CN117461095A - Coated particle, method for producing coated particle, resin composition, and connection structure - Google Patents
Coated particle, method for producing coated particle, resin composition, and connection structure Download PDFInfo
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- CN117461095A CN117461095A CN202280041129.XA CN202280041129A CN117461095A CN 117461095 A CN117461095 A CN 117461095A CN 202280041129 A CN202280041129 A CN 202280041129A CN 117461095 A CN117461095 A CN 117461095A
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- Prior art keywords
- particles
- conductive
- particle
- insulating
- coated
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- 239000002245 particle Substances 0.000 title claims abstract description 777
- 239000011342 resin composition Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 15
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- 239000000463 material Substances 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims description 126
- 238000000576 coating method Methods 0.000 claims description 126
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- 239000011347 resin Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 47
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- 239000011230 binding agent Substances 0.000 claims description 26
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- 239000000126 substance Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000002612 dispersion medium Substances 0.000 claims description 11
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- 239000007788 liquid Substances 0.000 claims description 8
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
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- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- OLXNZDBHNLWCNK-UHFFFAOYSA-N [Pb].[Sn].[Ag] Chemical compound [Pb].[Sn].[Ag] OLXNZDBHNLWCNK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- 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
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention provides a coated particle which can inhibit aggregation of particles, and can improve conduction reliability and insulation reliability when electric connection is realized between electrodes. The coated particle of the present invention comprises a coated portion and an insulating particle-containing conductive particle, wherein the insulating particle-containing conductive particle comprises a conductive particle and a plurality of insulating particles disposed on the surface of the conductive particle, the conductive particle comprises a base particle and a conductive portion disposed on the surface of the base particle, the coated portion coats at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle, the material of the coated portion comprises a polymerizable monomer, the polymerizable monomer comprises a crosslinkable monomer, and the content of the crosslinkable monomer is 10.0 wt% or more based on 100 wt% of the polymerizable monomer.
Description
Technical Field
The present invention relates to coated particles using conductive particles with insulating particles. The present invention also relates to a method for producing the coated particles, a resin composition using the coated particles, and a connection structure.
Background
Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are well known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin.
The anisotropic conductive material is used to obtain various connection structures. Examples of the connection using the anisotropic conductive material include: connection (FOG (Fil m on Glass)) of the flexible printed substrate and the glass substrate, connection (COF (Chip on Film)) of the semiconductor chip and the flexible printed substrate, connection (COG (Chip on Glass)) of the semiconductor chip and the glass substrate, connection (FOB (Film on Board)) of the flexible printed substrate and the glass epoxy substrate, and the like.
Further, as the conductive particles, conductive particles with insulating particles, in which insulating particles are disposed on the surface of the conductive particles, may be used. In the conductive particles with insulating particles, in order to prevent the insulating particles from being detached from the conductive particle body before conductive connection, a coating portion may be formed on the surface.
Patent documents 1 and 2 below disclose conductive particles with insulating particles having a coating portion on the surface thereof.
Patent document 1 discloses a conductive particle (coated particle) containing insulating particles, which comprises: a conductive particle body having a conductive layer on a surface thereof, an insulating resin layer (coating film) coating the surface of the conductive particle body, and a plurality of insulating particles arranged on the surface of the conductive particle body. In patent document 1, the average thickness of the resin layer is 1/6 or less of the average particle diameter of the conductive particle main body, and the average particle diameter of the insulating particles is 1.5 to 3.5 times the average thickness of the resin layer.
Patent document 2 below discloses conductive particles (coated particles) with insulating particles, which include a conductive particle body with insulating particles and a coating film coating the surface of the conductive particle body with insulating particles. The conductive particle body with insulating particles includes conductive particles having conductive portions at least on the surface thereof, and a plurality of insulating particles disposed on the surface of the conductive particles. In patent document 2, the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, and the average height of the protrusions is 0.05 μm or more and 0.5 μm or less. In patent document 2, the coating film includes a first coating film portion that coats the conductive particles and a second coating film portion that coats the surface of the insulating particles, and the ratio of the thickness of the first coating film portion to the average particle diameter of the insulating particles is 2/3 or more and 3 or less.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-187332
Patent document 2: japanese patent laid-open publication 2016-085988
Disclosure of Invention
Technical problem to be solved by the invention
In the conventional coated particles as described in patent documents 1 and 2, when a coating film is formed on the surface of the conductive particles containing insulating particles, the particles are likely to aggregate in the dispersion liquid, and therefore the surface may not be sufficiently coated with the coating film, and the coating film may be detached from the surface. As a result, when the electrodes are electrically connected by the conductive particles, it may be difficult to improve insulation reliability.
Further, if an anisotropic conductive material prepared using conductive particles with insulating particles that have agglomerated or coated particles that have agglomerated and a binder resin is used, the particles cannot be uniformly arranged between upper and lower electrodes to be connected after the application of the anisotropic conductive material, and as a result, it may be difficult to sufficiently improve the on-state reliability. In addition, if agglomerated particles are present, short circuits between electrodes adjacent in the lateral direction, which should not be connected, tend to occur, and the insulation reliability between electrodes adjacent in the lateral direction sometimes becomes low.
The purpose of the present invention is to provide a coated particle that can suppress aggregation of particles, and that can improve conduction reliability and insulation reliability when an electrical connection is made between electrodes. The present invention also provides a method for producing the coated particles, a resin composition using the coated particles, and a connection structure.
Means for solving the technical problems
According to a broad aspect of the present invention, there is provided a coated particle comprising a coated portion and an insulating particle-containing conductive particle, wherein the insulating particle-containing conductive particle comprises a conductive particle and a plurality of insulating particles disposed on a surface of the conductive particle, the conductive particle comprises a base particle and a conductive portion disposed on a surface of the base particle, the coated portion coats at least a part of a surface of the conductive portion and at least a part of a surface of the insulating particle, a material of the coated portion comprises a polymerizable monomer, the polymerizable monomer comprises a crosslinkable monomer, and a content of the crosslinkable monomer is 10.0 wt% or more based on 100 wt% of the polymerizable monomer.
In a specific aspect of the coated particle of the present invention, the crosslinkable monomer comprises divinylbenzene.
In a specific aspect of the coated particle of the present invention, the polymerizable monomer comprises a compound represented by the following formula (1).
[ chemical formula 1]
In the formula (1), X1 represents a hydroxyl group, an alkoxy group, or an alkyl group having 1 to 12 carbon atoms, X2 represents an organic group containing an unsaturated bond, and the organic group containing an unsaturated bond contains a (meth) acryloyl group.
In a specific aspect of the coated particle of the present invention, the polymerizable monomer comprises a non-crosslinkable monomer comprising styrene.
In a specific aspect of the coated particle of the present invention, the insulating particle is a resin particle.
In a specific aspect of the coated particle of the present invention, the insulating particle comprises a polymer.
In a specific aspect of the coated particle of the present invention, the ratio of the thickness of the coating portion to the particle diameter of the insulating particle is 1/2 or less.
In a specific aspect of the coated particle of the present invention, the area of the portion coated with the coating portion is 80% or more of 100% of the total surface area of the conductive particle with insulating particles.
According to a broad aspect of the present invention, there is provided a method for producing coated particles, comprising: and a step of polymerizing the material of the coating portion in a dispersion liquid in which the conductive particles with insulating particles are dispersed in a dispersion medium, and forming the coating portion on the surface of the conductive portion of the conductive particles and the surface of the insulating particles, thereby obtaining coated particles.
In a specific aspect of the method for producing coated particles according to the present invention, the method for producing coated particles comprises: a step of disposing the conductive portions on the surfaces of the base particles to obtain conductive particles; and disposing a plurality of insulating particles on the surface of the conductive portion of the conductive particles to obtain conductive particles with insulating particles.
According to a broad aspect of the present invention, there is provided a resin composition comprising the coated particles described above and a binder resin.
According to a broad aspect of the present invention, there is provided a connection structure comprising: a first connection object member having a first electrode on a surface thereof; a second connection object member having a second electrode on a surface thereof; and a connection portion for connecting the first connection object member and the second connection object member, wherein a material of the connection portion includes the coating particles, and the first electrode and the second electrode are electrically connected by the conductive particles.
