
  • connection part In the connection part, the conductive part in the conductive particles is metal diffused with the copper electrode pattern and the gold electrode pattern.
  • B In the connection part, the conductive part in the conductive particles is the copper electrode pattern, the gold electrode pattern and the metal. Not spread
  • connection structure obtained in the evaluation of (1) above was prepared.
  • the prepared connection structure was placed in "Technobit 4000” manufactured by Kulzer and cured to prepare an embedded resin body for inspection of the connection structure.
  • a cross section of the conductive particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the connection structure in the embedded resin body for inspection.
  • the melt-deformed state of the conductive portion was determined according to the following criteria.
  • connection structure obtained in the evaluation of (1) above was prepared.
  • the prepared connection structure was placed in "Technobit 4000” manufactured by Kulzer and cured to prepare an embedded resin body for inspection of the connection structure.
  • a cross section of the conductive particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the connection structure in the embedded resin body for inspection.
  • the bonding state of the conductive portion was confirmed by observing the cross section of the obtained connection structure using a scanning electron microscope (FE-SEM).
  • the bonding state of the conductive portion was determined according to the following criteria.
  • connection part In the connection part, 5 or more of 10 conductive particles are melt-deformed and then solidified and bonded to the electrode.
  • B 1 out of 10 conductive particles in the connection part. In the above 5 or less particles, the conductive part is melt-deformed and then solidified and bonded to the electrode.
  • C Among the 10 conductive particles, there are no particles in which the conductive part is melt-deformed, only metal diffusion. Bonded to the electrode D: None of the 10 conductive particles are bonded in the connection
  • Particle Diameter of Conductive Particles The particle diameter of the obtained conductive particles was calculated using a particle size distribution measuring device (“Multisizer 4” manufactured by Beckman Coulter). Specifically, it was obtained by measuring the particle diameters of about 100,000 conductive particles and calculating the average value.
  • Thickness of Conductive Part The obtained conductive particles were added to "Technobit 4000” manufactured by Kulzer and dispersed so as to have a content of 30% by weight to prepare an embedded resin body for inspection. A cross section of the conductive particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedded resin body for inspection.
  • IM4000 manufactured by Hitachi High-Technologies Corporation
  • FE-TEM field emission transmission electron microscope
  • Small agglutination means agglutination in which 4 or less particles are connected by a plating film
  • large agglutination means agglutination in which 5 or more particles are connected by a plating film.
  • FE-SEM field emission scanning electron microscope
  • the aspect ratio of solder grains is the ratio of the height of the solder grains to the width of the solder grains (height of the solder grains / width of the solder grains), and the height of the solder grains and the width of the solder grains. It was calculated from the width of.
  • the width of the solder grains was measured as follows.
  • An embedded resin body for conducting conductive particle inspection was prepared by adding and dispersing the obtained conductive particles to "Technobit 4000" manufactured by Kulzer so that the content was 30% by weight.
  • a cross section of the conductive particles was cut out using an ion milling device (“IM4000” manufactured by Hitachi High-Technologies Corporation) so as to pass near the center of the conductive particles dispersed in the embedded resin body for inspection.
  • FE-SEM field emission scanning electron microscope
  • Conductive particles 2 ... Base particles 3 ... Conductive parts 3A ... First conductive parts 3B ... Second conductive parts (solder parts) 11 ... Conductive particles 12 ... Conductive part 12A ... Conductive part of the first a 12B ... Conductive part of the first b 12C ... Second conductive part (solder part) 21 ... Conductive particles 22 ... Conductive part 22A ... First conductive part 22B ... Second conductive part (solder part) 22Ba ... Melted second conductive part (solder part) 31 ... Conductive particles 32 ... Conductive part 32A ... First conductive part 32B ... Second conductive part (solder part) 32C ... Third conductive part 41 ... Conductive particles 42 ...

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  • Chemical & Material Sciences (AREA)
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  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

L'invention concerne des particules conductrices qui peuvent supprimer efficacement la survenue d'une agrégation entre elles. Les particules conductrices selon la présente invention comportent chacune une particule de matériau de base et une partie conductrice disposée sur la surface de la particule de matériau de base, la partie conductrice comprenant un composant qui permet une diffusion métallique à 400 °C ou moins, ou peut être fondu et déformé à 400 °C ou moins ; la partie conductrice comprenant des parties de soudure ; et la proportion surfacique d'une portion comportant les parties de soudure étant de 99 % ou moins par rapport à une proportion surfacique totale de 100 % de la particule de matériau de base.
PCT/JP2020/023304 2019-06-13 2020-06-12 Particules conductrices, matériau conducteur et structure de connexion WO2020251043A1 (fr)

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JP2018046010A (ja) * 2016-09-09 2018-03-22 積水化学工業株式会社 金属原子含有粒子、接続材料、接続構造体及び接続構造体の製造方法

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CN106463200B (zh) * 2014-09-18 2019-05-31 积水化学工业株式会社 导电糊剂、连接结构体及连接结构体的制造方法

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JP2018046010A (ja) * 2016-09-09 2018-03-22 積水化学工業株式会社 金属原子含有粒子、接続材料、接続構造体及び接続構造体の製造方法
JP2018045906A (ja) * 2016-09-15 2018-03-22 積水化学工業株式会社 導電材料、導電材料の製造方法及び接続構造体

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