WO2021246523A1 - 導電性粒子、導電材料及び接続構造体 - Google Patents

導電性粒子、導電材料及び接続構造体 Download PDF

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Publication number
WO2021246523A1
WO2021246523A1 PCT/JP2021/021408 JP2021021408W WO2021246523A1 WO 2021246523 A1 WO2021246523 A1 WO 2021246523A1 JP 2021021408 W JP2021021408 W JP 2021021408W WO 2021246523 A1 WO2021246523 A1 WO 2021246523A1
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Prior art keywords
conductive
particles
conductive particles
weight
resin
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PCT/JP2021/021408
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English (en)
French (fr)
Japanese (ja)
Inventor
秀平 大日方
寛人 松浦
武司 脇屋
Original Assignee
積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2022528916A priority Critical patent/JPWO2021246523A1/ja
Priority to CN202180039684.4A priority patent/CN115699218A/zh
Priority to KR1020227036521A priority patent/KR20230019815A/ko
Publication of WO2021246523A1 publication Critical patent/WO2021246523A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • 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
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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

Definitions

  • the present invention relates to conductive particles that can be used for electrical connection between electrodes and the like.
  • the present invention also relates to a conductive material and a connecting structure using the above conductive particles.
  • Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known.
  • the conductive particles are dispersed in the binder resin.
  • conductive particles having a base material particles and a conductive portion arranged on the surface of the base material particles may be used.
  • the anisotropic conductive material is used to obtain various connection structures. Connections using the anisotropic conductive material include a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a connection between a semiconductor chip and a flexible printed circuit board (COF (Chip on Film)), and a semiconductor chip. And the connection between the glass substrate and the glass substrate (COG (Chip on Glass)), and the connection between the flexible printed circuit board and the glass epoxy substrate (FOB (Film on Board)) and the like.
  • FOG Flexible printed circuit board and a glass substrate
  • COF Chip on Film
  • conductive particles as shown in the following Patent Documents 1 and 2, magnetic conductive particles may be used.
  • Patent Document 1 describes, as the above-mentioned magnetic conductive particles, magnetic conductive particles that are at least partially composed of a magnetic material and can be magnetized. Further, Patent Document 1 describes gold / nickel-coated resin particles, nickel-coated resin particles, nickel metal particles, phosphorus element-containing nickel-coated resin particles, and the like as the magnetic conductive particles.
  • Patent Document 2 discloses conductive particles including mother particles and insulating child particles that cover the surface of the mother particles.
  • the mother particle has a plastic nuclei and a plating layer that covers the surface of the plastic nuclei.
  • the plating layer has a nickel / phosphorus alloy layer.
  • the particle size of the mother particle is 2.0 ⁇ m or more and 3.0 ⁇ m or less, the saturation magnetization of the mother particle is 45 emu / cm 3 or less, and the particle size of the insulating child particle is 180 nm or more and 500 nm or less.
  • magnetic conductive particles may be used.
  • the conventional conductive particles as described in Patent Documents 1 and 2 it is difficult to exhibit both the characteristics of increasing the saturation magnetization and decreasing the residual magnetization.
  • conductive particles having a high residual magnetization for example, magnetic aggregation of the conductive particles is likely to occur.
  • a conductive particle comprising a resin particle and a conductive portion arranged outside the outer surface of the resin particle, and having the following constitution A, structure B, or structure C. Will be done.
  • Configuration A A magnetic material portion including a magnetic material arranged between the resin particles and the conductive portion is provided, and the ratio of the residual magnetization in the conductive particles to the saturation magnetization is 0.4 or less.
  • Configuration B The conductive portion contains a magnetic material, and the ratio of the residual magnetization in the conductive particles to the saturation magnetization is 0.4 or less.
  • Configuration C The resin particles contain a magnetic substance.
  • the conductive particles include the configuration A.
  • the conductive particles include the configuration B.
  • the conductive particles include the configuration C.
  • the content of the magnetic substance contained in the conductive particles is 5% by volume or more and 85% by volume or less in 100% by volume of the conductive particles.
  • the content of the magnetic substance contained in the conductive particles is 10% by weight or more and 99% by weight or less in 100% by weight of the conductive particles.
  • the particle size of the conductive particles is 0.1 ⁇ m or more and 1000 ⁇ m or less.
  • the magnetic material is a metal or a metal oxide.
  • the magnetic material comprises iron, cobalt, ferrite, nickel or an alloy thereof.
  • the conductive particles further include an insulating substance disposed on the outer surface of the conductive portion.
  • the conductive particles have protrusions on the outer surface of the conductive portion.
  • a conductive material including the above-mentioned conductive particles and a binder resin is provided.
  • 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 resin.
  • 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 resin particles and a conductive portion arranged on the outside of the outer surface of the resin particles, and have the following configurations A, B, or C.
  • Configuration A A magnetic material portion including a magnetic material arranged between the resin particles and the conductive portion is provided, and the ratio of the residual magnetization in the conductive particles to the saturation magnetization is 0.4 or less.
  • Configuration B The conductive portion contains a magnetic material, and the ratio of the residual magnetization in the conductive particles to the saturation magnetization is 0.4 or less.
  • Configuration C The resin particles contain a magnetic substance. Since the conductive particles according to the present invention have the above-mentioned structure, the saturation magnetization can be increased, the residual magnetization can be decreased, and the electrodes are electrically connected to each other. Conduction reliability can be improved.
  • FIG. 1 is a cross-sectional view schematically showing conductive particles according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing the conductive particles according to the second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing the conductive particles according to the third embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing the conductive particles according to the fourth embodiment of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing the conductive particles according to the fifth embodiment of the present invention.
  • FIG. 6 is a cross-sectional view showing an example of a connection structure using conductive particles according to the first embodiment of the present invention.
  • the conductive particles according to the present invention include resin particles and a conductive portion arranged outside the outer surface of the resin particles, and include the following configurations A, B, or C.
  • Configuration A A magnetic material portion including a magnetic material arranged between the resin particles and the conductive portion is provided, and the ratio of the residual magnetization in the conductive particles to the saturation magnetization is 0.4 or less.
  • Configuration B The conductive portion contains a magnetic material, and the ratio of the residual magnetization in the conductive particles to the saturation magnetization is 0.4 or less.
  • Configuration C The resin particles contain a magnetic substance.
  • the saturation magnetization can be increased, the residual magnetization can be decreased, and the electrodes are electrically connected to each other. Conduction reliability can be improved.
  • the conductive particles according to the present invention can have a high saturation magnetization, even if the conductive material has a high viscosity, a vertical electrode to which the conductive particles contained in the conductive material should be connected by a magnetic field. It can be arranged well in between.
  • the residual magnetization can be lowered, so that the magnetic aggregation of the conductive particles can be effectively suppressed.
  • the conductive particles according to the present invention can enhance the conduction reliability.
  • the connection resistance between the electrodes in the vertical direction to be connected can be effectively reduced, and the lateral electrodes must not be connected.
  • the insulation reliability between the electrodes in the direction can be improved.
  • the conductive particles according to the present invention have at least one of the above-mentioned constitution A, the above-mentioned structure B, and the above-mentioned structure C.
  • the conductive particles according to the present invention may have only the above-mentioned structure A, may have only the above-mentioned structure B, or may have only the above-mentioned structure C.
  • the conductive particles according to the present invention may have at least two configurations of the above-mentioned constitution A, the above-mentioned structure B, and the above-mentioned structure C.