Effects of the invention
The coated particle of the present invention comprises a coating portion and conductive particles with insulating particles. In the coated particle of the present invention, the conductive particle with insulating particles includes conductive particles and a plurality of insulating particles disposed on the surface of the conductive particles. In the coated particle of the present invention, the conductive particle includes a base particle and a conductive portion disposed on a surface of the base particle. In the coated particle of the present invention, the coating portion coats at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle. In the coated particle of the present invention, the material of the coating portion includes a polymerizable monomer, the polymerizable monomer includes a crosslinkable monomer, and the content of the crosslinkable monomer is 10.0 wt% or more in 100 wt% of the polymerizable monomer. In the coated particles of the present invention, since the above-described structure is provided, aggregation of particles can be suppressed, and when the electrodes are electrically connected, the conduction reliability can be improved, and the insulation reliability can be improved.
Drawings
Fig. 1 is a cross-sectional view showing a coated particle according to a first embodiment of the present invention.
Fig. 2 is a cross-sectional view showing coated particles according to a second embodiment of the present invention.
Fig. 3 is a cross-sectional view showing coated particles according to a third embodiment of the present invention.
Fig. 4 is a cross-sectional view schematically showing a connection structure using coated particles according to the first embodiment of the present invention.
Detailed Description
The present invention will be described in detail below.
(coated particles)
The coated particle of the present invention comprises a coating portion and conductive particles with insulating particles. In the coated particle of the present invention, the conductive particle with insulating particles includes conductive particles and a plurality of insulating particles disposed on the surface of the conductive particles. In the coated particle of the present invention, the conductive particle includes a base particle and a conductive portion disposed on a surface of the base particle. In the coated particle of the present invention, the coating portion coats at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle. In the coated particle of the present invention, the material of the coating portion includes a polymerizable monomer, and the polymerizable monomer includes a crosslinkable monomer. In the coated particles of the present invention, the content of the crosslinkable monomer is 10.0 wt% or more based on 100 wt% of the polymerizable monomer.
In the conventional coated particles, since a non-crosslinkable monomer is used as a material of the coating film, when the coating film is formed on the surface of the conductive particles with insulating particles, the particles (conductive particles with insulating particles) are likely to aggregate in the dispersion liquid, and the surface of the conductive particles with insulating particles may not be sufficiently coated. As a result, since the insulating particles are separated from the surface of the conductive particles, when the electrodes are electrically connected by the conductive particles, it may be difficult to improve the insulation reliability. In addition, if the particles agglomerate at the time of forming the coating film, the obtained coated particles also become agglomerated.
Further, if an anisotropic conductive material prepared using conductive particles with insulating particles that have agglomerated or coated particles that have agglomerated and a binder resin is used, the particles cannot be uniformly arranged between upper and lower electrodes to be connected after the application of the anisotropic conductive material, and as a result, it may be difficult to sufficiently improve the on-state reliability. In addition, if agglomerated particles are present, short circuits between electrodes adjacent in the lateral direction, which should not be connected, tend to occur, and the insulation reliability between electrodes adjacent in the lateral direction sometimes becomes low.
On the other hand, in the coated particles of the present invention, since the coating particles have the above-described structure, aggregation of particles can be suppressed, and when the electrodes are electrically connected, the conduction reliability can be improved, and the insulation reliability can be improved.
Hereinafter, a specific embodiment of the present invention will be described with reference to the drawings. In fig. 1 and the later-described drawings, different portions may be replaced with each other. In fig. 1 and the drawings described later, the size and thickness of each component may be different from the actual size and thickness for convenience of illustration.
Fig. 1 is a cross-sectional view showing a coated particle according to a first embodiment of the present invention.
The coated particle 1 shown in fig. 1 includes conductive particles 2 with insulating particles and a coating portion 3. The conductive particles 2 with insulating particles in the coated particles 1 include conductive particles 11 and a plurality of insulating particles 12 arranged on the surface of the conductive particles 11. In the coated particle 1, the conductive particle 11 includes a base particle 21 and a conductive portion 22 disposed on the surface of the base particle 21.
In the coated particle 1, the coating portion 3 coats the surface of the conductive particle 11 (the surface of the conductive portion 22) and the surface of the insulating particle 12. In the coated particle 1, the coating portion 3 is disposed on the surface of the conductive particle 11 (the surface of the conductive portion 22) and the surface of the insulating particle 12, and is in contact with the conductive particle 11 (the conductive portion 22) and the insulating particle 12. In the coated particle 1, the coating portion 3 coats the surface of the conductive particle 2 with the insulating particle.
In the coated particle 1, the insulating particles 12 are disposed on the surface of the conductive particle 11. In the coated particle 1, the insulating particles 12 are disposed on the surface of the conductive portion 22 and contact the conductive portion 22.
The conductive portion 22 covers the surface of the base particle 21. In the conductive particles 11, the surface of the base particles 21 is covered with the conductive portions 22. The conductive particles 11 have conductive portions 22 on the surface.
In the coated particle 1, the conductive portion 22 is a conductive layer. The conductive portion 22 is a single-layer conductive layer. In the conductive particles, the conductive portion may cover the entire surface of the base material particle, and the conductive portion may cover a part of the surface of the base material particle.
The coated particle 1 can be obtained, for example, by using the conductive particle 2 with the insulating particle (the conductive particle 11 to which the insulating particle 12 is attached) before the coating portion 3 is disposed, and polymerizing the material of the coating portion 3 in the dispersion liquid to form the coating portion 3. The polymerization may be performed in a dispersion in which the conductive particles 2 containing insulating particles are dispersed in a dispersion medium. The coated particles 1A and 1B described later can be obtained in the same manner as the coated particles 1.
Fig. 2 is a cross-sectional view showing a coated particle according to a second embodiment of the present invention.
The coated particle 1A shown in fig. 2 includes conductive particles 2A with insulating particles and a coating portion 3A. In the coated particle 1A, the conductive particle 2A with insulating particles includes conductive particles 11A and a plurality of insulating particles 12A arranged on the surface of the conductive particles 11A. In the coated particle 1A, the conductive particle 11A includes a base particle 21A and a conductive portion 22A disposed on the surface of the base particle 21A.
In the coated particle 1A, the coating portion 3A coats the surface of the conductive particle 11A (the surface of the conductive portion 22A) and the surface of the insulating particle 12A. In the coated particle 1A, the coating portion 3A is disposed on the surface of the conductive particle 11A (the surface of the conductive portion 22A) and the surface of the insulating particle 12A, and is in contact with the conductive particle 11A (the conductive portion 22A) and the insulating particle 12A. In the coated particle 1A, the coating portion 3A coats the surface of the conductive particle 2A with the insulating particle.
In the coated particles 1A, the insulating particles 12A are disposed on the surface of the conductive particles 11A. In the coated particle 1A, the insulating particle 12A is disposed on the surface of the conductive portion 22A, and contacts the conductive portion 22A.
In the coated particle 1A, the conductive portion 22A is a 2-layer conductive layer. The conductive portion 22A includes a first conductive portion 22AA and a second conductive portion 22AB. In the conductive portion 22A, a first conductive portion 22AA is laminated on the surface of the base material particle 21A, and a second conductive portion 22AB is laminated on the surface of the first conductive portion 22 AA.
The composition of the conductive portion is different between the coated particle 1 and the coated particle 1A. The conductive portion may be 1 conductive layer or may be a plurality of conductive layers.
Fig. 3 is a cross-sectional view showing a coated particle according to a third embodiment of the present invention.
The coated particle 1B shown in fig. 3 includes conductive particles 2B with insulating particles and a coating portion 3B. In the coated particle 1B, the conductive particle 2B having the insulating particles includes the conductive particle 11B and a plurality of insulating particles 12B disposed on the surface of the conductive particle 11B. In the coated particle 1B, the conductive particle 11B includes a base particle 21B, a conductive portion 22B disposed on the surface of the base particle 21B, and a plurality of core materials 23B disposed on the surface of the base particle 21B.
