Classifications

• • 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
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
  • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
  • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
  • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

Definitions

• the present invention relates to a conductive particle in which a conductive portion is arranged on the surface of a base particle.
• the present invention also relates to a conductive material and a connection structure using the conductive particles.
• Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
• anisotropic conductive material conductive particles are dispersed in a binder resin.
• conductive particles conductive particles having base particles and conductive portions arranged on the surface of the base particles may be used.
• the anisotropic conductive material is used to obtain various connection structures.
• Connections using the above anisotropic conductive materials include connections between flexible printed circuit boards and glass substrates ( ⁇ ⁇ (1 1 1 1 1 1 1 0 n 0 1 3 3 3)), connections between semiconductor chips and flexible printed circuit boards. ( ⁇ ⁇ ( ⁇ 1 ⁇ n 1 1 ⁇ ⁇ ), Connection between semiconductor chip and glass substrate ( ⁇ ⁇ ⁇ ( ⁇ ⁇ ⁇ n 0 1 3 3 3)), and Connection between flexible printed circuit board and glass epoxy substrate ( ⁇ (( 1 1 1 1 0 n Etc.
• Patent Document 1 discloses conductive particles including a nickel layer and a gold layer formed on the nickel layer.
• the average film thickness of the gold layer is 300 or less.
• the metal layer is the outermost layer.
• the elemental composition ratio ((//)) of nickel and gold on the surface of the conductive particle by X-ray photoelectron spectroscopy analysis is 0.4 or less.
• Patent Document 2 discloses conductive particles including core particles, a 1 ⁇ 1 plating layer, a noble metal plating layer, and an antimony film.
• the above-mentioned iron plating layer covers the above core particles.
• the precious metal plating layer is less than the above-mentioned precious metal plating layer.
• the noble metal plating layer includes at least one of 8 and 01.
• the anti-rust coating covers at least one of the gold plating layer and the noble metal plating layer.
• the anti-rust film contains an organic compound.
• Patent Document 1 Japanese Patent Laid-Open No. 20 09 _ 1 0 2 7 3 1
• Patent Document 2 JP 2 0 1 3 _ 2 0 7 2 1 Publication
• the thickness of the conductive portion may be increased. However, if the thickness of the conductive portion is increased, the conductive particles may aggregate when forming the conductive portion by plating. When the conductive particles agglomerate with each other, the electrodes adjacent in the lateral direction tend to be easily connected to each other, and it may be difficult to improve the insulation reliability between the electrodes adjacent in the lateral direction.
• An object of the present invention is to effectively reduce the connection resistance between electrodes, and ⁇ 0 2020/175691 3 ⁇ (: 171? 2020 /008458
• the purpose of the present invention is to provide conductive particles capable of effectively suppressing the occurrence of aggregation of conductive particles. Moreover, the objective of this invention is providing the electrically conductive material and connection structure which used the said electroconductive particle.
• [001 1] it is provided with base particles and a conductive portion arranged on the surface of the base particles, and the base particles have conductivity inside the base particles.
• conductive particles containing a conductive metal are provided.
• the porosity of the base particle is 10% or more.
• the conductive metal includes nickel, gold, palladium, silver, or copper.
• the conductive portion contains nickel, gold, palladium, silver, or copper.
• 10% ⁇ value of the conductive particles is 1 0 0 1 ⁇ 1/ ⁇ 1 ⁇ 1 2 or more 2 5 0 0 0 1 ⁇ 1 / ⁇ 1 ⁇ 12 or less.
• 30% ⁇ value of the conductive particles is 1 0 0 1 ⁇ 1/ ⁇ 1 ⁇ 1 2 or more 1 5 0 0 0 1 ⁇ 1 / ⁇ 1 ⁇ 12 or less.
• the ratio of 10% ⁇ value of the conductive particles to 30% ⁇ value of the conductive particles is...! .5 or more and 5 or less.
• the particle diameter of the conductive particle is not less than 0.101 and not more than 100.
• the content of the conductive metal contained in the base particles is 0.1% by volume. It is above 30% by volume.
• the conductive particle has a protrusion on an outer surface of the conductive portion.
• the conductive particles are ⁇ 0 2020/175691 4 ⁇ (: 171? 2020 /008458
• An insulating material is disposed on the outer surface of the conductive portion.
• a conductive material including the above-mentioned conductive particles and a binder resin.
• the conductive material includes a plurality of the conductive particles described above, and particles of the base material particle from an outer surface of the base material particle toward a center thereof.
• the area having a distance of 1/2 of the diameter is defined as the area 1
• the total number of the conductive particles is 100%
• the conductive metal is present in the area 1 of the base particle.
• the ratio of the number of particles is 50% or more.
• the conductive material includes a plurality of the conductive particles described above, and particles of the base material particle from the center of the base material particle toward the outer surface thereof.
• area 2 the total number of the conductive particles is 100%, and the conductive metal is present in the area 2 of the base particles.
• the ratio of the number of particles is 5% or more.
• 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
• a connecting member connecting the target member and the second connection target member, wherein the material of the connecting portion is the above-mentioned conductive particles, or the conductive particles and the binder resin.
• a connection structure is provided, which is a conductive material containing: and the first electrode and the second electrode are electrically connected by the conductive particles.
• the conductive particles according to the present invention include base particles, and conductive portions arranged on the surfaces of the base particles.
• the base material particle contains a conductive metal inside the base material particle. Since the conductive particles according to the present invention are provided with the above configuration, the connection resistance between the electrodes can be effectively reduced, and the occurrence of aggregation of the conductive particles can be effectively suppressed. can do.
• FIG. 1 is a cross-sectional view showing a conductive particle according to a first embodiment of the present invention. ⁇ 02020/175691 5 (: 17 2020/008458
• FIG. 2 is a cross-sectional view showing a conductive particle according to a second embodiment of the present invention.
• FIG. 3 is a sectional view showing a conductive particle according to a third embodiment of the present invention.
• FIG. 4 is a schematic diagram for explaining each region in the base particle for confirming the presence or absence of a conductive metal.
• FIG. 5 is a front sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
• the conductive particles according to the present invention include base particles and conductive parts arranged on the surfaces of the base particles.
• the base material particle contains a conductive metal inside the base material particle.
• the conductive particles according to the present invention are provided with the above configuration, the connection resistance between the electrodes can be effectively reduced, and the occurrence of aggregation of the conductive particles is effective. Can be suppressed.
• the conductive particles are used.
• the thickness of the conductive portion may be increased.
• the conductive particles may aggregate during the formation of the conductive portion by plating.
• the electrodes adjacent in the lateral direction tend to be easily connected to each other, and it may be difficult to improve the insulation reliability between the electrodes adjacent in the lateral direction.
• the present inventors use both specific conductive particles to reduce both the connection resistance between electrodes and to suppress the occurrence of aggregation of conductive particles. I found that you can.
• the conductive particles are compressed at the time of connection between the electrodes in the vertical direction, so that not only a conductive path is formed on the surface (conductive portion) of the conductive particles, but also inside the conductive particles (conductive Conductive metal) can also form a conductive path. Further, the conductive metal inside the conductive particles contributes to the reduction of the connection resistance to some extent even if the conductive path is not completely formed. As a result, the connection resistance between the electrodes in the vertical direction can be made sufficiently low even if the thickness of the conductive portion is relatively thin.
• the conductive portion is relatively thin, it is possible to suppress the occurrence of aggregation of conductive particles and to effectively improve the insulation reliability between the electrodes that are adjacent to each other and that are not connected. it can.
• the connection resistance between the electrodes can be effectively reduced, and the aggregation of the conductive particles can be effectively suppressed. ..
• the conductive path (conductive portion) is formed not only on the surface of the base material particle but also inside the base material particle, and the conductive path (conductive portion) can enter the inside of the base material particle. As a result, the adhesiveness of the conductive part of the conductive particles can be effectively enhanced, and the peeling of the conductive part of the conductive particles can be effectively suppressed.
• the 10% ⁇ value (compressive elastic modulus when compressed by 10%) of the conductive particles is preferably More preferably
• connection resistance between the electrodes can be lowered more effectively, ⁇ 0 2020/1756 91 7 ⁇ (: 171? 2020 /008458
• the generation of cracks in the conductive particles can be suppressed more effectively, and the connection reliability between the electrodes can be improved more effectively.