  • the conductive particles according to the present invention may have the above-mentioned structure A and the above-mentioned structure B, may have the above-mentioned structure B and the above-mentioned structure C, and may have the above-mentioned structure A and the above-mentioned structure C. You may.
  • the conductive particles according to the present invention may have the above-mentioned structure A, the above-mentioned structure B, and the above-mentioned structure C.
  • the ratio (residual magnetization / saturation magnetization) of the residual magnetization in the conductive particles to the saturated magnetization is 0.4 or less. If the above ratio (residual magnetization / saturation magnetization) exceeds 0.4, magnetic aggregation may easily occur or conduction reliability may decrease.
  • the ratio of the residual magnetization to the saturation magnetization is preferably 0.3 or less, more preferably less than 0.1, and further preferably 0. It is less than 05.
  • the ratio (residual magnetization / saturation magnetization) is equal to or less than the upper limit or less than the upper limit, magnetic aggregation can be suppressed more effectively, and conduction reliability can be further improved.
  • the ratio of the residual magnetization to the saturation magnetization may be 0.01 or more.
  • the ratio of the residual magnetization to the saturation magnetization is preferably 0.4 or less, more preferably 0.3 or less, still more preferably less than 0.1, particularly. It is preferably less than 0.05.
  • the ratio (residual magnetization / saturation magnetization) is equal to or less than the upper limit or less than the upper limit, magnetic aggregation can be suppressed more effectively, and conduction reliability can be further improved.
  • the ratio of the residual magnetization to the saturation magnetization may be 0.01 or more.
  • the residual magnetization of the conductive particles is preferably less than 2.0 emu / g, more preferably 1.8 emu / g or less, still more preferably 1.5 emu. It is less than / g, particularly preferably less than 1.2 emu / g.
  • the residual magnetization of the conductive particles may be 0.5 emu / g or more, or 1.0 emu / g or more.
  • the saturation magnetization of the conductive particles is preferably 15 emu / g or more, more preferably 20 emu / g or more, still more preferably 25 emu / g or more, and particularly preferably. Is 30 emu / g or more.
  • the saturation magnetization of the conductive particles may be 50 emu / g or less.
  • the residual magnetization and saturation magnetization of the conductive particles can be measured using a magnetic property measuring device (for example, "MPMS2" manufactured by Japan Quantum Design Co., Ltd.). Specifically, it can be measured as follows.
  • the sample holder is installed in the main body of the apparatus, and a magnetization curve is obtained by measurement under the conditions of a temperature of 25 ° C. (constant temperature) and a maximum applied magnetic field of 10 kOe.
  • the residual magnetization and saturation magnetization are obtained from the obtained magnetization curve.
  • the particle size of the conductive particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, still more. It is preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the particle diameter of the conductive particles is equal to or greater than the above lower limit and equal to or less than the above upper limit, the contact area between the conductive particles and the electrodes becomes sufficiently large when the electrodes are connected using the conductive particles, and the conductivity is increased. It becomes difficult to form agglomerated conductive particles when forming a portion.
  • the distance between the electrodes connected via the conductive particles does not become too large, and the conductive portion does not easily peel off from the surface of the resin particles.
  • the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conductive particles can be suitably used for the use of the conductive material.
  • the particle diameter of the conductive particles means the diameter when the conductive particles are spherical, and when the conductive particles have a shape other than the spherical shape, it is assumed to be a true sphere corresponding to the volume thereof. Means the diameter of.
  • the particle size of the conductive particles is preferably an average particle size, more preferably a number average particle size.
  • observe 50 arbitrary conductive particles with an electron microscope or an optical microscope calculate the average value of the particle size of each conductive particle, or use a particle size distribution measuring device. Desired. In observation with an electron microscope or an optical microscope, the particle size of each conductive 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 conductive particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent sphere diameter. In the particle size distribution measuring device, the particle size of each conductive particle is determined as the particle size in the equivalent diameter of a sphere. The 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 20% or less, more preferably 10% or less, still more preferably 5% or less.
  • the coefficient of variation (CV value) of the particle size of the conductive particles may be 1% or more.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of particle size of conductive particles Dn: Average value of particle size of conductive particles
  • 10% K value of the conductive particles is preferably 100 N / mm 2 or more, more preferably 1000 N / mm 2 or more, preferably 25000N / mm 2 or less, more It is preferably 20000 N / mm 2 or less.
  • the 10% K value of the conductive particles is equal to or higher than the lower limit and lower than the upper limit, the connection resistance between the electrodes can be lowered more effectively, and the occurrence of cracking of the conductive particles is even more effective. It is possible to further effectively improve the connection reliability between the electrodes.
  • 30% K value of the conductive particles is preferably 100 N / mm 2 or more, more preferably 1000 N / mm 2 or more, preferably 15000 N / mm 2 or less, more It is preferably 10000 N / mm 2 or less.
  • the 30% K value of the conductive particles is equal to or higher than the lower limit and lower than the upper limit, the connection resistance between the electrodes can be lowered more effectively, and the occurrence of cracking of the conductive particles is even more effective. It is possible to further effectively improve the connection reliability between the electrodes.
  • the ratio of the 10% K value of the conductive particles to the 30% K value of the conductive particles (10% K value of the conductive particles / 30% K value of the conductive particles) is preferably 1.5 or more. It is more preferably 1.55 or more, preferably 5 or less, and more preferably 4.5 or less.
  • the connection resistance between the electrodes can be further effectively lowered. The occurrence of cracking of the conductive particles can be suppressed more effectively, and the connection reliability between the electrodes can be further effectively improved.
  • the 10% K value and the 30% K value in the conductive particles can be measured as follows.
  • the compressive elastic modulus 10% K value and 30% K value
  • the 10% K value and the 30% K value in the conductive particles can be calculated by arithmetically averaging the 10% K value and the 30% K value of 50 arbitrarily selected conductive particles. preferable.
  • the compressive elastic modulus universally and quantitatively represents the hardness of the conductive particles.
  • the hardness of the conductive particles can be quantitatively and uniquely expressed.
  • the above ratio (10% K value of the conductive particles / 30% K value of the conductive particles) can quantitatively and uniquely represent the physical properties of the conductive particles at the time of initial compression.
  • 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 schematically showing conductive particles according to the first embodiment of the present invention.
  • the conductive particles 1 shown in FIG. 1 are conductive particles having the above configuration A.
  • the conductive particle 1 has a resin particle 2, a conductive portion 3, and a magnetic material portion 4.
  • the magnetic material portion 4 contains a magnetic material.
  • the conductive portion 3 is arranged on the outside of the outer surface of the resin particles 2.
  • the magnetic material portion 4 is arranged between the resin particles 2 and the conductive portion 3. Therefore, in the conductive particles 1, the magnetic material portion 4 is arranged on the outer surface of the resin particles 2, and the conductive material portion 3 is arranged on the outer surface of the magnetic material portion 4.
  • the conductive portion 3 is a single conductive layer.
  • the magnetic material portion 4 is a single-layer magnetic layer.
  • the conductive portion may be a single conductive layer or a multilayer conductive layer composed of two or more layers.
  • the magnetic material portion may be a single magnetic layer or a multi-layered magnetic layer composed of two or more layers.
  • FIG. 2 is a cross-sectional view schematically showing the conductive particles according to the second embodiment of the present invention.
  • the conductive particles 1A shown in FIG. 2 are conductive particles having the above configuration B.
  • the conductive particles 1A have resin particles 2A and a conductive portion 3A.
  • the conductive portion 3A contains a magnetic material.
  • the conductive portion 3A is arranged on the outer surface of the resin particles 2A.
  • the conductive portion 3A is a single conductive layer.