In the coated particle 1B, the coating portion 3B coats the surface of the conductive particle 11B (the surface of the conductive portion 22B) and the surface of the insulating particle 12B. In the coated particle 1B, the coating portion 3B is disposed on the surface of the conductive particle 11B (the surface of the conductive portion 22B) and the surface of the insulating particle 12B, and is in contact with the conductive particle 11B (the conductive portion 22B) and the insulating particle 12B. In the coated particles 1B, the coating portion 3B coats the surface of the conductive particles 2B with insulating particles.
In the coated particles 1B, the insulating particles 12B are disposed on the surface of the conductive particles 11B. In the coated particle 1B, the insulating particle 12B is disposed on the surface of the conductive portion 22B, and contacts the conductive portion 22B.
In the coated particle 1B, the conductive portion 22B coats the base particle 21B and the core material 23B. The core material 23B is covered with the conductive portion 22B, so that the covered particles 1B, the conductive particles 2B with insulating particles, and the conductive particles 11B have a plurality of protrusions 11Ba on the surface. The surface of the conductive portion 22B is raised by the core material 23B, and a plurality of protrusions 11Ba are formed.
The coated particles 1 and the coated particles 1B are different in the presence or absence of the use of the core material and the presence or absence of the protrusions. The coated particles may or may not have protrusions on the surface.
Hereinafter, other details of the coated particles will be described.
In the present specification, "(meth) acrylate" means both acrylate and methacrylate. "(meth) acrylic" means acrylic and methacrylic. "(meth) acryl" means acryl and methacryl.
The particle diameter of the coated particles is preferably 0.5 μm or more, more preferably 1.0 μm or more, further preferably 2.0 μm or more, preferably 20 μm or less, more preferably 10 μm or less, further preferably 5.0 μm or less. When the particle diameter of the coated particles is equal to or larger than the lower limit and equal to or smaller than the upper limit, the contact area between the coated particles and the electrodes becomes sufficiently large when the electrodes are connected using the coated particles, and the coated particles that have aggregated are not easily formed when the conductive portions are formed. In addition, the interval between the electrodes connected via the coated particles does not become excessively large, and the conductive portion is not easily peeled off from the surface of the base material particles.
The particle diameter of the coated particles is preferably an average particle diameter. The average particle diameter is a number average particle diameter. The particle diameter of the coated particles can be obtained by observing 50 arbitrary coated particles with an electron microscope or an optical microscope, calculating the average value of the particle diameters of the coated particles, or measuring the particle size distribution by laser diffraction, for example.
From the viewpoint of more effectively exhibiting the effects of the present invention, the coefficient of variation (CV value) of the particle diameter of the coated particles is preferably 10% or less, more preferably 5% or less.
The coefficient of variation (CV value) can be determined as follows.
CV value (%) = (ρ/Dn) ×100
ρ: standard deviation of particle size of coated particles
Dn: average particle diameter of coated particles
The shape of the coated particles is not particularly limited. The shape of the coated particles may be spherical, may be other than spherical, may be flat, or the like.
The coated particles are dispersed in a binder resin and are suitable for use in obtaining a resin composition.
Hereinafter, other details of the coated particles will be described.
< substrate particle >
The substrate particles may be: resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles, metal particles, and the like. The substrate particles are preferably substrate particles other than metal particles, more preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles. The substrate particle may be a core-shell particle including a core and a shell disposed on a surface of the core. The core may be an organic core and the shell may be an inorganic shell.
The material of the resin particles may be: polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonates, polyamides, phenolic resins, melamine formaldehyde resins, benzoguanamine formaldehyde resins, urea formaldehyde resins, phenolic resins, melamine resins, benzoguanamine resins, urea formaldehyde resins, epoxy resins, unsaturated polyester resins, saturated polyester resins, polyethylene terephthalate, polysulfones, polyphenylene oxides, polyacetals, polyimides, polyamideimides, polyetheretherketones, polyethersulfones, and divinylbenzene polymers. The divinylbenzene polymer may be a divinylbenzene copolymer. Examples of the divinylbenzene copolymer include: divinylbenzene-styrene copolymers, divinylbenzene- (meth) acrylate copolymers, and the like. The material of the resin particles is preferably a polymer obtained by polymerizing 1 or 2 or more polymerizable monomers having an ethylenically unsaturated group, from the viewpoint that the hardness of the resin particles can be easily controlled within a suitable range.
In the case where the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, examples of the polymerizable monomer having an ethylenically unsaturated group include: a non-crosslinkable monomer and a crosslinkable monomer.
Examples of the non-crosslinkable monomer include: styrene monomers such as styrene and α -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid and maleic anhydride; alkyl (meth) acrylate compounds such as 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, and isobornyl (meth) acrylate; oxygen atom-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; vinyl acetate compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, chlorostyrene and other halogen-containing monomers, and the like.
Examples of the crosslinkable monomer include: polyfunctional (meth) acrylate compounds such as tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethyleneglycol di (meth) acrylate, and 1, 4-butanediol di (meth) acrylate; silane-containing monomers such as triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, and gamma- (meth) acryloxypropyl trimethoxysilane, trimethoxysilyl styrene, and vinyl trimethoxysilane. The crosslinkable monomer is preferably (poly) ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, or dipentaerythritol poly (meth) acrylate, from the viewpoint that the resin particles maintain shape even at the glass transition temperature of the resin particles.
The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of the method include a method of performing suspension polymerization in the presence of a radical polymerization initiator and a method of performing polymerization by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
In the case where the base particles are inorganic particles or organic-inorganic hybrid particles other than metal particles, examples of the inorganic substance used for forming the base particles include: silica, alumina, barium titanate, zirconia, carbon black, and the like. The mineral is preferably not a metal. Examples of the particles formed of the silica include: and (c) a particle obtained by hydrolyzing a silicon compound having 2 or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and firing the crosslinked polymer particles as needed. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
The organic-inorganic hybrid particles are preferably core-shell type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core. Preferably, the core is an organic core. The shell is preferably an inorganic shell. The substrate particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core, from the viewpoint of effectively reducing the connection resistance between the electrodes.
Examples of the material of the organic core include materials of the resin particles.
The inorganic shell material may be an inorganic material as the material of the base particles. The material of the inorganic shell is preferably silica. The inorganic shell is preferably formed by forming a shell of a metal alkoxide on the surface of the core by a sol-gel method and then firing the shell. The metal alkoxide is preferably a silanol salt. The inorganic shell is preferably formed from a silanolate.
When the base particles are metal particles, examples of the metal as a material of the metal particles include silver, copper, nickel, silicon, gold, titanium, and the like.
The particle diameter of the base particles is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 10 μm or less, more preferably 5.0 μm or less. When the particle diameter of the base material particles is not less than the lower limit and not more than the upper limit, the interval between the electrodes becomes small, and even if the thickness of the conductive portion is increased, small conductive particles (coated particles) can be obtained. In addition, the conductive portion is formed on the surface of the base material particle, and aggregation is not easily generated when the coating portion is disposed, and the conductive particle and the coating particle with insulating particles, in which aggregation is generated, are not easily formed.
The shape of the base particles is not particularly limited. The shape of the base material particles may be spherical, may be other than spherical, may be flat, or the like.
The particle diameter of the base material particles represents a number average particle diameter. The particle diameter of the base material particles is determined using a particle size distribution measuring apparatus or the like. The particle diameter of the base material particles is preferably obtained by observing arbitrary 50 base material particles with an electron microscope or an optical microscope and calculating an average value. In the case of measuring the particle diameter of the base particles in the coated particles, the measurement can be performed, for example, as follows.
The coated particles were added to "TECHNOVI T4000" manufactured by Kulzer corporation so that the content of the coated particles was 30% by weight, and dispersed, to prepare an embedded resin body for inspection containing the coated particles. The cross section of the coated particles was cut out using an ion milling device (IM 4000, manufactured by hitachi high technology corporation) so as to pass through the vicinity of the center of the coated particles dispersed in the resin body for inspection. Then, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 25000 times, 50 coated particles were randomly selected, and the base particles of each coated particle were observed. The particle diameters of the base particles in the coated particles were measured, and the base particles were arithmetically averaged to obtain the particle diameters of the base particles.