• the value of 30% ⁇ value (compressive elastic modulus when compressed by 30%) of the conductive particles is preferably More preferably
• connection resistance between the electrodes can be further effectively reduced, and the occurrence of cracking of the conductive particles can be further improved. It can be effectively suppressed, and the connection reliability between the electrodes can be more effectively enhanced.
• the ratio of 10% ⁇ value of the conductive particles to 30% ⁇ value of the conductive particles (10% of conductive particles ⁇ value/30% of conductive particles ⁇ value) is Preferably 1.
• connection resistance between the electrodes is 5 or more, more preferably 1.5 or more, preferably 5 or less, more preferably 4.5 or less.
• measure the load value (1 ⁇ !) and compressive displacement ( ⁇ .) From the measured value, calculate the above-mentioned compressive modulus (1 ⁇ % ⁇ value and 30% ⁇ value) by the following formula.
• the above-mentioned micro compression tester "Fisher Scope 1 to 1-100" manufactured by Fisher Co., Ltd. is used, etc.
• the above 10% ⁇ value and the above 30% ⁇ of the above conductive particles are used.
• the value is preferably calculated by arithmetically averaging the 10% ⁇ value and the 30% ⁇ value of the arbitrarily selected 50 conductive particles. ⁇ 02020/175691 8 ⁇ (: 171? 2020 /008458
• 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% ⁇ value of conductive particles/30% ⁇ value of conductive particles) can quantitatively and uniquely express the physical properties of the conductive particles at the time of initial compression.
• the particle diameter of the conductive particles is preferably 0.1 or more, and more preferably
• the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the contact area between the conductive particles and the electrode becomes sufficiently large when the electrodes are connected using the conductive particles. In addition, it is difficult for the conductive particles to aggregate when forming the conductive portion. In addition, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive parts are less likely to peel off from the surface of the base material particles.
• the particle size of the conductive particles is preferably an average particle size, and more preferably a number average particle size.
• the particle size of the above conductive particles can be calculated by, for example, observing 50 arbitrary conductive particles with an electron microscope or an optical microscope, calculating the average particle size of each conductive particle, and measuring the particle size distribution. It is calculated using the device. When observed with an electron microscope or an optical microscope, the particle size of each conductive particle is calculated as the particle size at the equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle size of any 50 conductive particles at the equivalent circle diameter is almost equal to the average particle size at the spherical equivalent diameter.
• the particle size of each conductive particle is calculated as the particle size in terms of a sphere equivalent diameter.
• the average particle size of the conductive particles is preferably calculated using a particle size distribution measuring device. ⁇ 02020/175691 9 boxes (: 171?2020/008458
• the coefficient of variation ( ⁇ 3 V value) of the particle diameter of the conductive particles is preferably 10% or less, more preferably 5% or less.
• the variation coefficient of the particle diameter of the conductive particles is equal to or less than the upper limit, it is possible to more effectively improve the conduction reliability and the insulation reliability between the electrodes.
• V value (%) ( ! ⁇ / 0 X 100 0
• the shape of the conductive particles is not particularly limited.
• the conductive particles may have a spherical shape, a shape other than a spherical shape, a flat shape or the like.
• FIG. 1 is a sectional view showing a conductive particle according to a first embodiment of the present invention.
• the conductive particles 1 shown in FIG. 1 have base particles 2 and conductive parts 3. Conductive part
• the conductive portion 3 is arranged on the surface of the base particle 2.
• the conductive portion 3 is in contact with the surface of the base particle 2.
• the conductive particle 1 is a coated particle in which the surface of the base material particle 2 is coated with the conductive portion 3.
• the conductive portion 3 is a single-layer conductive layer.
• the base material particles 2 contain a conductive metal inside the base material particles 2.
• the conductive portion may cover the entire surface of the base material particle, or the conductive portion may cover a part of the surface of the base material particle.
• the conductive portion may be a single-layer conductive layer or a multi-layer conductive layer composed of two or more layers.
• the conductive particles 1 do not have a core substance.
• the conductive particle 1 has no protrusion on the surface.
• the conductive particles 1 are spherical.
• the conductive part 3 has no protrusion on the outer surface.
• the conductive particles according to the present invention may not have protrusions on the conductive surface and may be spherical.
• the conductive particle 1 does not have an insulating material.
• the conductive particles 1 may have an insulating substance disposed on the outer surface of the conductive portion 3.
• FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
• the conductive particles 11 shown in FIG. 2 have a base particle 2, a conductive portion 12, a plurality of core substances 13 and a plurality of insulating substances 14.
• the conductive portion 12 is arranged on the surface of the base material particle 2 so as to be in contact with the base material particle 2.
• the conductive portion 12 is a single conductive layer. Conductive particles 1
• the base particle 2 contains a conductive metal inside the base particle 2.
• the conductive part may cover the entire surface of the base particle, or the conductive part may cover a part of the surface of the base particle.
• the conductive portion may be a single-layer conductive layer or a multi-layer conductive layer composed of two or more layers.
• the conductive particles 11 have a plurality of protrusions 11 13 on the conductive surface.
• the 2 has a plurality of protrusions 1 2 3 on its outer surface.
• a plurality of core substances 13 are arranged on the surface of the base particle 2.
• a plurality of core substances 13 are embedded in the conductive portion 12.
• the core substance 13 is arranged inside the protrusions 1 1 3 and 1 2 3.
• the conductive part 12 covers a plurality of core substances 13.
• the outer surface of the conductive part 12 is raised by the plurality of core substances 13 and the protrusions 1 1 2 3 are formed.
• the conductive particles 11 have the insulating substance 14 arranged on the outer surface of the conductive portion 12. At least a part of the outer surface of the conductive portion 12 is covered with the insulating substance 14.
• the insulating substance 14 is formed of a material having an insulating property 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 may not necessarily have an insulating substance.
• FIG. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.
• the conductive particles 21 shown in Fig. 3 include a base material particle 2, a conductive portion 22 and a plurality of cores. ⁇ 0 2020/1756 91 1 1 ⁇ (: 171? 2020 /008458
• the conductive portion 22 as a whole has a first conductive portion 22 28 on the base material particle 2 side and a second conductive portion 22 2 on the opposite side to the base material particle 2 side.
• the conductive particles 11 and the conductive particles 21 are different only in the conductive part. That is, in the conductive particle 11 the conductive part 12 having a one-layer structure is formed, while in the conductive particle 21 the first conductive part 2 28 and the second conductive part having a two-layer structure are formed.
• the conductive part 22 is formed.
• the first conductive portion 22 8 and the second conductive portion 22 2 are formed as separate conductive portions.
• the first conductive portion 22 8 is arranged on the surface of the base particle 2.
• the first conductive portion 22 8 is arranged between 2 and the second conductive portion 22.
• the first conductive portion 22 8 is in contact with the base particle 2.
• the second conductive part 22 is in contact with the first conductive part 22 8. Therefore, the first conductive portion 22 8 is arranged on the surface of the base particle 2, and the second conductive portion 22 2 is arranged on the surface of the first conductive portion 22 8. ..
• the conductive particles 21 have a plurality of protrusions 2 13 on the conductive surface.
• Conductive part 2 2 has a plurality of projections 2 2 3 on the outer surface.
• the first conducting portion 22 8 has a plurality of protrusions 22 8 3 on its outer surface.
• the second conductive portion 2 2 observed on the outer surface, having a plurality of projections 2 2 Serpent 3.
• the material of the base particles is not particularly limited.
• the material of the base particles may be an organic material or an inorganic material.
• Examples of the base material particles formed of only the organic material include resin particles.
• Examples of the base particles formed of only the above inorganic material include inorganic particles excluding metals.
• Examples of the base particles formed of both the organic material and the inorganic material include organic organic hybrid particles. From the viewpoint of further improving the compression characteristics of the base particles, the base particles are preferably resin particles or organic-inorganic hybrid particles, and more preferably resin particles.
• Examples of the organic material include polyethylene, polypropylene, polystyrene, ⁇ 02020/175691 12 ((171?2020/008458
• Polyolefin resins such as polyvinyl chloride, polyvinylidene chloride, polyisoptyrene, polybutadiene, etc.; acrylic resins such as polymethylmethacrylate and polymethylacrylate; polycarbonates, polyamides, phenolformaldehyde resins, melamine formaldehyde resins, benzoguanamine formaldehyde resins, 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, Polyamide imido, Examples thereof include polyether ether ketone, polyether sulfone, divinylbenzene polymer, and divinylbenzene copolymer.