  • the conductive portion 3A is a single magnetic layer.
  • the conductive portion may be a single-layer conductive layer, or may be a multi-layered conductive layer composed of two or more layers.
  • FIG. 3 is a cross-sectional view schematically showing the conductive particles according to the third embodiment of the present invention.
  • the conductive particles 1B shown in FIG. 3 are conductive particles having the above configuration C.
  • the conductive particles 1B have resin particles 2B and a conductive portion 3B.
  • the resin particles 2B include a magnetic material 4B.
  • the resin particles 2B contain a magnetic material 4B.
  • the resin particles 2B and the magnetic material 4B constitute magnetic inclusion resin particles.
  • the conductive portion 3B is arranged on the outer surface of the resin particles 2B.
  • FIG. 4 is a cross-sectional view schematically showing the conductive particles according to the fourth embodiment of the present invention.
  • the conductive particles 1C shown in FIG. 4 are conductive particles having the above configuration C.
  • the conductive particles 1C have resin particles 2C, a conductive portion 3C, a plurality of core substances 5, and a plurality of insulating substances 6.
  • the resin particles 2C include a magnetic material 4C.
  • the resin particles 2C contain a magnetic material 4C.
  • the resin particles 2C and the magnetic material 4C constitute magnetic inclusion resin particles.
  • the conductive portion 3C is arranged on the outer surface of the resin particles 2C so as to be in contact with the resin particles 2C.
  • the conductive portion may be a single conductive layer or a multilayer conductive layer composed of two or more layers.
  • the conductive particles 1C have a plurality of protrusions 1Ca on the conductive surface.
  • the conductive portion 3C has a plurality of protrusions 3Ca on the outer surface.
  • a plurality of core substances 5 are arranged on the surface of the resin particles 2C.
  • the plurality of core substances 5 are embedded in the conductive portion 3C.
  • the core substance 5 is arranged inside the protrusions 1Ca and 3Ca.
  • the conductive portion 3C covers a plurality of core substances 5.
  • the outer surface of the conductive portion 3C is raised by the plurality of core substances 5, and the protrusions 1Ca and 3Ca are formed.
  • the conductive particles 1C have an insulating substance 6 arranged on the outer surface of the conductive portion 3C. At least a part of the outer surface of the conductive portion 3C is covered with the insulating substance 6.
  • the insulating substance 6 is formed of an insulating material and is an insulating particle.
  • the conductive particles according to the present invention may have an insulating substance arranged on the outer surface of the conductive portion. However, the conductive particles according to the present invention do not necessarily have an insulating substance.
  • FIG. 5 is a cross-sectional view showing conductive particles according to a fifth embodiment of the present invention.
  • the conductive particles 1D shown in FIG. 5 are conductive particles having the above configuration A.
  • the conductive particle 1D has a resin particle 2D, a conductive portion 3D, a magnetic material portion 4D, a plurality of core substances 5, and a plurality of insulating substances 6.
  • the conductive portion 3D is arranged on the outside of the outer surface of the resin particles 2D.
  • the magnetic material portion 4D is arranged between the resin particles 2D and the conductive portion 3D. Therefore, in the conductive particles 1D, the magnetic material portion 4D is arranged on the outer surface of the resin particles 2D, and the conductive portion 3D is arranged on the outer surface of the magnetic material portion 4D.
  • the conductive portion 3D is a single conductive layer.
  • the magnetic material portion 4D is a single-layer magnetic layer.
  • the conductive portion may be a single conductive layer or a multilayer conductive layer composed of two or more layers. Further, in the conductive particles, the magnetic material portion may be a single magnetic layer or a multi-layered magnetic layer composed of two or more layers.
  • the conductive particles 1D have a plurality of protrusions 1Da on the conductive surface.
  • the conductive portion 3D has a plurality of protrusions 3Da on the outer surface.
  • the magnetic material portion 4D has a plurality of protrusions 4Da on the outer surface.
  • a plurality of core substances 5 are arranged on the surface of the resin particles 2D.
  • the plurality of core substances 5 are embedded in the conductive portion 3D and the magnetic material portion 4D.
  • the core material 5 is arranged inside the protrusions 1Da, 3Da, 4Da.
  • the magnetic material portion 4D covers a plurality of core substances 5.
  • the outer surfaces of the conductive portion 3D and the magnetic body portion 4D are raised by the plurality of core substances 5, and protrusions 1Da, 3Da, and 4Da are formed.
  • the conductive particles 1D have an insulating substance 6 arranged on the outer surface of the conductive portion 3D. At least a part of the outer surface of the conductive portion 3D is covered with the insulating substance 6.
  • the insulating substance 6 is formed of an insulating material and is an insulating particle.
  • the conductive particles according to the present invention may have an insulating substance arranged on the outer surface of the conductive portion. However, the conductive particles according to the present invention do not necessarily have an insulating substance.
  • (meth) acrylate means one or both of “acrylate” and “methacrylate”
  • (meth) acrylic means one or both of “acrylic” and “methacrylic”.
  • resin particles examples of the material of the resin particles include conventionally known organic materials.
  • 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 a polyether ether ketone, a polyether sulfone, a divinylbenzene polymer, and a divinylbenzene copolymer.
  • the divinylbenzene copolymer include a divinylbenzene-styrene copolymer and a divinylbenzene- (meth) acrylic acid ester copolymer.
  • the material of the resin particles is preferably a polymer obtained by polymerizing one or more kinds of polymerizable monomers having an ethylenically unsaturated group.
  • the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group.
  • the above polymerization method is not particularly limited, and examples thereof include known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, polycondensation), addition condensation, living polymerization, and living radical polymerization. Further, as another polymerization method, suspension polymerization in the presence of a radical polymerization initiator can be mentioned.
  • the particle size of the resin particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 20 ⁇ m or less, and further. It is more preferably 10 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the particle diameter of the resin 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 electrodes becomes large, so that the conduction reliability between the electrodes can be further improved, and the conductive particles can be obtained.
  • the connection resistance between the electrodes connected via the electrodes can be further reduced.
  • the conductive portion or the magnetic material portion is formed on the surface of the resin particles by electroless plating, it is possible to make it difficult for the aggregated conductive particles to be formed.
  • the particle size of the resin particles is not more than the above upper limit, the conductive particles are easily sufficiently compressed, the connection resistance between the electrodes can be further reduced, and the distance between the electrodes can be further reduced. ..
  • the particle diameter of the resin particles means a diameter when the resin particles are spherical, and when the resin particles have a shape other than the spherical shape, it is assumed to be a true sphere corresponding to the volume thereof. Means diameter.
  • the particle size of the resin particles is preferably an average particle size, more preferably a number average particle size.
  • the particle size of the resin particles can be obtained by observing 50 arbitrary resin particles with an electron microscope or an optical microscope, calculating the average value of the particle size of each resin particle, or using a particle size distribution measuring device. In observation with an electron microscope or an optical microscope, the particle size of each resin 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 resin particles in the equivalent circle diameter is substantially equal to the average particle diameter in the equivalent sphere diameter. In the particle size distribution measuring device, the particle size of each resin particle is obtained as the particle size in the equivalent diameter of a sphere.
  • the particle size of the resin particles is preferably calculated using a particle size distribution measuring device. When measuring the particle size of the resin particles in the conductive particles, for example, the measurement can be performed as follows.
  • the coefficient of variation (CV value) of the particle size of the resin particles is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less. When the coefficient of variation of the particle size of the resin particles is not more than the upper limit, the conduction reliability and the insulation reliability between the electrodes can be further effectively improved.