< core substance and protrusions >
The coated particles preferably have protrusions on the outer surface of the conductive part. The protrusions are preferably a plurality. The conductive particles preferably have protrusions on the outer surface of the conductive portion. The protrusions are preferably a plurality. In general, an oxide film is often formed on the surface of an electrode in contact with the coated particles. In the case of using coated particles having protrusions on the surface, the oxide film can be effectively removed by the protrusions at the time of conductive connection. Therefore, the electrode and the coated particle are more reliably contacted, the contact area between the coated particle and the electrode can be sufficiently increased, and the connection resistance can be more effectively reduced. In addition, when the coated particles are dispersed in a binder resin and used as a resin composition or a conductive material, the binder resin between the coated particles and the electrode can be more effectively eliminated by the projections of the coated particles. Therefore, the contact area between the coated particles and the electrode can be sufficiently increased, and the connection resistance can be reduced more effectively.
Examples of the method of forming the protrusions on the surfaces of the coated particles and the conductive particles include: a method in which a core material is attached to the surface of a base material particle and then a conductive portion is formed by electroless plating; and a method in which a conductive portion is formed on the surface of the base material particles by electroless plating, and then a core material is attached thereto, and further a conductive portion is formed by electroless plating.
Examples of the method for attaching the core material to the surface of the base material particle include: a method in which a core material is added to a dispersion of base particles, and the core material is aggregated and attached to the surfaces of the base particles by, for example, van der Waals force; and a method in which a core material is added to a container in which base particles are placed, and the core material is attached to the surface of the base particles by a mechanical action such as rotation of the container. Among them, in order to easily control the amount of the core material to be adhered, a method of accumulating the core material on the surface of the base material particles in the dispersion and adhering the core material is preferable.
The conductive particles may have a first conductive portion on a surface of the base material particles and a second conductive portion on a surface of the first conductive portion. In this case, the core material may be attached to the surface of the base material particles, or the core material may be attached to the surface of the first conductive portion. The core material is preferably coated with the second conductive portion, more preferably with the first conductive portion and the second conductive portion. The conductive particles are preferably obtained by attaching a core material to the surface of a base particle, forming a first conductive portion on the surface of the base particle and the core material, and then forming a second conductive portion on the surface of the first conductive portion.
Examples of the substance constituting the core substance include a conductive substance and a nonconductive substance. Examples of the conductive substance include a conductive nonmetal such as a metal, an oxide of a metal, and graphite, and a conductive polymer. The conductive polymer may be polyacetylene or the like. Examples of the nonconductive material include silica, alumina, and zirconia. The substance constituting the core substance is preferably a metal from the viewpoint of improving conductivity. From the viewpoint of improving conductivity, the core material is preferably metal particles.
Examples of the metal include: metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and alloys composed of 2 or more metals such as tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy, and tungsten carbide. Among them, nickel, copper, silver or gold is preferable. The metal constituting the core material may be the same as or different from the metal constituting the conductive portion (conductive layer).
The shape of the core material is not particularly limited. The core material is preferably in the shape of a block. Examples of the core material include a particulate block, an aggregated block formed by aggregating a plurality of fine particles, and an amorphous block.
The average height of the plurality of protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, preferably 0.9 μm or less, more preferably 0.2 μm or less. If the average height of the protrusions is equal to or greater than the lower limit and equal to or less than the upper limit, the connection resistance between the electrodes can be effectively reduced.
< conductive portion >
In the present invention, the conductive particles have conductive portions on the surface. The conductive portion is disposed on the surface of the base material particle.
The conductive portion preferably comprises metal. The metal constituting the conductive portion is not particularly limited. The metal may be: gold, silver, copper, tin, platinum, palladium, zinc, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, alloys thereof, and the like. Further, as the metal, tin-doped indium oxide (ITO) may be used. The metal may be used in an amount of 1 or 2 or more.
The conductive portion preferably contains tin, nickel, palladium, copper or gold, more preferably contains tin or nickel, and still more preferably contains nickel, from the viewpoint of further improving the conduction reliability.
From the viewpoint of further improving the conduction reliability, the conductive portion preferably contains nickel as a main metal. The nickel content in the conductive portion 100 wt% is preferably 15 wt% or more, more preferably 20 wt% or more, still more preferably 25 wt% or more, and particularly preferably 30 wt% or more, from the viewpoint of further improving the conduction reliability. The content of nickel in 100 wt% of the conductive portion may be 100 wt% (total) or 90 wt% or less.
The conductive portion may be formed of 1 layer. The conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of 2 or more layers. In the case where the conductive portion is formed of a plurality of layers, the metal constituting the outermost layer is preferably tin, nickel, palladium, copper or gold, more preferably tin, nickel, palladium or nickel, and still more preferably palladium or gold. In the case where the metal constituting the outermost layer is the above-mentioned preferable metal, the connection resistance between the electrodes is further reduced. In addition, when the metal constituting the outermost layer is gold, the corrosion resistance is further improved.
The area of the portion covered with the conductive portion (the covering ratio by the conductive portion) is preferably 80% or more, more preferably 90% or more, of 100% of the total surface area of the base material particles. The upper limit of the coating ratio by the conductive portion is not particularly limited. The coating ratio based on the conductive portion may be 99% or less. When the coating ratio of the conductive portion is equal to or higher than the lower limit and equal to or lower than the upper limit, the conduction reliability can be more effectively improved when the electrodes are electrically connected.
The thickness of the conductive portion is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 1.0 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. If the thickness of the conductive portion is equal to or greater than the lower limit and equal to or less than the upper limit, the conduction reliability can be more effectively improved, and the conductive particles are not excessively hard, so that the conductive particles are sufficiently deformed at the time of connection between the electrodes.
When the conductive portion is formed of a plurality of layers, the thickness of the conductive portion of the outermost layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably 0.3 μm or less. When the thickness of the outermost conductive portion is equal to or greater than the lower limit and equal to or less than the upper limit, the outermost conductive portion becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes can be sufficiently reduced.
When the conductive portion is formed of a plurality of layers, the thickness of the conductive portion of the innermost layer is preferably 0.005 μm or more, more preferably 0.01 μm or more, preferably 0.5 μm or less, more preferably 0.3 μm or less. When the thickness of the conductive portion of the innermost layer is equal to or greater than the lower limit and equal to or less than the upper limit, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes can be further reduced.
The thickness of the conductive portion can be measured, for example, by observing a cross section of the coated particle using a Transmission Electron Microscope (TEM).
The method for forming the conductive portion on the surface of the base material particle is not particularly limited. Examples of the method for forming the conductive portion include a method using electroless plating, a method using electroplating, a method using physical collision, a method using mechanochemical reaction, a method using physical vapor deposition or physical adsorption, and a method of applying a metal powder or paste containing a metal powder and a binder to the surface of a base particle. The method of forming the conductive portion is preferably a method using electroless plating, electroplating, or physical impact. Examples of the method using physical vapor deposition include vacuum vapor deposition, ion plating, and ion sputtering. In addition, in the method using physical collision, for example, a THETA COMP OSER (manufactured by Desholtzia Co., ltd.) or the like is used.
< insulating particles >
The coated particles of the present invention comprise a plurality of insulating particles disposed on the surface of the conductive particles. Since the coated particles have the above-described structure, if the coated particles are used for connection between electrodes, short-circuiting between adjacent electrodes can be prevented. Specifically, when the plurality of coated particles are in contact with each other, insulating particles are present between the plurality of electrodes, and therefore, it is possible to prevent a short circuit between electrodes adjacent in the lateral direction, not between upper and lower electrodes. In the case of connecting electrodes, the insulating particles between the conductive particles and the electrodes can be easily removed by pressurizing the coated particles with 2 electrodes. In addition, in the case where the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, insulating particles between the conductive particles and the electrode can be more easily eliminated.