• the divinyl benzene copolymer and the like examples include divinylbenzene-styrene copolymer and divinylbenzene-(meth)acrylic acid ester copolymer. Since the compression characteristics of the base particles can be easily controlled to a suitable range, the material of the base particles is a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group. It is preferable that they are united.
• the base particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group
• the polymerizable monomer having an ethylenically unsaturated group is a non-crosslinkable monomer. Examples thereof include a body and a crosslinkable monomer.
• non-crosslinkable monomer examples include vinyl compounds such as styrene, ⁇ styrene monomer such as methylstyrene and chlorostyrene; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc.
• Vinyl ether compounds vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, and other vinyl ester compounds; vinyl chloride, vinyl fluoride, and other halogen-containing monomers; (meth) acrylic compound, methyl (meth) acrylate , Ethyl (meth) acrylate, Propyl (meth) acrylate, Butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, Lauryl (meth) acrylate, Cetyl (meth) acrylate, Stearyl (meth) acrylate, cyclohexyl (Meth)acrylate, isobornyl (meth)acry ⁇ 02020/175691 13 Alkyl (meth)acryloyl compound such as: (171?2020/008458 rate; 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, glycidyl Ox
• crosslinkable monomer examples include vinyl compounds such as divinylbenzene and
• Vinyl monomers such as 1,4-divinyloxybutane and divinyl sulfone; (meth) as an acrylic compound, tetramethylolmethane tetra (meth) acrylate, polytetramethylene glycol diacrylate, tetramethylol methanetri (meth) Acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate ) Acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, polytetramethylene glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate
• Phenyltrimethoxysilane dimethyldimethoxysilane, dimethyldioxysilane, diisopropyldimethoxysilane, trimethoxysilylstyrene, 7-(meth)acryloxypropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, diphenyldimethoxysilane, etc.
• Silane alkoxide compounds vinyltrimethoxysilane, vinyltrietoxysilane, dimethoxymethylvinylsisilane, dimethoxetylvinylsilane, jetoxymethylvinylsilane, jetoxetylvinylsilane, ethylmethyldivinylsilane, methylvinyldimethoxysilane, ethylvinyldime Toxysilane, Methyl vinyl jetoxy silane, Ethyl vinyl jetoxy silane, _Styryltrimethoxy silane,
• the base particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group.
• the above-mentioned polymerization method is not particularly limited, and examples thereof include known methods such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, condensation polymerization), addition condensation, living polymerization, and living radical polymerization.
• Another polymerization method is suspension polymerization in the presence of a radical polymerization initiator.
• Examples of the above-mentioned inorganic materials include silica, alumina, barium titanate, zirconia, carbon black, silicate glass, borosilicate glass, lead glass, soda lime glass, and alumina silicate glass.
• the base particles may be organic-inorganic hybrid particles.
• the child may be a core-shell particle.
• the base particles are organic-inorganic hybrid particles
• examples of the inorganic material that is a material of the base particles include silica, alumina, barium titanate, zirconia, and carbon black. It is preferable that the inorganic substance is not a metal.
• the substrate particles formed of the above silica are not particularly limited, but after hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form a crosslinked polymer particle, if necessary, Base material particles obtained by performing firing are mentioned.
• Examples of the above-mentioned organic/inorganic hybrid particles include organic/inorganic hybrid particles formed by a crosslinked alkoxysilyl polymer and an acrylic resin.
• the organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell arranged on the surface of the core.
• the core is preferably an organic core.
• the shell is preferably an inorganic shell.
• the base material particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell arranged on the surface of the organic core.
• Examples of the material of the organic core include the organic materials described above.
• Examples of the material of the inorganic shell include the inorganic materials listed as the materials of the base particle.
• the material of the inorganic shell is preferably silica.
• the inorganic shell is preferably formed by forming a metal alkoxide into a shell-like material by a sol-gel method on the surface of the core, and then firing the shell-like material.
• the metal alkoxide is preferably silane alkoxide.
• the inorganic shell is preferably formed of silane alkoxide.
• the Mitsumi specific surface area of the base particles is preferably 8 2 /9 or more, more preferably 1 2 2 /9 or more, and preferably 1 2 0 2 /9 or less, more preferably More preferably 10 It is the following.
• the conductive metal can be contained more easily in the base particles. ⁇ 0 2020/175691 16 ⁇ (: 171? 2020 /008458
• the connection resistance between the electrodes can be reduced more effectively, and the occurrence of aggregation of the conductive particles is further enhanced. Can be suppressed.
• the insulation reliability between the electrodes can be more effectively enhanced.
• the above-mentioned Mitsumi ratio table area is not less than the above lower limit and not more than the above upper limit, the adhesion of the conductive part in the conductive particle can be more effectively enhanced, and the conductive part in the conductive particle is peeled off. Can be suppressed more effectively.
• the Mitsumi specific surface area of the base particles can be measured from the adsorption isotherm of nitrogen according to the Mitsumi method.
• Examples of a device for measuring the specific surface area of the Nitsubing Ding of the above-mentioned base particles include "1 ⁇ 10 8 4 2 0 0 6" manufactured by Kantachrome Instruments Co., Ltd.
• Total pore volume of [0076] the base particles is preferably 0.0 1 ⁇ 3/9 or more, more favorable Mashiku ⁇ . Or more, preferably 3_Rei 3/9 or less, and more favorable Mashiku is 1. 5_Rei_rei! 3/9 or less.
• the conductive metal can be more easily contained in the base particles.
• the connection resistance between the electrodes can be further effectively reduced, and the occurrence of aggregation of the conductive particles can be suppressed more effectively. can do.
• the insulation reliability between the electrodes can be more effectively enhanced.
• the total pore volume is not less than the above lower limit and not more than the above upper limit, it is possible to further effectively enhance the adhesion of the conductive portion in the conductive particle, and the peeling of the conductive portion in the conductive particle occurs. Can be suppressed more effectively.
• the total pore volume of the substrate particles snake “compliant 1 to 1 method, it is possible to measure the adsorption isotherm or these nitrogen.
• An example of a device for measuring the total pore volume of the base particles is "1 ⁇ 10 8 4 2 0 0 6" manufactured by Kantachrome Instruments Co., Ltd. ⁇ 0 2020/175691 17 ⁇ (: 171? 2020 /008458
• the average pore diameter of the base particles is preferably 10 n. Or less, more preferably
• the lower limit of the average pore size of the base particles is not particularly limited.
• the average pore size of the base particles is 1 It may be more.
• the conductive metal can be contained in the base material particles more easily.
• the connection resistance between the electrodes can be further effectively reduced, and the aggregation of the conductive particles can be more effectively generated. Can be suppressed.
• insulation reliability between electrodes can be more effectively enhanced.
• the adhesion of the conductive part in the conductive particle can be more effectively enhanced, and the conductive part in the conductive particle can be improved.
• the occurrence of peeling can be suppressed more effectively.
• the average pore diameter of the base particles snake “compliant 1 to 1 method, it is possible to measure the adsorption isotherm or these nitrogen.
• An example of a device for measuring the average pore diameter of the base particles is "1 ⁇ 10 8 4 2 0 0 6" manufactured by Kantachrome Instruments Co., Ltd. and the like.
• the porosity of the base particles is preferably 5% or more, more preferably 10% or more, preferably 90% or less, more preferably 70% or less.
• the conductive metal can be contained in the base material particles more easily.
• the porosity is equal to or higher than the lower limit and equal to or lower than the upper limit, the connection resistance between the electrodes can be reduced more effectively, and the occurrence of aggregation of the conductive particles can be suppressed more effectively. You can Further, when the porosity is equal to or higher than the lower limit and equal to or lower than the upper limit, the insulation reliability between the electrodes can be more effectively enhanced.
• the porosity is not less than the above lower limit and not more than the above upper limit, it is possible to more effectively enhance the adhesion of the conductive part in the conductive particle, and the peeling of the conductive part in the conductive particle occurs. Can be suppressed more effectively.
• the porosity of the above-mentioned base particles is determined by measuring the mercury content against the pressure applied by the mercury penetration method. ⁇ 0 2020/175691 18 ⁇ (: 171? 2020 /008458
• the base material particles satisfying the preferable ranges of the above-mentioned specific surface area and the porosity can be obtained, for example, by the method for producing base material particles including the following steps.
• the polymerizable monomer include monofunctional monomers and polyfunctional monomers.
• the organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is incompatible with a polar solvent such as water that is a polymerization medium.
• examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methylethylketone.
• the amount of the organic solvent added is 100 parts by weight of the polymerizable monomer component.
• the amount of the organic solvent added is in the above-mentioned preferred range, the Mitsumi specific surface area, the porosity, etc. can be controlled to a more suitable range, and the fine pores inside the particles can be controlled. It will be easier to obtain.
• the base material particles satisfying the preferable ranges such as the above-mentioned specific surface area of Mitsumi and the above-mentioned porosity have a relatively large number of voids inside the base material particles, so that the conductive part is present on the surface of the base material particles.
• the conductive part enters into the fine voids inside the base material particles, and the conductive metal can be easily contained inside the base material particles.
• the conductive particles may be compressed when the electrodes are connected in the vertical direction, so that the conductive metals inside the base material particles may come into contact with each other to form a conduction path.
• the surface of the conductive particles (conductive part ⁇ 0 2020/175691 19 ⁇ (: 171? 2020 /008458
• a conductive path is formed not only in the conductive particles but also in the conductive particles (conductive metal).
• the connection resistance between the electrodes in the vertical direction can be made sufficiently low even when the conductive portion is relatively thin.
• the thickness of the conductive part is relatively thin, it is possible to suppress the occurrence of aggregation of conductive particles, and to effectively increase the insulation reliability between the electrodes that are not connected and are laterally adjacent to each other.
• the conductive part when forming the conductive part on the surface of the base material particle, the conductive part enters into the fine voids inside the base material particle, so that the adhesion of the conductive part in the conductive particle is improved. It can be effectively increased, and peeling of the conductive portion of the conductive particles can be effectively suppressed.
• the particle diameter of the base particles is preferably 0.1 or more, and more preferably 1 or more.
• the particle size of the base particles is preferably 100 or less, more preferably 500 or less, even more preferably 300 or less, further preferably 50 or less, and still more preferably 10 or less. is there.
• the contact surface area between the conductive particles and the electrodes becomes large, so that the conduction reliability between the electrodes can be further enhanced, and the conductive particles can be It is possible to further lower the connection resistance between the electrodes connected through.
• the electroconductive portion is formed on the surface of the base material particle by electroless plating, it is possible to make it difficult for the aggregated electroconductive particles to be formed.
• the particle size of the base material particles is equal to or less than the above upper limit, the conductive particles are easily compressed, the connection resistance between the electrodes can be further reduced, and the distance between the electrodes can be further reduced. be able to.
• the particle diameter of the base particles is 1 or more and 3 or less.
• the particle diameter of the base particles is in the range of 1 or more and 3 or less, it becomes difficult to aggregate when forming the conductive portion on the surface of the base particles, and it becomes difficult to form the aggregated conductive particles.
• the particle diameter of the above-mentioned base particles indicates the number average particle diameter.
• the particle diameter of the above-mentioned base particles is calculated by observing 50 arbitrary base material particles with an electron microscope or an optical microscope and calculating the average value of the particle diameters of each base material particle. Sought using ⁇ 02020/175691 20 units (: 171?2020/008458
• the particle size of each base particle is determined as the particle size in terms of equivalent circle diameter.
• the average particle size of the circle equivalent diameter of any 50 base particles is almost equal to the average particle diameter of the spherical equivalent diameter.
• the particle size of each base particle is calculated as the particle size in terms of sphere equivalent diameter.
• the average particle size of the base material particles is preferably calculated using a particle size distribution measuring device. In the case of measuring the particle size of the above-mentioned base particles in the conductive particles, it can be measured as follows, for example.
• the content of the conductive particles was adjusted to 30% by weight. It is added to "Technobit 400 00 manufactured by the company” and dispersed to prepare an embedded resin for conductive particle inspection. Ion milling equipment (“Hitachi High Technologies Co., Ltd.” 1 ⁇ /1400) so that it passes through the center of the conductive particles dispersed in the inspection resin
• the conductive particles according to the present invention include base particles and conductive parts arranged on the surfaces of the base particles.
• the base material particle contains a conductive metal inside the base material particle.
• the conductive portion preferably contains a metal.
• the metal forming the conductive part is not particularly limited.
• the conductive metal is not particularly limited.
• the metal forming the conductive part and the conductive metal may be the same metal or different metals. It is preferable that the metal most contained in the conductive portion and the metal most contained in the conductive metal are the same.
• Examples of the metal forming the conductive part and the conductive metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium. ⁇ 02020/175691 21 ⁇ (: 171?2020/008458
• examples of the metal and the conductive metal forming the conductive portion include tin-doped indium oxide (poor) and solder. Only one type of metal or the conductive metal may be used, or two or more types may be used in combination.
• the conductive portion preferably contains nickel, gold, palladium, silver, or copper, and may contain nickel, gold, or palladium. More preferable.
• the content of nickel in 100% by weight of the conductive portion containing nickel is preferably
• the amount is 10% by weight or more, more preferably 50% by weight or more, even more preferably 60% by weight or more, further preferably 70% by weight or more, and particularly preferably 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, or 97.5% by weight or more,
• hydroxyl groups often exist on the surface of the conductive portion due to oxidation. Generally, hydroxyl groups are present on the surface of the conductive portion formed of nickel due to oxidation. An insulating substance can be arranged on the surface of the conductive part having such a hydroxyl group (the surface of the conductive particles) through a chemical bond.
• the conductive section may be formed of one layer.
• the conductive part may be formed of a plurality of layers. That is, the conductive part may have a laminated structure of two or more layers.
• the metal forming the outermost layer is preferably gold, nickel, palladium, copper or an alloy containing tin and silver, and is preferably gold. More preferable.
• the connection resistance between the electrodes becomes even lower.
• the metal forming the outermost layer is gold, the corrosion resistance is further enhanced.
• the method for forming the conductive portion on the surface of the base particle is not particularly limited. the above ⁇ 0 2020/175691 22 ⁇ (: 171? 2020 /008458
• 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 metal powder or metal examples thereof include a method of coating the surface of the base particles with a paste containing a powder and a binder.
• the method for forming the conductive portion is preferably electroless plating, electroplating, or physical collision.
• the physical vapor deposition method include vacuum vapor deposition, ion plating, and ion sputtering.
• a sheet composer manufactured by Tokuju Kosakusho Co., Ltd.
• the method of incorporating a conductive metal into the base particles is not particularly limited.
• a method of electroless plating using base material particles (base material body) that are porous particles, and a base material particle that is porous particles examples include electroplating using a base particle main body. Since the base particles (main body of the base particles), which are porous particles, have a relatively large number of voids inside the base particles, the base particles cannot be used when the conductive part is formed on the surface of the base particles.
• the conductive part forming material (plating solution, etc.) can enter into the minute voids inside. By depositing the conductive metal from the conductive part forming material that has entered the inside of the base material particle, the conductive metal can be easily contained inside the base material particle.
• the base particles that are porous particles include base particles that satisfy the preferable ranges of the above-mentioned specific surface area of Mitsumi and the above-mentioned porosity.
• the thickness of the conductive portion is preferably 0.005 or more, more preferably 0.01 or more, preferably 10 or less, more preferably 1 or less, still more preferably 0.3 or less. Is.
• the thickness of the conductive portion is the thickness of the entire conductive portion when the conductive portion is a multilayer. When the thickness of the conductive portion is not less than the above lower limit and not more than the above upper limit, sufficient conductivity is obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently deformed when connecting between electrodes. Can be done.
• the thickness of the conductive portion of the outermost layer ⁇ 0 2020/175691 23 ⁇ (: 171? 2020 /008458
• the thickness of the conductive portion of the outermost layer is not less than the above lower limit and not more than the above upper limit, the coating of the conductive portion of the outermost layer is uniform, the corrosion resistance is sufficiently high, and the connection resistance between the electrodes is increased. Can be low enough.
• the metal forming the outermost layer is gold, the thinner the outermost layer is, the lower the cost can be.
• the thickness of the conductive part can be measured by observing the cross section of the conductive particle using, for example, a transmission electron microscope (Chome 1 ⁇ /1).
• Chome 1 ⁇ /1 a transmission electron microscope
• the thickness of the conductive portion is preferably obtained by calculating the average value of the thickness of the conductive portion of each conductive particle for 10 arbitrary conductive particles.
• the content of the above conductive metal is preferably 5 volume% or more, more preferably 10 volume% or more, and preferably 70 volume% or less, It is more preferably 50% by volume or less.