  • the coefficient of variation (CV value) of the particle size of the resin particles may be 1% or more.
  • the coefficient of variation (CV value) can be measured as follows.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of the particle size of the resin particles Dn: Average value of the particle size of the resin particles
  • the conductive particles include a conductive portion arranged on the outside of the outer surface of the resin particles. Further, whether the conductive particles include a magnetic material portion containing a magnetic material arranged between the resin particles and the conductive portion (Structure A), or whether the conductive portion contains a magnetic material (Structure B). Or, the resin particles contain a magnetic substance (Structure C).
  • the conductive portion may contain a magnetic material.
  • the conductive portion preferably contains a magnetic material.
  • the conductive portion it is preferable that the conductive portion contains a magnetic material. That is, the conductive particles preferably include the above-mentioned structure A and the above-mentioned structure B, and preferably include the above-mentioned structure B and the above-mentioned structure C.
  • the magnetic material contained in the magnetic material portion and the magnetic material contained in the conductive portion may be the same or different. ..
  • the magnetic material contained in the resin particles and the magnetic material contained in the conductive portion may be the same or different.
  • the conductive portion preferably contains a metal. Further, the conductive portion may contain a substance other than metal. Hereinafter, the metal contained in the conductive portion may be referred to as "metal constituting the conductive portion" for convenience. Further, the "metal constituting the conductive portion” also includes a compound of the metal, for example, an oxide of the metal.
  • the metal constituting the conductive portion is not particularly limited, but gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, tarium, and germanium. , Cadmium, silicon, tungsten, molybdenum and alloys thereof. Examples of the metal constituting the conductive portion include tin-doped indium oxide (ITO) and solder. As the metal constituting the conductive portion, only one kind may be used, or two or more kinds may be used in combination.
  • ITO tin-doped indium oxide
  • the conductive portion preferably contains nickel, gold, palladium, silver or copper, more preferably nickel, gold or palladium, and nickel. Is particularly preferable.
  • the content of nickel in 100% by weight of the conductive portion containing nickel is preferably 10% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably. Is 90% by weight or more.
  • the content of nickel in 100% by weight of the conductive portion containing nickel may be 97% by weight or more, 97.5% by weight or more, 98% by weight or more, 100%. It may be% by weight.
  • hydroxyl groups are present on the surface of the conductive portion due to oxidation.
  • a hydroxyl group is present on the surface of a conductive portion formed of nickel due to oxidation.
  • An insulating substance can be arranged on the surface of the conductive portion having such a hydroxyl group (the surface of the conductive particles) via a chemical bond.
  • 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.
  • the metal constituting the outermost layer is preferably gold, nickel, palladium, copper or an alloy containing tin and silver, and is preferably gold. More preferred.
  • the connection resistance between the electrodes is further lowered.
  • the metal constituting the outermost layer is gold, the corrosion resistance is further improved.
  • the metal constituting the outermost layer may be nickel.
  • the thickness of the conductive portion is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 0.3 ⁇ m or less.
  • the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes. Can be made to.
  • the thickness of the conductive portion of the outermost layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably. Is 0.1 ⁇ m or less.
  • the thickness of the conductive portion of the outermost layer is equal to or higher than the lower limit and lower than the upper limit, the conductive portion of the outermost layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes is sufficiently lowered. be able to.
  • the thickness of the conductive portion can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the magnetic material is preferably a metal or a metal oxide, and more preferably a ferromagnetic material or a paramagnetic material. Only one kind of the above magnetic material may be used, or two or more kinds may be used in combination.
  • the magnetic material examples include iron, cobalt, nickel, ruthenium, lanthanoid, ferrite and the like.
  • ferrite chromite into mug ( ⁇ Fe 2 O 3), and MFe compounds represented by 2 O 4 (in MFe 2 O 4, M is, Co, Ni, Mn, Zn , Mg, Cu, Fe, Li 0.5 Fe 0.5 etc.).
  • the magnetic material may be an alloy.
  • the alloy include nickel-cobalt alloy, cobalt-tungsten alloy, iron-platinum alloy, iron-cobalt alloy and the like.
  • the metal may be a metal ion.
  • the magnetic material preferably contains iron, cobalt, ferrite, nickel or an alloy thereof, more preferably iron, cobalt, or ferrite, and iron, cobalt, or iron. It is more preferable to contain triiron tetroxide (Fe 3 O 4).
  • the content of the magnetic material contained in the magnetic material portion is contained in the total 100% by volume of the content of the resin particles and the content of the magnetic material portion (A1). ).
  • the content (A1) is preferably 3% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, still more preferably 15% by volume or more, still more preferably 18% by volume or more. It is particularly preferably 20% by volume or more, preferably 45% by volume or less, more preferably 40% by volume or less, and further preferably 35% by volume or less.
  • the content of the magnetic material contained in the magnetic material portion is contained in 100% by weight of the total of the content of the resin particles and the content of the magnetic material portion (A2). ).
  • the content (A2) is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 30% by weight or more, still more preferably 40% by weight or more, still more preferably 45% by weight or more. Particularly preferably 50% by weight or more, preferably 80% by weight or less, more preferably 75% by weight or less, still more preferably 70% by weight or less.
  • the content of the magnetic substance contained in the conductive particles in 100% by volume of the conductive particles is defined as the content (A3). Therefore, in the above-mentioned content (A3), when the conductive particles contain the magnetic material in the portion other than the magnetic material portion (for example, the conductive portion or the resin particles), it is the content of the magnetic material including these.
  • the content (A3) is preferably 2% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, still more preferably 30% by volume or more, still more preferably 35% by volume or more.
  • the content of the magnetic substance contained in the conductive particles in 100% by weight of the conductive particles is defined as the content (A4). Therefore, in the above content (A4), when the conductive particles contain a magnetic substance in a portion other than the magnetic substance portion (for example, the conductive portion or the resin particles), the content of the magnetic substance includes these as well.
  • the content (A4) is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, still more preferably 50% by weight or more, still more preferably 70% by weight or more. It is particularly preferably 75% by weight or more, most preferably 80% by weight or more, preferably 97% by weight or less, and more preferably 95% by weight or less. When the content (A4) is at least the above lower limit and at least the above upper limit, the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive portion is defined as the content (B1) in the total of 100% by volume of the content of the resin particles and the content of the conductive portion. do.
  • the content (B1) is preferably 3% by volume or more, more preferably 5% by volume or more, further preferably 7% by volume or more, particularly preferably 10% by volume or more, preferably 60% by volume or less, and more preferably 55. By volume or less, more preferably 50% by volume or less.
  • the content of the magnetic substance contained in the conductive portion is defined as the content (B2) in the total of 100% by weight of the content of the resin particles and the content of the conductive portion. do.
  • the content (B2) is preferably 10% by weight or more, more preferably 15% by weight or more, further preferably 20% by weight or more, preferably 98% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight. It is less than% by weight.
  • the content (B2) is at least the above lower limit and at least the above upper limit, the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive particles in 100% by volume of the conductive particles is defined as the content (B3). Therefore, in the above-mentioned content (B3), when the conductive particles contain a magnetic material in a portion other than the above-mentioned conductive portion (for example, a magnetic material portion or a resin particle), it is the content of the magnetic material including these.
  • the content (B3) is preferably 2% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, still more preferably 15% by volume or more, still more preferably 18% by volume or more.
  • the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive particles in 100% by weight of the conductive particles is defined as the content (B4). Therefore, in the above-mentioned content (B4), when the conductive particles contain a magnetic material in a portion other than the above-mentioned conductive portion (for example, a magnetic material portion or a resin particle), it is the content of the magnetic material including these.