The insulating particles are preferably polymers of polymerizable compounds. The polymerizable compound is not particularly limited. Examples of the polymerizable compound include materials of the resin particles. In the case where the electrodes are electrically connected, the insulating particles are preferably resin particles from the viewpoint of more effectively improving the conduction reliability and the insulation reliability. In addition, in the case where electrical connection is achieved between the electrodes, the insulating particles preferably contain a polymer from the viewpoint of more effectively improving the conduction reliability and the insulation reliability.
In the case where the electrodes are electrically connected, the molecular weight of the polymer is preferably 1 ten thousand or more, more preferably 5 ten thousand or more, further preferably 10 ten thousand or more, preferably 200 ten thousand or less, more preferably 150 ten thousand or less, further preferably 100 ten thousand or less, from the viewpoint of more effectively improving the conduction reliability and the insulation reliability.
In the case where electrical connection is made between the electrodes, the material of the insulating particles preferably contains divinylbenzene-styrene copolymer from the viewpoint of more effectively improving the conduction reliability and the insulation reliability.
In the case where the electrodes are electrically connected, the divinylbenzene content is preferably 1 wt% or more, more preferably 2 wt% or more, still more preferably 20 wt% or less, still more preferably 15 wt% or less, and still more preferably 10 wt% or less in 100 wt% of the material of the insulating particles, from the viewpoint of more effectively improving the conduction reliability and the insulation reliability.
Examples of the method for disposing the insulating particles on the surface of the conductive portion include a chemical method, a physical method, and a mechanical method. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. In the case where the electrodes are electrically connected, the method of disposing the insulating particles on the surface of the conductive portion is preferably a physical method from the viewpoint of more effectively improving the conduction reliability and the insulation reliability.
The particle diameter of the insulating particles may be appropriately selected according to the particle diameter of the coated particles, the use of the coated particles, and the like. The particle diameter of the insulating particles is preferably 10nm or more, more preferably 100nm or more, further preferably 200nm or more, particularly preferably 300nm or more, preferably 2000nm or less, more preferably 1000nm or less, further preferably 800nm or less, particularly preferably 500nm or less. When the particle diameter of the insulating particles is not less than the lower limit, the plurality of coated particles are less likely to aggregate with each other when the coated particles are dispersed in the binder resin. When the particle diameter of the insulating particles is equal to or smaller than the upper limit, it is not necessary to excessively increase the pressure to exclude the insulating particles between the electrodes and the conductive particles at the time of connection between the electrodes, and it is not necessary to heat the insulating particles to a high temperature.
The particle diameter of the insulating particles is preferably an average particle diameter, and preferably a number average particle diameter. The particle diameter of the insulating particles is determined using a particle size distribution measuring apparatus or the like. The particle diameter of the insulating particles is preferably an average value calculated by observing 50 arbitrary insulating particles with an electron microscope or an optical microscope; or by measuring the particle size distribution by laser diffraction. In the case of measuring the particle diameter of the insulating particles, the coated particles can be measured, for example, as follows.
The coated particles were added to "TECHNOVI T4000" manufactured by Kulzer corporation so as to be 30% by weight, and dispersed, to prepare an embedded resin body for inspection containing the coated particles. An ion milling device (IM 4000, manufactured by hitachi high technology corporation) was used to cut out a cross section of the insulating particles so as to pass through the vicinity of the center of the insulating particles among the dispersed coated particles embedded in the resin body for inspection. Then, 50 insulating particles were randomly selected and observed by setting the image magnification to 5 ten thousand times using a field emission scanning electron microscope (FE-SEM). The equivalent circle diameter of the insulating particles was measured as the particle diameter, and the average was arithmetically performed as the particle diameter of the insulating particles.
In the coated particles of the present invention, 2 or more kinds of insulating particles having different particle diameters may be used in combination. By using 2 or more kinds of insulating particles having different particle diameters in combination, insulating particles having small particle diameters can enter gaps covered with insulating particles having large particle diameters, and insulating particles can be more effectively disposed on the surfaces of conductive particles.
The coefficient of variation (CV value) of the particle diameter of the insulating particles is preferably 20% or less. When the coefficient of variation in the particle diameter of the insulating particles is equal to or less than the upper limit, the thickness of the insulating particles in the obtained coated particles becomes more uniform, and pressure can be more easily and uniformly applied during conductive connection, so that the connection resistance between electrodes can be further reduced.
The coefficient of variation (CV value) can be determined as follows.
CV value (%) = (ρ/Dn) ×100
ρ: standard deviation of particle diameter of insulating particles
Dn: average value of particle diameter of insulating particles
The shape of the insulating particles is not particularly limited. The insulating particles may have a spherical shape, a shape other than a spherical shape, or a flat shape.
In the case where the electrodes are electrically connected, the area of the portion covered with the insulating particles (the covering ratio based on the insulating particles) is preferably 30% or more, more preferably 40% or more, still more preferably 70% or less, and still more preferably 60% or less, of 100% of the total surface area of the conductive portion, from the viewpoint of more effectively improving the conduction reliability and the insulation reliability.
The coating ratio of the insulating particles can be measured, for example, by the following method. The conductive particles with insulating particles are observed from one direction by a Scanning Electron Microscope (SEM), and the total area occupied by the insulating particles in the circle of the outer peripheral edge portion of the surface of the conductive portion in the observation image is calculated from the total area occupied by the insulating particles in the whole area of the circle of the outer peripheral edge portion of the surface of the conductive portion. The coating ratio based on the insulating particles is preferably calculated as an average coating ratio obtained by observing 20 conductive particles with insulating particles and averaging the measurement results of the conductive particles with insulating particles.
The coating ratio of the insulating particles may be measured by mapping analysis such as EDX attached to SEM.
The coating ratio of the insulating particles is not particularly limited, and may be adjusted by, for example, the amount of the insulating particles to be added to the base particles, the mixing time, or the like.
< coating portion >
In the coated particle of the present invention, the coating portion coats at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle. The coating portion coats at least a part of the surface of the conductive particles with insulating particles. In the coated particles, the coating portion is disposed on at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle. In the coated particles, the coating portion is disposed on at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle. The coating portion may be a coating film.
The coating portion may not be disposed between the conductive portion and the insulating particle. From the viewpoint of more effectively exhibiting the effects of the present invention, it is preferable that the coating portion is disposed in a region of the surface of the conductive portion where the insulating particles are not disposed. In this case, the coating portion may be disposed between the conductive portion and the insulating particle, or the coating portion may not be disposed. The conductive portion and the insulating particle may be in direct contact without via the coating portion.
From the viewpoint of more effectively exhibiting the effects of the present invention, the coating portion preferably coats the entire surface of the conductive particles with insulating particles. From the viewpoint of more effectively exhibiting the effects of the present invention, the coating portion preferably coats the surface of the conductive portion and the surface of the insulating particle.
The material of the coating portion includes a polymerizable monomer including a crosslinkable monomer. The material of the coating portion includes a polymerizable component including a crosslinkable monomer. The coating preferably comprises a backbone derived from a polymerizable monomer, preferably a backbone derived from a crosslinkable monomer. Examples of the crosslinkable monomer include: polyfunctional (meth) acrylate compounds such as tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethyleneglycol di (meth) acrylate, and 1, 4-butanediol di (meth) acrylate; silane-containing monomers such as triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, and gamma- (meth) acryloxypropyl trimethoxysilane, trimethoxysilyl styrene, and vinyl trimethoxysilane. The crosslinkable monomer may be used in an amount of 1 or 2 or more. The crosslinkable monomer preferably contains divinylbenzene or (poly) ethylene glycol di (meth) acrylate, more preferably divinylbenzene, from the viewpoint of further suppressing aggregation of particles at the time of forming the coating portion and favorably coating the surface of the conductive particles with insulating particles.
The molecular weight of the crosslinkable monomer is preferably 50 or more, more preferably 100 or more, preferably 500 or less, more preferably 300 or less, from the viewpoint of further suppressing aggregation of particles at the time of forming the coating portion and favorably coating the surface of the conductive particles with the insulating particles.