• the content of the conductive metal is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be reduced more effectively, and the occurrence of aggregation of conductive particles is further enhanced. Can be suppressed.
• the insulation reliability between the electrodes can be more effectively enhanced.
• the content of the conductive metal is not less than the above lower limit and not more than the above upper limit, it is possible to further effectively improve the adhesion of the conductive portion in the conductive particle, and the conductive portion in the conductive particle The occurrence of peeling can be suppressed even more effectively.
• the content of the conductive metal in 100% by volume of the conductive particles is preferably 5% by volume or more, more preferably 10% by volume. % Or more, preferably 50% by volume or less, more preferably 40% by volume or less.
• the content of the above-mentioned conductive metal in 100% by volume of the conductive particles is preferably 10% by volume or more, more preferably 20% by volume or more, It is preferably 50% by volume or less, more preferably 40% by volume or less.
• the content of the conductive metal in 100% by volume of the conductive particles is particularly preferably 10% by volume or more and 40% by volume or less.
• the content of the conductive metal means the total content of the metal forming the conductive portion and the conductive metal contained inside the base particles. It is preferable to judge whether or not the conductive metal is contained inside the base material particles by the first ratio and the second ratio described later.
• the content of the conductive metal can be calculated as follows.
• Conductive metal content 0 X 1 ⁇ / 0 01 6 1 3 I X I 0 0
• the metallization rate of the conductive particles can be calculated by using optical emission analysis or the like, and the specific gravity of the conductive particles can be measured by using a true specific gravity meter or the like. Further, the specific gravity of the conductive metal can be calculated using a value specific to the metal.
• the metallization rate of the conductive particles is a ratio of the content (9) of the conductive metal contained in the conductive particles 19, that is, the metal content of the conductive metal contained in the conductive particles 19. Content (9) / Refers to conductive particles 19.
• the content of the conductive metal contained in the base material particles is preferably 0.1% by volume or more, more preferably 1% by volume or more, and preferably Is 30% by volume or less, more preferably 20% by volume or less.
• the connection resistance between the electrodes can be further effectively reduced, and the coagulation of the conductive particles can be reduced.
• the content of the conductive metal is not less than the lower limit and not more than the upper limit, the adhesion of the conductive part in the conductive particle can be more effectively enhanced, and the conductive part in the conductive particle is peeled off. Can be suppressed more effectively.
• the conductive particles are
• the content of the above-mentioned conductive metal contained in the above-mentioned conductive portion is preferably 0.1% by volume or more, more preferably 1% by volume or more, and preferably 30% by volume or less. , And more preferably 20% by volume or less.
• the content of the conductive metal contained in the conductive part in the conductive particles of 100% by volume is preferably 0.1 volume. % Or more, more preferably 1% by volume or more, preferably 30% by volume or less, more preferably 20% by volume or less.
• 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 protrusions are plural.
• 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 eliminated by the protrusions by disposing the conductive particles between the electrodes and pressing them. For this reason, the electrodes and the conductive portion are more surely brought into contact with each other, and the connection resistance between the electrodes is further reduced.
• the conductive particles include an insulating material, or when the conductive particles are dispersed in a binder resin and used as a conductive material, the protrusions of the conductive particles cause a gap between the conductive particles and the electrode.
• the insulating material or binder resin can be eliminated even more effectively. Therefore, the connection resistance between the electrodes can be further reduced.
• the core substance is formed of a metal and the core substance exists in the conductive part, the core substance is regarded as a part of the conductive part.
• a core substance was attached to the surface of the base material particles. ⁇ 0 2020/1756 91 26 ⁇ (: 171? 2020 /008458
• a method of adding a core substance in the middle of forming the conductive portion on the surface of the base material particles may be mentioned.
• the conductive material is formed on the base particles by electroless plating without using the above core substance, and then plating is deposited in the form of protrusions on the surface of the conductive portion. You may use the method of forming a conductive part by.
• the core substance is added to the dispersion liquid of the base material particle, and the core substance is accumulated on the surface of the base material particle by Van der Waalsca. And a method of adhering the core substance to the surface of the base material particles by a mechanical action such as rotation of the container.
• the method of attaching the core substance to the surface of the base material particles is a method of accumulating and attaching the core substance on the surface of the base material particles in the dispersion liquid. Is preferred.
• Examples of the substance forming 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.
• Examples of the non-conductive substance include silica, alumina and zirconia. From the viewpoint of more effectively eliminating the oxide film, the core substance is preferably hard. From the viewpoint of effectively lowering the connection resistance between the electrodes, the core substance is preferably a metal.
• the above metal is not particularly limited.
• the metal include gold, silver, copper, platinum, lead, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead alloys. , Tin-copper alloy, tin-silver alloy, tin-lead-silver alloy, and tungsten carbide alloys composed of two or more metals. Between electrodes ⁇ 02020/175691 27 ⁇ (: 171?2020/008458
• the metal is preferably nickel, copper, silver or gold.
• the metal may be the same as or different from the metal forming the conductive part (conductive layer).
• the shape of the core substance is not particularly limited.
• the shape of the core substance is preferably massive.
• Examples of the core substance include particulate lumps, agglomerates of a plurality of fine particles, and amorphous lumps.
• the particle diameter of the core substance is preferably ⁇ 0.011 or more, more preferably ⁇ 0.0501 or more, preferably ⁇ 0.9 ⁇ ! or less, more preferably ⁇ 0.2 ⁇ ! is there.
• the particle size of the core substance is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be lowered more effectively.
• the particle diameter of the core substance is preferably an average particle diameter, and more preferably a number average particle diameter.
• the particle size of the core substance can be obtained by observing 50 arbitrary core substances with an electron microscope or an optical microscope and calculating the average value of the particle size of each core substance, or by using a particle size distribution measuring device. .. When observed with an electron microscope or an optical microscope, the particle size of each core substance can be calculated as the particle size at the equivalent circle diameter. When observed with an electron microscope or an optical microscope, the average particle diameter of any 50 core substances at the circle equivalent diameter is almost equal to the average particle diameter at the sphere equivalent diameter. With a particle size distribution analyzer, the particle size of each core substance is calculated as the particle size in terms of sphere equivalent diameter.
• the average particle size of the core substance 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 protrusions is not particularly limited.
• the upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles and the like. When the number of protrusions is equal to or more than the lower limit, the connection resistance between the electrodes can be reduced more effectively.
• 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 the average of the number of protrusions in each conductive particle when 50 conductive particles are observed with an electron microscope or an optical microscope. ⁇ 0 2020/175691 28 (:171? 2020/008458) It is preferable to obtain by calculating the value.
• the height of the protrusions is preferably ⁇ 0.01 or more, more preferably ⁇ .
• the connection resistance between the electrodes can be reduced more effectively.
• the height of the protrusions can be calculated by observing the protrusions in arbitrary conductive particles with an electron microscope or an optical microscope.
• the height of the projections is preferably calculated by taking the average value of the heights of all the projections per conductive particle as the height of the projection of one conductive particle.
• the height of the projections is preferably obtained by calculating an average value of the heights of the projections of the conductive particles for 50 arbitrary conductive particles.
• the conductive particles preferably include an insulating substance arranged on the outer surface of the conductive portion.
• an insulating substance exists between the plurality of electrodes, so that it is possible to prevent a short circuit between laterally adjacent electrodes instead of between the upper and lower electrodes.
• the conductive particles are pressed by the two electrodes, so that the insulating substance between the conductive portion of the conductive particles and the electrodes can be easily eliminated.
• the insulating substance between the conductive portion of the conductive particles and the electrode can be more easily eliminated.
• the insulating substance is preferably insulating particles because the insulating substance can be more easily removed during pressure bonding between the electrodes.
• Examples of the material of the insulating substance include the above-mentioned organic materials, the above-mentioned inorganic materials, and the above-mentioned inorganic materials as the material of the base particles.
• the material of the insulating substance is preferably the organic material described above.
• Examples of other materials of the above insulating material include polyolefin compounds, (meth)acrylate polymers, (meth)acrylate copolymers, block polymers, and heat. ⁇ 0 2020/175691 29 ⁇ (: 171? 2020 /008458
• Examples thereof include a plastic resin, a crosslinked product of a thermoplastic resin, a thermosetting resin, and a water-soluble resin.
• a plastic resin a crosslinked product of a thermoplastic resin, a thermosetting resin, and a water-soluble resin.
• the material of the insulating material only one kind may be used, or two or more kinds may be used in combination.