  • the content (B4) is preferably 3% by weight or more, more preferably 7% by weight or more, still more preferably 10% by weight or more, still more preferably 30% by weight or more, still more preferably 45% by weight or more. It is particularly preferably 50% by weight or more, and most preferably 60% by weight or more.
  • the content (B4) is preferably 99% by weight or less, more preferably 98% by weight or less, and further preferably 97% by weight or less.
  • the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the resin particles is defined as the content (C1) in the content of the resin particles of 100% by volume.
  • the content (C1) is preferably 3% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, still more preferably 15% by volume or more, still more preferably 18% by volume or more. It is particularly preferably 20% by volume or more, preferably 85% by volume or less, and more preferably 80% by volume or less.
  • the content of the magnetic substance contained in the resin particles is defined as the content (C2) in the content of 100% by weight of the resin particles.
  • the content (C2) is preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably 20% by weight or more, still more preferably 40% by weight or more, still more preferably 45% by weight or more. Particularly preferably 50% by weight or more, preferably 99% by weight or less, more preferably 97% by weight or less, still more preferably 95% by weight or less.
  • the content (C2) is at least the above lower limit and at least the above upper limit, the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive particles in 100% by volume of the conductive particles is defined as the content (C3). Therefore, in the above content (C3), when the conductive particles contain a magnetic substance in a portion other than the resin particles (for example, a conductive portion or a magnetic substance portion), the content is the content of the magnetic substance including these.
  • the content (C3) is preferably 3% by volume or more, more preferably 7% by volume or more, still more preferably 10% by volume or more, still more preferably 15% by volume or more, still more preferably 18% by volume or more.
  • the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive particles in 100% by weight of the conductive particles is defined as the content (C4). Therefore, in the above content (C4), when the conductive particles contain a magnetic substance in a portion other than the resin particles (for example, a conductive portion or a magnetic substance portion), the content is the content of the magnetic substance including these.
  • the content (C4) is preferably 3% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, still more preferably 30% by weight or more, still more preferably 60% by weight or more.
  • the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive particles in 100% by volume of the conductive particles is defined as the content (D).
  • the content (D) is preferably 3% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, still more preferably 25% by volume or more, particularly preferably 50% by volume or more, preferably 50% by volume or more. It is 85% by volume or less.
  • the content (D) is at least the above lower limit and at least the above upper limit, the magnetism collection can be further enhanced.
  • the content of the magnetic substance contained in the conductive particles in 100% by weight of the conductive particles is defined as the content (E).
  • the content (E) is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, still more preferably 25% by weight or more, particularly preferably 40% by weight or more, preferably 40% by weight or more. It is 99% by weight or less, more preferably 97% by weight or less.
  • the contents (A1) to (A4), (B1) to (B4), (C1) to (C4), (D), and (E) can be measured by ICP emission spectrometry. Specifically, it can be measured as follows.
  • the conductive particles are completely dissolved using hydrochloric acid or the like, and the amount of metal ions contained in the conductive particles is quantified. From the quantified amount of metal ions, the content (% by weight) of the magnetic substance present in the conductive particles is calculated. In addition, the volume of the magnetic material can be calculated from the density of the magnetic material. The volume of the conductive particles can be calculated from the radius of the conductive particles measured by observing the cross section of the conductive particles, and the content (% by volume and% by weight) of the magnetic substance can be calculated.
  • the magnetic material portion may be a continuous layer or an aggregate layer which is an aggregate of magnetic material fine particles.
  • the magnetic material portion is preferably an aggregate layer which is an aggregate of magnetic material fine particles.
  • the primary average particle diameter of the magnetic fine particles constituting the aggregate layer which is an aggregate of the magnetic fine particles is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more. It is preferably 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and particularly preferably 20 nm or less.
  • the primary average particle diameter of the magnetic material is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, preferably 500 nm or less, still more preferably 100 nm or less, still more preferably. It is 50 nm or less, particularly preferably 20 nm or less.
  • the primary average particle size of the magnetic fine particles can be measured, for example, by observing with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the content of the conductive portion contained in the conductive particles is preferably 15% by weight or more in 100% by weight of the conductive particles. It is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 95% by weight or less, more preferably 85% by weight or less, still more preferably 75% by weight or less.
  • the content of the conductive portion contained in the conductive particles is equal to or higher than the lower limit and lower than the upper limit, and the primary average particle diameter of the magnetic fine particles constituting the aggregate layer is equal to or higher than the lower limit and lower than the upper limit.
  • the content of the conductive portion contained in the conductive particles in 100% by weight of the conductive particles is preferably 15% by weight or more, more preferably 30% by weight or more, still more preferably. Is 40% by weight or more, preferably 95% by weight or less, more preferably 85% by weight or less, still more preferably 75% by weight or less.
  • the content of the conductive portion contained in the conductive particles is not less than the above lower limit and not more than the above upper limit, the ratio of the residual magnetization to the saturation magnetization can be easily adjusted to 0.4 or less. That is, the conductive particles having the above configuration B can be obtained satisfactorily.
  • the content of the conductive portion contained in the conductive particles is preferably 15% by weight or more in 100% by weight of the conductive particles. It is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 95% by weight or less, more preferably 85% by weight or less, still more preferably 75% by weight or less.
  • the content of the conductive portion contained in the conductive particles is equal to or higher than the lower limit and lower than the upper limit, and the primary average particle diameter of the magnetic material is equal to or higher than the lower limit and lower than the upper limit, the residual magnetization is saturated. It is easy to adjust the ratio to magnetization to 0.4 or less. That is, the conductive particles having the above-mentioned structure C and the above-mentioned structure B can be satisfactorily obtained.
  • the content of the conductive portion contained in the conductive particles in 100% by weight of the conductive particles is energy dispersive X-ray analysis using an electric field radiation transmission electron microscope (“JEM-2010FEF” manufactured by JEOL Ltd.). It can be measured by EDX) and ICP emission analysis method. Specifically, 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 inspection containing the conductive particles.
  • 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
  • the conductive particles are completely dissolved using hydrochloric acid or the like, and the amount of metal ions contained in the conductive particles is quantified. From the quantified amount of metal ions, the content (% by weight) of the conductive portion present in the conductive particles is calculated. Further, the volume of the conductive portion can be calculated from the density of the metal contained in the conductive portion. The volume of the conductive particles can be calculated from the radius of the conductive particles measured by observing the cross section of the conductive particles, and the content (volume% and weight%) of the conductive portion can be calculated.
  • the thickness of the magnetic material portion is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably 0.3 ⁇ m or less. More preferably, it is 0.2 ⁇ m or less.
  • the thickness of the magnetic material portion is not less than the above lower limit and not more than the above upper limit, sufficient magnetic performance can be obtained and the effect of the present invention can be more effectively exhibited.
  • the thickness of the magnetic material portion can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the method of forming the conductive portion or the magnetic material portion on the surface of the resin particles is not particularly limited.
  • the method for forming the conductive portion or the magnetic material portion include a method by electroless plating, a method by electroplating, a method by physical collision, a method by mechanochemical reaction, a method by physical vapor deposition or physical adsorption. , And a method of coating the surface of the resin particles with a metal powder or a paste containing the metal powder and a binder.
  • the method for forming the conductive portion or the magnetic material portion is preferably electroless plating, electroplating, or a method by physical collision.
  • Examples of the method by physical vapor deposition include vacuum deposition, ion plating, and ion sputtering. Further, in the above-mentioned physical collision method, for example, a seater composer (manufactured by Tokuju Kosakusho Co., Ltd.) or the like is used.