In the material for the coating portion, the content of the crosslinkable monomer is 10.0 wt% or more based on 100 wt% of the polymerizable monomer. The content of the crosslinkable monomer in 100 wt% of the polymerizable monomer is preferably 12 wt% or more, more preferably 15 wt% or more, still more preferably 50 wt% or less, still more preferably 30 wt% or less, and still more preferably 25 wt% or less, from the viewpoint of further suppressing aggregation of particles at the time of forming the coating portion and thereby coating the surface of the conductive particles with insulating particles satisfactorily.
The polymerizable monomer may comprise a non-crosslinkable monomer. The coating may comprise a backbone derived from a non-crosslinkable monomer. Examples of the non-crosslinkable monomer include: styrene monomers such as styrene and α -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid and maleic anhydride; alkyl (meth) acrylate compounds such as 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, and isobornyl (meth) acrylate; oxygen atom-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate; nitrile-containing monomers such as (meth) acrylonitrile; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; vinyl acetate compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene; trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride, chlorostyrene and other halogen-containing monomers, and the like. The non-crosslinkable monomer may be used alone or in combination of 1 or more than 2. In order to further suppress aggregation of particles at the time of forming the coating portion and to satisfactorily coat the surface of the conductive particles with insulating particles, it is preferable that the polymerizable monomer contains a non-crosslinkable monomer containing styrene.
The molecular weight of the non-crosslinkable monomer is preferably 50 or more, more preferably 100 or more, preferably 500 or less, more preferably 300 or less, from the viewpoint of further suppressing aggregation of particles at the time of forming the coating portion and favorably coating the surface of the conductive particles with insulating particles.
When the polymerizable monomer contains a non-crosslinkable monomer, the content of the non-crosslinkable monomer is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 75% by weight or more, preferably 90% by weight or less, more preferably 85% by weight or less, based on 100% by weight of the polymerizable monomer. When the content of the non-crosslinkable monomer is not less than the lower limit and not more than the upper limit, aggregation of particles can be further suppressed at the time of forming the coating portion, and the surface of the conductive particles with insulating particles can be well coated.
The polymerizable monomer preferably contains a compound represented by the following formula (1). In the following formula (1), X1 represents a hydroxyl group, an alkoxy group, or an alkyl group having 1 to 12 carbon atoms, and X2 represents an organic group containing an unsaturated bond, the organic group containing an unsaturated bond containing a (meth) acryloyl group. When the material for the coating portion includes a compound represented by the following formula (1), aggregation of particles in the dispersion liquid at the time of forming the coating portion can be further suppressed, and the surface of the conductive particles with insulating particles can be sufficiently coated. As a result, when the electrodes are electrically connected using the coated particles, the insulation reliability can be more effectively improved.
[ chemical formula 2]
In the formula (1), X1 is preferably a hydroxyl group. That is, the compound represented by the formula (1) is preferably a compound represented by the following formula (1A). In this case, the effects of the present invention can be more effectively exhibited.
[ chemical formula 3]
In the formula (1A), X2 represents an organic group containing an unsaturated bond, and the organic group containing an unsaturated bond contains a (meth) acryloyl group.
The compound represented by the formula (1A) may be: and phosphoryloxy ethyl methacrylate (Acid phosphoxyethyl methacrylate), phosphoryloxy propyl methacrylate (Acid phosp hoxypropyl methacrylate), phosphoryloxy polyethylene glycol methacrylate (Acid phos phoxy polyoxyethylene glycol methacrylate), and phosphoryloxy polypropylene glycol methacrylate. The compound represented by the formula (1A) may be used alone or in combination of 1 or more than 2.
The compound represented by the formula (1A) is preferably phosphoryloxy ethyl methacrylate or phosphoryloxy polyethylene glycol methacrylate, more preferably phosphoryloxy polyethylene glycol methacrylate. In this case, aggregation of particles can be further suppressed at the time of forming the coating portion, and the surface of the conductive particles with insulating particles can be well coated.
From the viewpoint of more effectively exhibiting the effects of the present invention, the thickness of the coating portion is preferably 10nm or more, more preferably 30nm or more, further preferably 50nm or more, preferably 500nm or less, more preferably 200nm or less, further preferably 150nm or less.
The thickness of the coating portion can be measured, for example, by observing a cross section of the coated particle using a Transmission Electron Microscope (TEM).
The ratio of the thickness of the coating portion to the particle diameter of the insulating particles is described as a ratio (thickness of the coating portion/particle diameter of the insulating particles). From the viewpoint of more effectively exhibiting the effects of the present invention, the ratio (thickness of the coating portion/particle diameter of the insulating particles) is preferably 1/20 or more, more preferably 1/10 or more, preferably 1/2 or less, and still more preferably 1/3 or less.
From the viewpoint of more effectively exhibiting the effects of the present invention, the area of the portion covered with the covering portion (the covering rate by the covering portion) is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and most preferably 100% of the total surface area of the conductive particles with insulating particles. The coating ratio by the coating portion can be measured by the following method.
The conductive particles with insulating particles were observed from one direction by a Scanning Electron Microscope (SEM), and the total area occupied by the coating portion in the circle of the outer peripheral edge portion of the surface of the conductive portion in the observation image was calculated from the total area occupied by the coating portion in the circle of the outer peripheral edge portion of the surface of the conductive portion. The coating ratio by the coating section is preferably calculated as an average coating ratio obtained by observing 20 coated particles and averaging the measurement results of the coated particles.
The content of the coating portion in the coated particle is preferably 0.01 wt% or more, more preferably 0.1 wt% or more, still more preferably 10 wt% or less, still more preferably 5.0 wt% or less, still more preferably 2.0 wt% or less, and particularly preferably 1.0 wt% or less, based on 100 wt% of the coated particle. If the content of the coating portion is not less than the lower limit and not more than the upper limit, aggregation of the coated particles can be more effectively suppressed.
(method for producing coated particles)
The method for producing coated particles of the present invention comprises the steps of: and polymerizing the material of the coating portion in a dispersion liquid in which the conductive particles with insulating particles are dispersed in a dispersion medium, thereby forming a coating portion on the surface of the conductive portion of the conductive particles and the surface of the insulating particles, and obtaining coated particles.
Examples of the dispersion medium include solvents. Examples of the dispersion medium include water, methanol, ethanol, and 2-propanol. The dispersion medium may be used in an amount of 1 or 2 or more. The dispersion medium is preferably water, from the viewpoint of further suppressing aggregation of particles at the time of forming the coating portion and favorably coating the surface of the conductive particles with insulating particles. The dispersion medium is removed as needed after the coating portion is formed on the surface of the conductive portion of the conductive particle with the insulating particle and on the surface of the insulating particle.
In the method for producing the coated particles, the coating portion can be formed by polymerizing the material of the coating portion by a known method. Examples of the method include a method of performing suspension polymerization in the presence of a radical polymerization initiator and a method of performing polymerization by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
The method for producing coated particles of the present invention preferably comprises: a step of disposing the conductive portions on the surfaces of the base particles to obtain conductive particles; and disposing a plurality of the insulating particles on the surface of the conductive portion of the conductive particles to obtain conductive particles with insulating particles. In this case, when the electrodes are electrically connected, the conduction reliability and the insulation reliability can be more effectively improved.
(resin composition)
The resin composition of the present invention comprises the coated particles and a binder resin. The coated particles are preferably dispersed in a binder resin. The coated particles are preferably dispersed in a binder resin and used as a resin composition. The resin composition is preferably a conductive material, more preferably an anisotropic conductive material. The conductive material is preferably used for electrical connection between the electrodes. The conductive material is preferably a conductive material for circuit connection. In the resin composition and the conductive material, since the coating particles are used, the conduction reliability and the insulation reliability can be more effectively improved when the electric connection between the electrodes is achieved.
The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. The binder resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, more preferably contains a curable component. Examples of 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 comprises a thermosetting compound and a thermosetting agent.
Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. The binder resin may be used in an amount of 1 or 2 or more.