• Examples of the above-mentioned polyolefin compounds include polyethylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, and the like.
• Examples of the above-mentioned (meth)acrylate polymer include polymethyl (meth)acrylate, polydodecyl (meth)acrylate, and polystearyl (meth)acrylate.
• Examples of the block polymer include polystyrene, a styrene-acrylic acid ester copolymer, a 3 type styrene-butadiene block copolymer, and 3 Examples thereof include type styrene-butadiene block copolymers, and hydrogenated products thereof.
• thermoplastic resin examples include vinyl polymers and vinyl copolymers.
• thermosetting resin examples include epoxy resin, phenol resin and melamine resin.
• crosslinked product of the thermoplastic resin examples include introduction of polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated pentaerythritol methacrylate and the like.
• water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylic amide, polyvinyl pyrrolidone, polyethylene oxide and methyl cellulose.
• a chain transfer agent may be used to adjust the degree of polymerization. Examples of chain transfer agents include thiol and carbon tetrachloride.
• Examples of the method of disposing the insulating substance on the surface of the conductive portion include a chemical method and a physical or mechanical method.
• Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
• Examples of the above-mentioned physical or mechanical method include spray drying, high pridization, electrostatic adhesion method, spraying method, diving and vacuum deposition.
• the method of arranging the insulating material on the surface of the conductive portion is a physical method. Preferably. ⁇ 0 2020/175691 30 ⁇ (: 171? 2020 /008458
• the outer surface of the conductive part and the outer surface of the insulating substance may be coated with a compound having a reactive functional group.
• the outer surface of the conductive part 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 through a polymer electrolyte such as polyethyleneimine.
• the particle size of the insulating particles can be appropriately selected depending on the particle size of the conductive particles, the use of the conductive particles, and the like.
• the particle size of the insulating particles is preferably 10 or more, more preferably 100 or more, and even more preferably 300 or more. Or more, particularly preferably 5 00 n or more, preferably 4 00 0 n or less, more preferably 2 00 0 n or less, and further preferably 1 5 0 0 The following are particularly preferred It is below.
• the particle diameter of the insulating particles is not less than the above lower limit, it becomes difficult for the conductive portions of the plurality of conductive particles to contact each other when the conductive particles are dispersed in the binder resin.
• the particle size of the insulating particles is less than or equal to the above upper limit, it is not necessary to increase the pressure to eliminate the insulating particles between the electrodes and the conductive particles when connecting the electrodes, There is no need to heat to a high temperature.
• the particle size of the insulating particles is preferably an average particle size, and more preferably a number average particle size.
• the particle diameter of the insulating particles can be calculated by observing 50 arbitrary insulating particles with an electron microscope or an optical microscope and calculating the average value of the particle diameter of each insulating particle, or by using a particle size distribution measuring device. Desired. In the observation with an electron microscope or an optical microscope, the particle size of each insulating particle is calculated as the particle size in equivalent circle diameter. In observation with an electron microscope or an optical microscope, the average particle diameter of any 50 insulating particles in terms of equivalent circle diameter is approximately equal to the average particle diameter in equivalent sphere diameter.
• the particle size of each insulating particle is calculated as the particle size in terms of a sphere equivalent diameter.
• the average particle size of the insulating particles is preferably calculated using a particle size distribution measuring device. Conductivity above ⁇ 02020/175691 31 ⁇ (: 171?2020/008458
• the particle diameter of the above-mentioned insulating particles for example, it can be measured as follows.
• 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. , Preferably 200 or less, more preferably 100 or less.
• the above ratio is not less than the above lower limit and not more than the above upper limit, insulation reliability and continuity reliability are obtained when electrodes are electrically connected. Can be more effectively increased.
• the conductive material according to the present invention contains the conductive particles described above and a binder resin.
• the conductive particles are preferably dispersed in a binder resin for use, and are preferably dispersed in a binder resin for use as a conductive material.
• the conductive material is preferably an anisotropic conductive material.
• the conductive material is preferably used for electrical connection between electrodes.
• the conductive material is preferably a conductive material for circuit connection. Since the above-mentioned conductive particles are used in the above-mentioned conductive material, the connection resistance between the electrodes can be reduced more effectively, and the occurrence of aggregation of conductive particles can be suppressed more effectively. can do. Since the above-mentioned conductive particles are used in the above-mentioned conductive material, the insulation reliability between the electrodes can be more effectively enhanced. ⁇ 0 2020/175691 32 ⁇ (: 171? 2020 /008458
• the conductive material preferably contains a plurality of the conductive particles. From the outer surface of the base material particle toward the center, a region of a distance of 1/2 of the particle diameter of the base material particle.
• the ratio of the number of conductive particles in which the conductive metal is present in the region 1 of the base particles in the total number of the conductive particles of 100% (hereinafter referred to as the first ratio) Is preferably 50% or more, more preferably 60% or more.
• the upper limit of the first ratio is not particularly limited.
• the first percentage may be 100% or less.
• the insulation reliability between the electrodes can be more effectively enhanced.
• the first ratio is equal to or higher than the lower limit and equal to or lower than the upper limit, it is possible to more effectively enhance the adhesiveness of the conductive portion in the conductive particle, and peeling of the conductive portion in the conductive particle. It is possible to more effectively suppress the occurrence of
• the first ratio exceeds 0%, it can be judged that the conductive metal is contained inside the base material particles.
• the above-mentioned region 1 is a region outside the broken line !_ 1 of the base particle 2 in FIG. Above area Is the outer surface portion of the base particles.
• the region 1 is a region different from the central part of the base particle.
• the ratio of the number of the conductive particles in which the conductive metal is present in the region 2 of the base material particles in 100% of the total number of the conductive particles is preferably 5% or more, more preferably 10% or more.
• the upper limit of the second ratio is not particularly limited.
• the second ratio may be 100% or less.
• the connection resistance between the electrodes can be reduced more effectively, and the occurrence of aggregation of conductive particles can be suppressed more effectively. ..
• the second ratio is not less than the lower limit, the insulation reliability between the electrodes can be more effectively enhanced.
• the second ratio above is ⁇ 2020/175691 33 ⁇ (: 171? 2020 /008458
• the region 2 is a region inside the broken line !_ 1 of the base particle 2 in FIG.
• the region 2 is the central portion of the base material particles.
• the region 2 is a region different from the outer surface portion of the base particle.
• the first ratio and the second ratio can be calculated as follows.
• the conductive particles are collected from the conductive material by filtration or the like.
• An embedded resin for conductive particle inspection was prepared by adding and dispersing the recovered conductive particles to X-recon ⁇ “Technobit 400 0” manufactured by the company so that the content of the conductive particles was 30% by weight. To do. Using an ion milling device (“Hitachi High-Technologies Inc. “ ⁇ 1 ⁇ /140 0 0”) so that it passes through the center of the conductive particles dispersed in the resin for inspection, one conductive particle is used. Cut out the cross section.
• the 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.
• binder resin examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers.
• binder resin examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers.
• Only one type of resin may be used, or two or more types may be used in combination.
• Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
• examples of the thermoplastic resin include a polyolefin resin, an ethylene-vinyl acetate copolymer, and a polyamide resin.
• examples of the curable resin include epoxy resin, urethane resin, polyimide resin and unsaturated polyester resin.
• the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin or a moisture curable resin.
• the curable resin may be used in combination with a curing agent.
• thermoplastic block copolymer examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated product of styrene-butadiene-styrene block copolymer, and Examples thereof include hydrogenated products of styrene-isoprene-styrene block copolymers.
• the elastomer examples include styrene-butadiene copolymer rubber, and acrylonitrile-styrene block copolymer rubber.
• the conductive material may be, for example, a filler, a filler, a softening agent, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, in addition to the conductive particles and the binder resin. It may contain various additives such as agents, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and flame retardants.
• a conventionally known dispersion method can be used and is not particularly limited.
• the method for dispersing the conductive particles in the binder resin include the following methods. A method in which the above conductive particles are added to the binder resin and then kneaded and dispersed by a planetary mixer or the like. After the conductive particles are dispersed evenly _ using Homoji in water or an organic solvent Naiza etc., added to the binder resin, planetary - mixers - How kneaded to disperse the like. A method in which the above binder resin is diluted with water, an organic solvent or the like, and then the above conductive particles are added and kneaded and dispersed by a planetary mixer or the like.