  • the magnetic material may be dispersed inside the resin particles or may be present in layers. From the viewpoint of reducing the residual magnetization, it is preferable that the magnetic material is dispersed inside the resin particles in the conductive particles having the configuration C.
  • resin particles in which the magnetic material is dispersed inside can be obtained.
  • the resin particles having a solid structure and the magnetic material are mixed, the outer surface of the resin particles is coated with the magnetic material, and then the outer surface of the magnetic material is coated with a resin to obtain magnetism. It is possible to obtain resin particles in which the body is present in layers.
  • 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.
  • the conductive particles preferably have a plurality of the protrusions.
  • An oxide film is often formed on the surface of the electrode connected by 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 arranging the conductive particles between the electrodes and crimping them. Therefore, the electrodes and the conductive portion come into contact with each other more reliably, and the connection resistance between the electrodes becomes even lower.
  • the conductive particles include an insulating substance, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the protrusions of the conductive particles between the conductive particles and the electrode. Insulating substances or binder resins can be eliminated even more effectively. Therefore, the connection resistance between the electrodes can be further reduced.
  • a method of adhering a core material to the surface of metal particles and then forming a conductive portion by electroless plating, and a method of forming a conductive portion by electroless plating on the surface of metal particles are performed. Examples thereof include a method of adhering a core material and further forming a conductive portion by electroless plating. Further, it is not necessary to use the core substance in order to form the protrusions.
  • a method of adding a core substance in the middle of forming a conductive portion on the surface of the metal particles can be mentioned.
  • the conductive portion is formed on the metal particles by electroless plating without using the above-mentioned core material, and then the plating is deposited in the shape of protrusions on the surface of the conductive portion, and further by electroless plating.
  • a method of forming a conductive portion or the like may be used.
  • a method of adhering the core substance to the surface of the metal particles a method of adding the core substance to the dispersion liquid of the metal particles and accumulating and adhering the core substance on the surface of the metal particles by van der Waals force, and a method of adhering the core substance to the surface of the metal particles.
  • Examples thereof include a method in which a core substance is added to a container containing metal particles and the core substance is attached to the surface of the metal particles by a mechanical action such as rotation of the container.
  • the method of adhering the core substance to the surface of the metal particles is preferably a method of accumulating and adhering the core substance to the surface of the metal particles in the dispersion liquid.
  • 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, it is preferable that the core substance is 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 metal may be the same as or different from the metal constituting the metal particles.
  • 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 aggregated, 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 substance is preferably an average particle size, 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 the core material per piece 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 sphere diameter. In the particle size distribution measuring device, the particle size of the core substance per piece 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 one conductive particle is preferably 3 or more, more preferably 5 or more.
  • the upper limit of the number of the 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 lowered.
  • 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 protrusions 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 lowered.
  • 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 conductive particle 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 instead of 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 resin and inorganic substances.
  • the material of the insulating substance is preferably the 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 above-mentioned inorganic substances include silica, alumina, barium titanate, zirconia, carbon black, silicate glass, borosilicate glass, lead glass, soda-lime glass and alumina silicate glass.
  • Other materials of the insulating substance include polyolefin compounds, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, thermoplastic resins, cross-linked products of thermoplastic resins, thermosetting resins and water-soluble materials. Examples include resin.
  • 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, an emulsion polymerization method and the like.
  • Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion method, spraying method, dipping and vacuum vapor deposition. From the viewpoint of further effectively enhancing the insulation reliability and 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 polyelectrolyte 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. Particularly preferably, it is 1000 nm or less.
  • the particle size of the insulating particles is not more than 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 resin.
  • the particle size of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating particles between the electrodes and the conductive particles at the time of connection between 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 the insulating particles per 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 sphere diameter.
  • the particle size of each insulating particle is determined as the particle size at the equivalent sphere diameter.
  • the average particle size of the insulating particles is preferably calculated using a particle size distribution measuring device.
  • the measurement can be performed 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 inspection containing the conductive particles.
  • 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 insulating particles in the conductive particles dispersed in the embedded resin body for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 50,000 times, 50 conductive particles were randomly selected, and the insulating particles of each conductive particle were selected. Observe. 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.
  • FE-SEM field emission scanning electron microscope
  • the ratio of the particle diameter of the conductive particles to the particle diameter of the insulating particles is preferably 4 or more, more preferably 8 or more, and preferably 8 or more. It is 200 or less, more preferably 100 or less.
  • the conductive material according to the present invention includes the above-mentioned conductive particles and a binder resin. It is preferable that the conductive particles are dispersed in the binder resin and used as a conductive material.
  • the conductive material is preferably an anisotropic conductive material.
  • the conductive material is suitably used for electrical connection of electrodes.
  • the conductive material is preferably a circuit connection material.
  • the above binder resin is not particularly limited.
  • the binder resin a known insulating resin is used.
  • the binder resin 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.
  • the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, elastomers and the like. Only one kind of the binder resin may be used, or two or more kinds thereof may be used in combination.
  • Examples of the vinyl resin include vinyl acetate resin, acrylic resin, styrene resin and the like.
  • 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, unsaturated polyester resin and the like.
  • 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.
  • -Hydrogen additives for styrene block copolymers and the like can be mentioned.
  • the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
  • 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 photostabilizing agent. It may contain various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant.
  • a conventionally known dispersion method can be used as a method for dispersing the conductive particles in the binder resin.
  • the method for dispersing the conductive particles in the binder resin include the following methods. A method in which the conductive particles are added to the binder resin 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 resin, and kneaded with a planetary mixer or the like to disperse the particles. A method in which the binder resin is diluted with water or an organic solvent, the conductive particles are added, and the binder resin is 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 component.
  • 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 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 resin 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, and particularly preferably 70% by weight or more. Is 99.99% by weight or less, more preferably 99.9% by weight or less.
  • the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further improved.
  • 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, and more preferably 60% by weight. % Or less, more preferably 40% by weight or less, still more preferably 20% by weight or less, and particularly 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 can be further effectively reduced. Can be enhanced.
  • 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 the binder resin, and the conductive particles are described above. It is a conductive particle, and the first electrode and the second electrode are electrically connected by the conductive particles.
  • the connection structure includes a step of arranging the conductive particles or the conductive material between the first connection target member and the second connection target member, and a step of conducting a conductive connection by thermocompression bonding. Can be obtained through.
  • the conductive particles have the insulating substance, it is preferable that the insulating substance is desorbed from the conductive particles at the time of thermocompression bonding.
  • the connecting portion itself is the conductive particles. That is, the first connection target member and the second connection target member are connected by the conductive particles.
  • the conductive material used to obtain the connection structure is preferably an anisotropic conductive material.
  • FIG. 6 schematically shows a connection structure using conductive particles according to the first embodiment of the present invention in a front sectional view.
  • connection structure 51 shown in FIG. 6 has a first connection target member 52, a second connection target member 53, and a connection portion 54 connecting the first and second connection target members 52 and 53. Be prepared.
  • the connecting portion 54 is formed by curing a conductive material containing the conductive particles 1.
  • the conductive particles 1 are shown schematically for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 1A, 1B, 1C, and 1D may be used.
  • the manufacturing method of the above connection structure is not particularly limited.
  • the method for manufacturing the connection structure preferably includes the following steps.
  • a step of applying a magnetic field or a magnetic force before or after the second placement step is a step of applying a magnetic field or a magnetic force before or after the second placement step.
  • connection structure in which the first electrode and the second electrode are electrically connected by the conductive particles.