Examples of the vinyl resin include: vinyl acetate resin, acrylic resin, styrene resin, and the like. Examples of the thermoplastic resin include: polyolefin resins, ethylene-vinyl acetate copolymers, polyamide resins, and the like. Examples of the curable resin include: epoxy resins, polyurethane resins, polyimide resins, unsaturated polyester resins, and the like. The curable resin may be a room temperature curable resin, a thermosetting resin, a photo curable resin, or a moisture curable resin. The curable resin may be used in combination with a curing agent. Examples of the thermoplastic block copolymer include: styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrides of styrene-butadiene-styrene block copolymers and hydrides of styrene-isoprene-styrene block copolymers. Examples of the elastomer include: styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
The resin composition may contain various additives such as a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, and a flame retardant, in addition to the coated particles and the binder resin.
The method for dispersing the coated particles in the binder resin is not particularly limited, and any conventionally known dispersing method can be used. Examples of the method for dispersing the coated particles in the binder resin include the following methods. And a method in which the coated particles are added to the binder resin and then kneaded and dispersed by a planetary mixer or the like. A method in which the coated particles are uniformly dispersed in water or an organic dispersion medium using a homogenizer or the like, and then added to the binder resin, and kneaded and dispersed by a planetary mixer or the like. And a method in which the binder resin is diluted with water, an organic dispersion medium, or the like, and the coated particles are added and kneaded and dispersed by a planetary mixer or the like.
The viscosity (. Eta.25) of the resin composition at 25℃is preferably 30 Pa.s or more, more preferably 50 Pa.s or more, preferably 400 Pa.s or less, more preferably 300 Pa.s or less. When the viscosity of the resin composition at 25 ℃ is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be more effectively improved, and the conduction reliability between the electrodes can be more effectively improved. The viscosity (. Eta.25) can be appropriately adjusted depending on the kind and the blending amount of the blending components.
The viscosity (. Eta.25) can be measured, for example, using an E-type viscometer (TVE 22L, manufactured by Tokyo industries Co., ltd.) under conditions of 25℃and 5 rpm.
In the case where the resin composition of the present invention is a conductive material, the conductive material can be used as a conductive paste, a conductive film, or the like. In the case where the conductive material is a conductive film, a film containing no conductive particles may be stacked over the conductive film containing conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.
In the resin composition, the content of the binder resin is preferably 10 wt% or more, more preferably 30 wt% or more, further preferably 50 wt% or more, particularly preferably 70 wt% or more, preferably 99.99 wt% or less, and more preferably 99.9 wt% or less, based on 100 wt% of the resin composition. When the content of the binder resin is not less than the lower limit and not more than the upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the members to be connected by the resin composition can be further improved.
In the resin composition, the content of the coated particles is preferably 0.01 wt% or more, more preferably 0.1 wt% or more, preferably 80 wt% or less, more preferably 60 wt% or less, further preferably 40 wt% or less, particularly preferably 20 wt% or less, and most preferably 10 wt% or less, based on 100 wt% of the resin composition. If the content of the coated particles is 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 improved.
(connection Structure)
The connection structure of the present invention comprises: a first connection object member having a first electrode on a surface thereof; a second connection object member having a second electrode on a surface thereof; and a connection unit that connects the first connection target member and the second connection target member. In the connection structure of the present invention, the material of the connection portion includes the coated particles. In the connection structure of the present invention, the first electrode and the second electrode are electrically connected by the conductive particles.
The connection structure may be obtained by a step of disposing the coating particles between the first connection object member and the second connection object member and a step of conducting conductive connection by thermocompression bonding. Preferably, the coating portion and the insulating particles are separated from the coated particles at the time of the thermocompression bonding. In addition, the resin composition may be disposed instead of the coated particles.
Fig. 4 is a cross-sectional view schematically showing a connection structure using coated particles according to the first embodiment of the present invention.
The connection structure 81 shown in fig. 4 includes a first member 82 to be connected, a second member 83 to be connected, and a connection portion 84 that connects the first member 82 to be connected and the second member 83 to be connected. The material of the connection 84 comprises the coated particles 1. The connection portion 84 may be formed of a resin composition containing the coated particles 1. The connection portion 84 is preferably formed by curing a resin composition containing a plurality of coated particles 1. In fig. 4, the coated particle 1 is schematically shown for convenience of illustration. Instead of the coated particles 1, coated particles 1A or coated particles 1B may be used.
The first connection object member 82 has a plurality of first electrodes 82a on a surface (upper surface). The second connection object member 83 has a plurality of second electrodes 83a on a surface (lower surface). The first electrode 82a and the second electrode 83a are electrically connected by 1 or more conductive particles 11 (omitted in fig. 4) among the coated particles 1. Accordingly, the first connection target member 82 and the second connection target member 83 are electrically connected by the conductive portions 22 (omitted in fig. 4) of the conductive particles 11 (omitted in fig. 4).
The method for producing the connection structure is not particularly limited. As an example of a method for producing the connection structure, there is a method in which the coating particles or the resin composition is disposed between the first connection object member and the second connection object member to obtain a laminate, and then the laminate is heated and pressurized. The pressure of the thermocompression bonding is preferably 40MPa or more, more preferably 60MPa or more, preferably 90MPa or less, more preferably 70MPa or less. The temperature of the thermocompression bonding (heating temperature) is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, preferably 140 ℃ or lower, more preferably 120 ℃ or lower. When the pressure and temperature of the thermocompression bonding are equal to or higher than the lower limit and equal to or lower than the upper limit, the coating portion and the insulating particles can be easily separated from the surface of the coated particles at the time of conductive connection, and the conduction reliability between the electrodes can be further improved.
When the laminate is heated and pressurized, the coating portion and the insulating particles existing between the conductive particles and the first electrode and the second electrode can be eliminated. For example, when the conductive particles are heated and pressurized, the insulating particles present between the conductive particles and the first and second electrodes are easily detached from the surfaces of the conductive particles with insulating particles. In the heating and pressurizing, a part of the insulating particles may be separated from the surface of the conductive particles with insulating particles, and the surface of the conductive portion may be partially exposed. By bringing the exposed portion of the surface of the conductive portion into contact with the first electrode and the second electrode, the first electrode and the second electrode can be electrically connected via the conductive particles.
The first connection target member and the second connection target member are not particularly limited. Specifically, examples of the first and second connection target members include electronic components such as semiconductor chips, semiconductor packages, LED chips, LED packages, capacitors, and diodes, and electronic components such as resin films, printed boards, flexible flat cables, rigid-flexible bonded boards, and circuit boards such as glass epoxy boards and glass substrates. Preferably, the first connection object member and the second connection object member are electronic components.
Examples of the electrode provided on the connection target member include: metal electrodes such as gold electrode, nickel electrode, tin electrode, aluminum electrode, copper electrode, molybdenum electrode, silver electrode, SUS electrode, and tungsten electrode. In the case where the connection target member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. In the case where the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. In the case where the electrode is an aluminum electrode, the electrode may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a 3-valent metal element, zinc oxide doped with a 3-valent metal element, and the like. Examples of the 3-valent metal element include Sn, al, and Ga.
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to the following examples.
Example 1
(1) Preparation of conductive particles with insulating particles
Conductive particles (average particle diameter 3.0 μm, thickness of conductive portion 0.15 μm) having a conductive portion obtained by forming a nickel plating layer on the surface of divinylbenzene resin particles (base material particles) were prepared.
Composition a was prepared in a 1000mL removable flask equipped with a 4-neck removable flask lid, stirring blade, three-way stopcock, cooling tube, and temperature probe. Composition A contained 97 parts by weight of styrene, 3 parts by weight of divinylbenzene, 0.5 parts by weight of phosphoryloxy polyethylene glycol methacrylate, and 0.1 parts by weight of 2,2' -azobis {2- [ N- (2-carboxyethyl) amidino ] propane }. Then, the composition A was weighed into distilled water so that the solid content became 10% by weight, stirred at 200rpm, and polymerized at 60℃for 24 hours under a nitrogen atmosphere. After the completion of the reaction, the resulting mixture was freeze-dried to obtain insulating particles (divinylbenzene-styrene copolymer, average particle diameter: 300 nm), and then dispersed in 30mL of pure water under ultrasonic irradiation to obtain a 10 wt% dispersion of the insulating particles.