• the viscosity (7 to 25) of the above conductive material at 25 ° ⁇ is preferably 3 0 3 3 or more. ⁇ 0 2020/175691 35 ⁇ (: 171? 2020 /008458
• the upper limit is more preferably 5033 or more, preferably 4003 or less, and more preferably 3003 or less.
• the viscosity of the above conductive material at 25° is not less than the above lower limit and not more than the above upper limit, the insulation reliability between the electrodes can be more effectively enhanced, and the conduction reliability between the electrodes can be further improved. It can be increased more effectively.
• the viscosity (7] 25) can be appropriately adjusted depending on the kind and the amount of the components to be mixed.
• the above-mentioned viscosity (7 to 25) can be calculated, for example, from a Mitsumi-type viscometer ("Tokimi 2 2
• the conductive material according to the present invention can be used as a conductive paste, a conductive film, or the like.
• a film containing no conductive particles may be laminated on a conductive film containing 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 is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 50% by weight or more, particularly preferably It is 70% by weight or more, preferably 99.99% by weight or less, and 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. Can be increased.
• the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and preferably 80% by weight.
• the amount is below, more preferably 60% by weight or less, further preferably 40% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.
• the content of the conductive particles is at least the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be lowered even more effectively.
• the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, it is possible to further enhance the communication reliability between electrodes and the insulation reliability.
• connection structure according to the present invention 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, and the first connection target member. And a connection portion connecting the second connection target member.
• the material of the connection portion is the above-mentioned conductive particles or a conductive material containing the above-mentioned conductive particles and a binder resin.
• the first electrode and the second electrode are electrically connected by the conductive particles.
• connection structure is formed by placing the conductive particles or the conductive material between the first connection target member and the second connection target member, and conducting thermocompression bonding to achieve conductivity. It can be obtained through the step of connecting.
• the conductive particles have the insulating substance, it is preferable that the insulating substance be desorbed from the conductive particles during the thermocompression bonding.
• connection 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. 5 is a schematic front sectional view of a connection structure using conductive particles according to the first embodiment of the present invention.
• connection structure 5 1 shown in Fig. 5 includes a first connection target member 52, a second connection target member 5 3 and first and second connection target members 5 2, 5 3. And a connecting portion 5 4 connected thereto.
• the connection portion 54 is formed by curing a conductive material containing the conductive particles 1.
• the conductive particles 1 are schematically illustrated for convenience of illustration. Instead of the conductive particles 1, other conductive particles such as the conductive particles 11 and 21 may be used.
• the first connection object member 5 2 on the surface (upper surface) to have a plurality of first electrode 5 2 3.
• the second connection target member 5 3 has a plurality of second electrodes 5 33 on the front surface (lower surface).
• the first electrode 5 2 3 and the second electrode 5 3 3 have one or more conductive ⁇ 0 2020/1756 91 37 ⁇ (: 171? 2020 /008458
• the first and second connection target members 5 2 and 5 3 are electrically connected by the conductive particles 1.
• the method for producing the connection structure is not particularly limited.
• the conductive material is arranged between the first connection target member and the second connection target member to obtain a laminated body, and then the laminated body is heated and heated.
• a method of applying pressure may be used.
• the pressure for the thermocompression bonding is preferably 4 0 1 ⁇ /1 3 or more, more preferably 6 or more, preferably 90 0 IV! 3 or less, more preferably 70 0 IV! 3 or less.
• the temperature of the heating of the thermo-compression bonding is preferably 8 0 ° ⁇ or more, more favorable Mashiku is 1 0 0 ° ⁇ As, preferably 1 4 0 ° ⁇ less, more preferably 1 2 0 ° ⁇ less is there.
• the pressure and temperature of the thermocompression bonding are not less than the lower limit and not more than the upper limit, the conduction reliability and insulation reliability between the electrodes can be further enhanced.
• the conductive particles have the insulating particles, the insulating particles can be easily detached from the surface of the conductive particles during conductive connection.
• the conductive particles have the insulating particles, between the conductive particles and the first electrode and the second electrode when the laminate is heated and pressed. It is possible to eliminate the above-mentioned insulating particles existing in the. For example, during the heating and pressurization, the insulating particles present between the conductive particles and the first electrode and the second electrode are removed from the surface of the conductive particles. Easily detach. In addition, during the heating and pressurization, a part of the insulating particles may be detached from the surface of the conductive particles, and the surface of the conductive portion may be partially exposed. The exposed portion of the surface of the conductive portion comes into contact with the first electrode and the second electrode to electrically connect the first electrode and the second electrode through the conductive particles. can do.
• connection structure since the above-mentioned conductive particles are used, the conductive particles are compressed during the heating and pressurization, so that the conductive particles are A conductive path is not only formed on the surface (conductive portion) of the conductive particles, but also a conductive path is formed by the conductive metals inside the conductive particles contacting each other. As a result, even if the conductive part is relatively thin, the connection resistance between the electrodes in the vertical direction ⁇ 0 2020/175691 38 ⁇ (: 171? 2020 /008458
• the thickness of the conductive portion is relatively thin, it is possible to suppress the occurrence of aggregation of conductive particles, and to effectively improve the insulation reliability between the electrodes that are laterally adjacent and must not be connected. You can
• the first connection target member and the second connection target member are not particularly limited.
• first connection target member and the second connection target member include a semiconductor chip, a semiconductor package, and a! _ _ 0 chips,! _ _ 0 Electronic components such as packages, capacitors and diodes, and electronic components such as resin films, printed circuit boards, flexible printed circuit boards, flexible flat cables, rigid flexible boards, circuit boards such as glass epoxy boards and glass boards Etc. It is preferable that the first connection target member and the second connection target member are 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, 3 II 3 electrodes, and tungsten electrodes. Is mentioned.
• 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 above electrode is an aluminum electrode, it may be an electrode formed of only aluminum or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer.
• the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element.
• the above-mentioned trivalent metal element include Sn, Hachijo, and ⁇ 3.
• Polystyrene particles having an average particle size of 0.5 were prepared as seed particles.
• a mixture 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 aqueous solution of polyvinyl alcohol. After the above mixed solution was dispersed by ultrasonic waves, it was placed in a separable flask and stirred uniformly.
• An emulsion was prepared by adding 50 parts by weight and 110 parts by weight of ion-exchanged water.
• the obtained base particles are washed and dried, and then 10 parts by weight of the base particles are dispersed in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser. After that, the base material particles were taken out by filtering the solution. Next, the base particles were added to 100 parts by weight of a 1 wt% solution of dimethylamine borane to activate the surface of the base particles. After thoroughly washing the surface-activated base material particles with water, the dispersion liquid was obtained by adding to 500 parts by weight of distilled water and dispersing. Next, nickel particle slurry (average particle size 100 n) 19 was added to the above dispersion over 3 minutes to obtain a suspension containing base material particles to which the core substance was attached.
• connection structure [0165]
• a transparent glass substrate with an electrode pattern (1st electrode, metal pickers hardness of the electrode surface of 100 0 ! ⁇ ) formed on the upper surface was prepared. Also, ! A semiconductor chip was prepared on the lower surface of which an eight-electrode electrode pattern (the second electrode, the Vickers hardness of the metal of the electrode surface was 5 01 to 1 V) whose _ / 3 was 10/10 was formed. The obtained anisotropic conductive paste was applied on the transparent glass substrate so as to have a thickness of 30 to form an anisotropic conductive paste layer. Next, the semiconductor chip was laminated on the anisotropic conductive paste layer so that the electrodes face each other.
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except that the amount of the solvent used was 10 parts by weight during the production of the base particles. ⁇ 0 2020/175691 41 ⁇ (: 171? 2020/008458
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except that the amount of the solvent used was 70 parts by weight when the base particles were prepared.
• a conductive material and a connection structure were obtained in the same manner as in Example 1 except that the amount of the base particles blended was 5 parts by weight when the conductive particles were produced.
• a conductive material and a connection structure were obtained in the same manner as in Example 1 except that the amount of the base particles mixed was 2.5 parts by weight in the production of the conductive particles.