  • thermocompression bonding step is performed after the second arrangement step and after the step of applying the magnetic field or the magnetic force.
  • the thermocompression bonding pressure is preferably 40 MPa or more, more preferably 60 MPa or more, preferably 90 MPa or less, and more preferably 70 MPa or less.
  • the heating temperature of the thermocompression bonding is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 140 ° C. or lower, and more preferably 120 ° C. or lower.
  • the pressure and temperature of the thermocompression bonding are at least the above lower limit and at least the above upper limit, the conduction reliability and the insulation reliability between the electrodes can be further improved. Further, when the conductive particles have the insulating particles, the insulating particles can be easily desorbed from the surface of the conductive particles at the time of conductive connection.
  • the conductive particles When the conductive particles have the insulating particles, they are present between the conductive particles and the first electrode and the second electrode when the laminated body is heated and pressurized. It is possible to eliminate the above-mentioned insulating particles. For example, during the heating and pressurization, the insulating particles existing between the conductive particles and the first electrode and the second electrode are removed from the surface of the conductive particles. Easily detached. During the heating and pressurization, some of the insulating particles may be separated from the surface of the conductive particles, and the surface of the conductive portion may be partially exposed. When the exposed surface of the conductive portion comes into contact with the first electrode and the second electrode, the first electrode and the second electrode are electrically connected via the conductive particles. can do.
  • 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 semiconductor chips, semiconductor packages, LED chips, LED packages, electronic components such as 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 electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode.
  • the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode.
  • the electrode When 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.
  • the trivalent metal element include Sn, Al and Ga.
  • Example 1 Preparation of Resin Particles Containing Magnetic Material
  • Polystyrene particles having an average particle diameter of 0.5 ⁇ m were prepared as seed particles.
  • a mixed solution was prepared by mixing 3.9 parts by weight of the polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight polyvinyl alcohol aqueous solution. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.
  • the emulsion was added to the mixed solution in the separable flask and stirred for 12 hours to allow the seed particles to absorb the monomer to obtain a suspension containing the seed particles swollen by the monomer.
  • a nickel plating solution (pH 8.5) containing nickel sulfate 0.35 mol / L, dimethylamine borane 1.38 mol / L and sodium citrate 0.5 mol / L was prepared.
  • the above nickel plating solution was gradually added dropwise to the suspension to perform electroless nickel plating. Then, by filtering the suspension, the particles are taken out, washed with water, and dried to form a nickel-boron conductive layer on the surface of the magnetic inclusion resin particles, and the conductive particles having a conductive portion on the surface are formed. Obtained.
  • conductive material anisotropic conductive paste 7 parts by weight of the obtained conductive particles, 25 parts by weight of bisphenol A type phenoxy resin, 4 parts by weight of fluorene type epoxy resin, and 30 parts by weight of phenol novolac type epoxy resin.
  • a conductive material anisotropic conductive paste was obtained by blending a weight portion and SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), defoaming and stirring for 3 minutes.
  • a transparent glass substrate having an IZO electrode pattern (first electrode, Vickers hardness of metal on the surface of the electrode 100 Hv) having an L / S of 10 ⁇ m / 10 ⁇ m formed on the upper surface was prepared. Further, a semiconductor chip having an Au electrode pattern (second electrode, Vickers hardness of metal on the surface of the electrode 50 Hv) having an L / S of 10 ⁇ m / 10 ⁇ m formed on the lower surface was prepared.
  • the obtained anisotropic conductive paste was applied onto the transparent glass substrate so as to have a thickness of 30 ⁇ m to form an anisotropic conductive paste layer. Next, the semiconductor chips were laminated on the anisotropic conductive paste layer so that the electrodes face each other.
  • the magnetizing process was performed from the upper part of the electrode. After that, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100 ° C., the pressurized heating head is placed on the upper surface of the semiconductor chip, and a pressure of 85 MPa is applied to form the anisotropic conductive paste layer. It was cured at 100 ° C. to obtain a connection structure.
  • Example 2 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the metal type of the conductive portion was changed to Ni—B / Au.
  • Example 3 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the metal type of the conductive portion was changed to Ni—B / Pd.
  • Example 4 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the metal type of the conductive portion was changed to Ni—B / Ag.
  • Example 5 The reducing agent used to prepare the conductive portion was changed from dimethylamine borane to sodium hypophosphite, and the concentration was further changed to 2.6 mol / L. The phosphorus content in the Ni plating film obtained at this time was 12% by weight. Furthermore, the metal type of the conductive part was changed to Ni-P / Au. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that these were changed. The obtained Ni—P / Au layer lost its function as a magnetic material.
  • Example 6 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 5 except that the metal type of the conductive portion was changed to Ni-P / Pd.
  • Example 7 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 5 except that the metal type of the conductive portion was changed to Ni-P / Ag.
  • Example 8 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of iron (II) chloride / tetrahydrate to be added was changed from 2 parts by weight to 5 parts by weight. ..
  • Example 9 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of iron (II) chloride / tetrahydrate to be added was changed from 2 parts by weight to 4 parts by weight. ..
  • Example 10 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of iron (II) chloride tetrahydrate to be added was changed from 2 parts by weight to 3 parts by weight. ..
  • Example 11 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of iron (II) chloride / tetrahydrate to be added was changed from 2 parts by weight to 1 part by weight. ..
  • Example 12 Conductive particles and conductive material in the same manner as in Example 1 except that the iron (II) chloride tetrahydrate and 28% aqueous ammonia to be added were changed to cobalt sulfate heptahydrate and dimethylamine borane. And a connection structure was obtained.
  • Example 13 Conductive particles and conductive material in the same manner as in Example 1 except that the iron (II) chloride tetrahydrate and 28% aqueous ammonia to be added were changed to nickel sulfate hexahydrate and dimethylamine borane. And a connection structure was obtained.
  • Example 14 Conductive particles and conductive material in the same manner as in Example 1 except that the iron (II) chloride tetrahydrate and 28% aqueous ammonia to be added were changed to iron sulfate heptahydrate and dimethylamine borane. And a connection structure was obtained.
  • Example 15 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of divinylbenzene to be added was changed from 150 parts by weight to 50 parts by weight.
  • Example 16 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of divinylbenzene to be added was changed from 150 parts by weight to 40 parts by weight.
  • Example 17 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that the amount of the magnetic inclusion resin particles charged was changed from 10 parts by weight to 15 parts by weight.
  • Example 18 (1) Preparation of Resin Particles with Magnetic Material Parts Resin particles were obtained in the same manner as in Example 1 except that the solvent used for producing the resin particles was changed from toluene to ethanol. The average particle size of the obtained resin particles was 2.75 ⁇ m. Next, 2.0 g of the resin particles were ultrasonically dispersed in 40.0 g of ion-exchanged water to obtain a core particle dispersion.
  • a nickel plating solution (pH 8.5) containing nickel sulfate 0.35 mol / L, dimethylamine borane 1.38 mol / L and sodium citrate 0.5 mol / L was prepared.
  • the above nickel plating solution was gradually added dropwise to the suspension to perform electroless nickel plating. Then, by filtering the suspension, the particles are taken out, washed with water, and dried to form a nickel-boron conductive layer on the surface of the resin particles containing the magnetic substance portion, and the conductive particles having the conductive portion on the surface.
  • connection structure was obtained in the same manner as in Example 1.
  • Example 19 Conductive particles, conductive materials, and connecting structures were prepared in the same manner as in Example 18, except that resin particles having an average particle diameter of 1.52 ⁇ m were used and the amount of magnetic fluid to be added was changed to 4 mL. Obtained.