• the conductive particles obtained in Example 1 were prepared. Further, a gold plating solution was prepared by adding potassium gold cyanide 59 to a solution 5009 containing 109/!_ sodium ethylenediamine tetraacetate and 109/1_ sodium citrate. 100 parts by weight of the conductive particles obtained in Example 1, was added to 500 parts by weight of the gold plating solution,
• a suspension was obtained by adding 10 parts by weight of the conductive particles obtained in Example 1 to 200 parts by weight of distilled water and dispersing them. Also, a palladium plating solution containing 109/1_ ethylene diamine, 3.09/1-palladium sulfate, 5.09/1-sodium formate was prepared. After heating the suspension to 700 ° C., 700 parts by weight of the palladium plating solution was added dropwise over 10 minutes to carry out electroless palladium plating. Then, the suspension is filtered to remove the particles, washed with water, and dried to form a nickel-boron-palladium conductive layer on the surface of the base particles, and conductive particles having a conductive portion on the surface. Got Got ⁇ 02020/175691 42 ((171?2020/008458
• a conductive material and a connection structure were obtained in the same manner as in Example 1 except that the conductive particles were used.
• a suspension was obtained by adding 10 parts by weight of the conductive particles obtained in Example 1 to 200 parts by weight of distilled water and dispersing them.
• a mixed solution containing 109/!-Ca silver cyanide, 809/1_ potassium cyanide, 59/1_ ethylenediaminetetraacetic acid, and 209/!_ sodium hydroxide was added to A silver plating solution adjusted to 1 to 16 with sodium was prepared. After the above suspension was heated to 500°, electroless silver plating was performed by dropping 700 parts by weight of the above silver plating solution over 30 minutes.
• the suspension is filtered to take out the particles, washed with water, and dried to form a nickel-boron-silver conductive layer on the surface of the base material particles, and to form conductive particles having conductive parts on the surface. Obtained.
• a conductive material and a connection structure were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.
• the base particles having a particle diameter of 1.001 were obtained by changing the seed particle diameter during the preparation of the base particles.
• Conductive particles, a conductive material and a connecting material were obtained in the same manner as in Example 1 except that the obtained base material particles were used and the amount of the obtained base material particles was changed to 5 parts by weight. The structure was obtained.
• the base particles having a particle diameter of 2.501 were obtained by changing the seed particle diameter during the preparation of the base particles.
• Conductive particles and conductive material were prepared in the same manner as in Example 1 except that the obtained base material particles were used and the amount of the obtained base material particles was changed to 12.5 parts by weight. And a connection structure was obtained.
• base particles having a particle size of 3.001 were obtained.
• Conductive particles, a conductive material and a connecting material were obtained in the same manner as in Example 1 except that the obtained base material particles were used and the amount of the obtained base material particles was changed to 15 parts by weight. The structure was obtained. ⁇ 02020/175691 43 ⁇ (: 171?2020/008458
• base particles having a particle size of 5.001 were obtained.
• Conductive particles, a conductive material and a connecting material were obtained in the same manner as in Example 1 except that the obtained base material particles were used and the amount of the obtained base material particles was changed to 25 parts by weight. The structure was obtained.
• base particles having a particle size of 10.0 were obtained.
• Conductive particles, conductive material and connection structure were obtained in the same manner as in Example 1 except that the obtained base material particles were used, and the amount of the obtained base material particles was changed to 50 parts by weight.
• the solid content of the following monomer composition Distilled water was added so that the concentration became 10% by weight, the mixture was stirred at 200 ", and polymerization was carried out at 60 °C for 24 hours under a nitrogen atmosphere.
• the above monomer composition was methyl methacrylate ⁇ ⁇ , glycidyl methacrylate 4 5 01 01 ⁇ ⁇ , parastyryl ethylphosphine 2 0 01 01 ⁇ I, Ethylene glycol dimethacrylate 1 ⁇ , polyvinylpyrrolidone ⁇ .
• the insulating particles obtained in (1) above were dispersed in distilled water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
• the conductive particles 109 obtained in Example 1 were dispersed in distilled water 500!, 10% by weight aqueous dispersion of insulating particles 19 was added, and the mixture was stirred at room temperature for 8 hours. After filtering with 3 mesh filter ⁇ 02020/175691 44 ⁇ (: 171?2020/008458
• Example 2 A conductive material and a connection structure were obtained in the same manner as in Example 1 except that the obtained conductive particles with insulating particles were used.
• nickel particle slurry (average particle size 100 Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except that the above was not used.
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except that the amount of the catalyst liquid was changed to 200 parts by weight when producing the conductive particles.
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except that the amount of the catalyst liquid was changed to 500 parts by weight in the production of the conductive particles.
• Example 15 The conductive particles obtained in Example 15 were prepared. Using the conductive particles obtained in Example 15 and in the same manner as in Example 14, conductive particles with insulating particles were obtained. A conductive material and a connection structure were obtained in the same manner as in Example 1 except that the obtained conductive particles with insulating particles were used.
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Example 1 except that the solvent was changed from toluene to ethanol during the production of the base particles.
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Comparative Example 1 except that the amount of the base particles blended was 5 parts by weight in the production of the conductive particles.
• a conductive material and a connection structure were obtained in the same manner as in Example 1 except that the obtained conductive particles with insulating particles were used.
• Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in Comparative Example 1 except that the amount of the base particles blended was 20 parts by weight during the production of the conductive particles.
• the particle size of the particles was calculated. Specifically, it was determined by measuring the particle size of about 100,000 base particles or conductive particles and calculating the average value.
• Kantachrome Instruments “1 ⁇ 108 8200 was used to measure the adsorption isotherm of nitrogen. From the measurement results, snake "in conformity with 1-1 method to calculate the total pore volume of the substrate particles.
• Kantachrome Instruments “1 ⁇ 108 8200 was used to measure the adsorption isotherm of nitrogen. From the measurement results, snake "in conformity with 1-1 method to calculate the total pore volume of the substrate particles.
• the cumulative penetration amount of mercury was measured with respect to the pressure applied by the mercury porosimetry, using a silver-silver porosimeter “Poremaster 60” manufactured by Kantachrome Instruments. From the measurement results, the porosity of the base particles was calculated. ⁇ 02020/175691 46 ⁇ (: 171? 2020 /008458
• the content of the conductive metal in 100% by volume of the conductive particles was calculated as follows.
• the content of the conductive metal contained in the conductive portion in 100% by volume of the conductive particles was calculated as follows.
• the metallization rate of the conductive part Is a ratio (9) of the content of the conductive metal in the conductive part contained in the conductive particles 19, that is, the conductive metal contained in the conductive part contained in the conductive particles 19.
• Content (9) / refers to conductive particles 19
• the metallization rate IV! 1 of the conductive portion was calculated using the following two relational expressions.
• the content of the conductive metal contained in the base material particles in 100% by volume of the conductive particles was calculated as follows.
• the ratio (first ratio) of the number of conductive particles in which the conductive metal is present in the region 1 of the base particle in the total number of 100% was calculated as follows. Further, using the obtained conductive material, when the area of the distance of 1/2 of the particle diameter of the base material particle is set to the area 2 from the center of the base material particle toward the outer surface, The ratio (second ratio) of the number of conductive particles in which the conductive metal is present in the region 2 of the base material particle in 100% of the total number of particles was calculated as follows.
• Conductive particles were collected by filtering the obtained conductive material. Set the content of the recovered conductive particles to 30% by weight, "techno ⁇ 0 2020/175 969 1 48 (: 171? 2020/008458
• the compression elastic modulus (10% ⁇ value and 30% ⁇ value) was measured by the above-described method using a micro compression tester (“Fisher Scope 1 to 1 _ 1 0 by Fisher”). 0"). From the measurement results, 10% ⁇ value and 30% ⁇ value were calculated.
• the obtained conductive material was observed and it was confirmed whether or not aggregation of conductive particles had occurred. Aggregation of the conductive particles was judged under the following conditions.
• Obtained conductive particles 1.09 and diameter 1 The zirconia beads of 509 and 1 are put in a mayonnaise bottle of 001. Further, add mayonnaise to toluene.
• the adhesion of the conductive part in the conductive particles was judged under the following conditions.
• connection resistance between the upper and lower electrodes of the obtained 20 connection structures was measured by the 4-terminal method.
• connection resistance The average value of the connection resistance is 1.50 or less
• connection resistance The average value of the connection resistance is more than 1.5 and not more than 2.0.
• connection resistance is more than 2.0 and not more than 5.00
• ⁇ The average value of the connection resistance exceeds 5.0 and 100 or less
• connection resistance The average value of connection resistance exceeds 100
• connection reliability In 20 connection structures obtained in (12) Evaluation of connection reliability, the presence or absence of leakage between adjacent electrodes was evaluated by measuring the resistance value with a tester. The insulation reliability was evaluated according to the following criteria.

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