  • Example 20 Conductive particles, conductive materials, and connecting structures were prepared in the same manner as in Example 18 except that resin particles having an average particle diameter of 1.08 ⁇ m were used and the amount of magnetic fluid to be added was changed to 2 mL. Obtained.
  • Example 21 The reducing agent used to prepare the conductive portion was changed from dimethylamine borane to sodium hypophosphite, and the concentration was further changed to 2.6 mol / L.
  • the phosphorus content in the Ni plating film obtained at this time was 12% by weight.
  • the metal type of the conductive part was changed to Ni-P / Au. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 18 except that these were changed.
  • the obtained Ni—P / Au layer lost its function as a magnetic material.
  • Example 22 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 21 except that the metal type of the conductive portion was changed to Ni-P / Pd.
  • Example 23 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 21 except that the metal type of the conductive portion was changed to Ni-P / Ag.
  • Example 24 The amount of 5% by weight polyvinyl alcohol aqueous solution to be added was changed from 490 parts by weight to 200 parts by weight, the amount of divinylbenzene to be added was changed from 150 parts by weight to 50 parts by weight, and the amount of magnetic inclusion resin particles charged.
  • conductive particles, a conductive material and a connecting structure were obtained, except that 10 parts by weight was changed to 15 parts by weight.
  • Example 25 The amount of 5% by weight polyvinyl alcohol aqueous solution to be added was changed from 490 parts by weight to 100 parts by weight, the amount of divinylbenzene to be added was changed from 150 parts by weight to 50 parts by weight, and the amount of magnetic inclusion resin particles charged.
  • conductive particles, a conductive material and a connecting structure were obtained, except that 10 parts by weight was changed to 15 parts by weight.
  • Example 26 The amount of divinylbenzene to be added was changed from 150 parts by weight to 50 parts by weight, and after the catalytic treatment, 1 g of nickel particle slurry (average particle diameter 100 nm) was added to the above dispersion liquid over 3 minutes, and the core material was added. Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1 except that a suspension containing the adhered magnetic inclusion resin particles was obtained.
  • Example 27 Conductive particles were obtained in the same manner as in Example 1 except that the amount of divinylbenzene to be added was changed from 150 parts by weight to 50 parts by weight. Using these conductive particles, conductive particles with insulating particles were produced as follows.
  • the monomer composition comprises 360 mmol of methyl methacrylate, 45 mmol of glycidyl methacrylate, 20 mmol of parastyryldiethylphosphine, 13 mmol of ethylene glycol dimethacrylate, 0.5 mmol of polyvinylpyrrolidone, and 2,2'-azobis ⁇ 2- [N- (2). -Carboxyethyl) Amidino] Propane ⁇ Contains 1 mmol. After completion of the reaction, the reaction was freeze-dried to obtain insulating particles (average particle diameter 360 nm) having a phosphorus atom derived from parastilyl diethylphosphine on the surface.
  • Example 28 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 27, except that Ni particles (average particle diameter of 100 nm) were attached to the resin particles at the time of producing the conductive particles.
  • Example 29 When the conductive layer was prepared, a mixed solution of copper sulfate 200 g / L, ethylenediaminetetraacetic acid 150 g / L, sodium gluconate 100 g / L, and formaldehyde 50 g / L was adjusted to pH 10.5 with ammonia. A plating solution was prepared. While stirring the suspension at 65 ° C., a copper plating solution was added dropwise to perform electroless copper plating. Then, the particles were taken out by filtration, washed with water, and dried to obtain conductive particles having a copper layer. Except for this, conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1.
  • Example 30 A tin plating solution was prepared in which 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. Further, a reducing solution was prepared in which a solution containing 5 g / L of sodium borohydride was adjusted to pH 10.0 with sodium hydroxide. The tin plating solution was dropped, electroless tin plating was performed, and then the solution was reduced with a reducing solution. Then, the particles were taken out by filtration, washed with water, and dried to obtain conductive particles having a tin layer. Except for this, conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 1.
  • Example 31 Conductive particles, conductive materials, and connecting structures were prepared in the same manner as in Example 30, except that the amount of iron (II) chloride tetrahydrate to be added was changed from 2 parts by weight to 0.5 parts by weight. Obtained.
  • Example 32 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 18 except that Cu plating was performed when forming the conductive layer.
  • Example 33 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 18 except that tin plating was performed when forming the conductive layer.
  • Example 34 Conductive particles, a conductive material, and a connecting structure were obtained in the same manner as in Example 33, except that the ultrasonic waves were not dispersed after the addition of the magnetic fluid.
  • Comparative Example 3 A conductive material and a connecting structure were obtained in the same manner as in Comparative Example 1 except that nickel fine particles (average particle diameter 3.0 ⁇ m, coefficient of variation 20%) were used as the conductive particles.
  • Comparative Example 4 The nickel fine particles used in Comparative Example 3 were Au-plated. A conductive material and a connecting structure were obtained in the same manner as in Comparative Example 1 except that the Au-plated nickel fine particles were used as the conductive particles.
  • CV value (%) ( ⁇ / Dn) ⁇ 100 ⁇ : Standard deviation of the particle size of the coefficient of variation Dn: Average value of the particle size of the coefficient of variation
  • FE-TEM electric field radiation transmission electron microscope
  • the content of the magnetic substance contained in the resin particles in 100% by volume or 100% by volume of the resin particles is (A3), (B3), (C3), (D). ) (Volume%), Content (A4), (B4), (C4), (E) (% by volume): In 100% by volume or 100% by weight of the conductive particles, of the magnetic material contained in the conductive particles Content
  • connection resistance value (between the upper and lower electrodes)
  • Connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance is more than 2.0 ⁇ and 5.0 ⁇ or less ⁇ : Connection resistance is more than 5.0 ⁇ and 10 ⁇ or less ⁇ : Connection resistance is more than 10 ⁇
  • connection resistance value was measured with a tester to see if there was a leak between adjacent electrodes, and the resistance value was 10. The ratio of connection structures with 8 ⁇ or less was evaluated as the short circuit occurrence rate.

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WO2024043047A1 (ja) * 2022-08-25 2024-02-29 日本化学工業株式会社 導電性粒子、その製造方法および導電性材料

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JPH03263801A (ja) * 1990-03-14 1991-11-25 Unitika Ltd 複合粒子の製造方法
JPH05190014A (ja) * 1992-01-09 1993-07-30 Sekisui Fine Chem Kk 電極接続用導電性微球体
WO2020004273A1 (ja) * 2018-06-25 2020-01-02 積水化学工業株式会社 導電性粒子、導電材料及び接続構造体

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JP5505225B2 (ja) 2010-09-21 2014-05-28 デクセリアルズ株式会社 接続構造体の製造方法
JP6079425B2 (ja) 2012-05-16 2017-02-15 日立化成株式会社 導電粒子、異方性導電接着剤フィルム及び接続構造体

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JPH03263801A (ja) * 1990-03-14 1991-11-25 Unitika Ltd 複合粒子の製造方法
JPH05190014A (ja) * 1992-01-09 1993-07-30 Sekisui Fine Chem Kk 電極接続用導電性微球体
WO2020004273A1 (ja) * 2018-06-25 2020-01-02 積水化学工業株式会社 導電性粒子、導電材料及び接続構造体

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Publication number Priority date Publication date Assignee Title
WO2024043047A1 (ja) * 2022-08-25 2024-02-29 日本化学工業株式会社 導電性粒子、その製造方法および導電性材料

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