10g of the conductive particles were dispersed in 500mL of distilled water, 1g of the dispersion of the insulating particles was added thereto, and the mixture was stirred at room temperature for 8 hours. The mixture was filtered through a 10 μm mesh filter, washed with methanol, and dried to obtain conductive particles having insulating particles.
(2) Preparation of coated particles
50g of the obtained conductive particles with insulating particles were dispersed in 500ml of distilled water under ultrasonic irradiation to obtain a 10 wt% dispersion of conductive particles with insulating particles. To the resulting dispersion was added 0.88g (88 parts by weight) of styrene, 0.1g (10 parts by weight) of divinylbenzene, 0.01g (1 part by weight) of phosphoryloxy polyethylene glycol methacrylate and 0.01g (1 part by weight) of 2,2' -azobis {2- [ N- (2-carboxyethyl) amidino ] propane }. Then, the mixture was stirred at 200rpm, and polymerization was carried out at 60℃under a nitrogen atmosphere for 24 hours. After the completion of the reaction, the mixture was filtered through a 10 μm mesh filter, further washed with methanol, and dried to obtain coated particles in which the surfaces of the conductive particles having insulating particles were coated with coating portions.
(3) Preparation of resin composition (Anisotropic conductive paste)
7 parts by weight of the obtained coated particles, 25 parts by weight of bisphenol A type phenoxy resin, 4 parts by weight of fluorene type epoxy resin, 30 parts by weight of phenol novolac type epoxy resin and SI-60L (manufactured by Sanxinshi chemical industry Co., ltd.) were blended, and deaeration and stirring were carried out for 3 minutes, thereby obtaining a resin composition (anisotropic conductive paste).
(4) Preparation of connection Structure
A transparent glass substrate having an IZO electrode pattern (first electrode, vickers hardness of metal on the surface of the electrode 100 Hv) with an L/S of 10 μm/10 μm formed on the upper surface was prepared. Further, a semiconductor chip having an Au electrode pattern (second electrode, vickers hardness of metal of the surface of the electrode 50 Hv) with an L/S of 10 μm/10 μm formed on the lower surface was prepared.
The obtained resin composition (anisotropic conductive paste) was applied to the transparent glass substrate to a thickness of 30 μm, thereby forming an anisotropic conductive paste layer. Next, the semiconductor chips are stacked on the anisotropic conductive paste layer in such a manner that electrodes face each other. Then, while adjusting the temperature of the head so that the temperature of the anisotropic conductive paste layer becomes 100 ℃, a pressurizing and heating head is placed on the upper surface of the semiconductor chip, and a pressure of 60MPa is applied to cure the anisotropic conductive paste layer at 100 ℃, to obtain a connection structure.
Examples 2 to 10 and comparative example 2
The same procedure as in example 1 was repeated except that the composition of the coated particles was changed to tables 1 to 3 below, to obtain coated particles, a resin composition, and a connection structure.
Comparative example 1
Conductive particles with insulating particles were obtained in the same manner as in example 1, except that the composition of the insulating particles was changed as shown in table 3 below. A resin composition 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 instead of the coated particles.
(evaluation)
(1) Ratio (thickness of coating portion/particle diameter of insulating particle)
The thickness of the coating portion and the particle diameter of the insulating particles were measured by the above method, and the ratio of the thickness of the coating portion to the particle diameter of the insulating particles (thickness of the coating portion/particle diameter of the insulating particles) was obtained.
(2) Separation inhibition of insulating particles before conductive connection
The residual rate of the insulating particles was determined by the following method. The dispersion liquid in which 0.1g of conductive particles containing insulating particles was dispersed in 5g of toluene was stirred for 1 minute by shaking using a shaker. The coating ratios of the insulating particles before and after the test were measured, and the residual ratio (%) = (coating ratio after the test/coating ratio before the test) ×100 was obtained. The detachment inhibition of the insulating particles before conductive connection was determined based on the following criteria.
[ criterion for determining detachment inhibition of insulating particles ]
O: the residual ratio of the insulating particles was 100%
O: the residual rate of the insulating particles is 80% or more and less than 100%
O: the residual rate of the insulating particles is 70% or more and less than 80%
X: the residual ratio of the insulating particles is less than 70%
(3) Aggregation inhibition of particles in resin composition
The obtained resin composition was applied onto a transparent glass substrate in a manner of 0.5mm in the longitudinal direction and 0.5mm in the transverse direction and 30 μm in the thickness, and the number of particles (conductive particles and coated particles having insulating particles) having undergone aggregation in the resin composition was measured using an optical microscope ("VH-Z450" manufactured by KEYENCE). The aggregation inhibition of particles in the resin composition was determined according to the following criteria.
[ criterion for determining aggregation inhibition of particles in resin composition ]
O: the number of agglomerated particles is 4 or less
O: the number of the agglomerated particles is 5 or more and 6 or less
O: the number of the agglomerated particles is 7 or more and 9 or less
X: the number of agglomerated particles is 10 or more
(4) Conduction reliability (upper and lower electrode)
The connection resistances between the upper and lower electrodes of the obtained 20 connection structures were measured by the 4-terminal method. The connection resistance can be obtained by measuring the voltage when a constant current flows, based on the relationship of voltage=current×resistance. The on-reliability is determined based on the following criteria.
[ criterion for determining on reliability ]
O: the connection resistance exceeds 1.5Ω and is 2.0Ω or less
O: the connection resistance exceeds 2.0Ω and is 5.0Ω or less
O: the connection resistance exceeds 5.0Ω and is 10Ω or less
X: the connection resistance exceeds 10Ω
(5) Insulation reliability (electrodes adjacent in transverse direction)
Of the 20 connection structures obtained, the presence or absence of electric leakage between adjacent electrodes was evaluated by measuring the resistance value by a tester. Insulation reliability was evaluated according to the following criteria.
[ criterion for insulation reliability ]
O: resistance value of 10 8 The number of the connection structures of Ω or more is 20
O: resistance value of 10 8 The number of the connection structures is 18 to 19
O: resistance value of 10 8 The number of the connection structures is 15 to 17
X: resistance value of 10 8 The number of the connection structures of Ω or more is 14 or less
The compositions and results of the coated particles and the conductive particles with insulating particles are shown in tables 1 to 3 below.
TABLE 1
TABLE 2
TABLE 3
Symbol description
1. 1A, 1B … coated particles
2. Conductive particles with insulating particles 2A, 2B …
3. 3A, 3B … coating
11. 11A, 11B … conductive particles
11Ba … projection
12. 12A, 12B … insulating particles
21. 21A, 21B … base material particles
22. 22A, 22B … conductive portions
22AA … first conductive part
22AB … second conductive part
23B … core material
81 and … connection structure
82 … first connection object part
82a … first electrode
83 … second connection object part
83a … second electrode
84 … connection
Claims (12)
1. A coated particle comprising a coating portion and conductive particles having insulating particles,
the conductive particles with insulating particles include conductive particles and a plurality of insulating particles disposed on the surface of the conductive particles,
the conductive particles have base particles and conductive portions disposed on the surfaces of the base particles,
the coating portion coats at least a part of the surface of the conductive portion and at least a part of the surface of the insulating particle,
the material of the coating part comprises a polymerizable monomer,
the polymerizable monomer comprises a crosslinkable monomer,
the content of the crosslinkable monomer in 100% by weight of the polymerizable monomer is 10.0% by weight or more.
2. The coated particle according to claim 1, wherein,
the crosslinkable monomer comprises divinylbenzene.
3. The coated particle according to claim 1 or 2, wherein,
the polymerizable monomer comprises a compound represented by the following formula (1),
[ chemical formula 1]
In the formula (1), X1 represents a hydroxyl group, an alkoxy group, or an alkyl group having 1 to 12 carbon atoms, X2 represents an organic group containing an unsaturated bond, and the organic group containing an unsaturated bond contains a (meth) acryloyl group.
4. The coated particle according to claim 1 to 3,
the polymerizable monomer comprises a non-crosslinkable monomer,
the non-crosslinkable monomer comprises styrene.
5. The coated particle according to any one of claims 1 to 4, wherein,
the insulating particles are resin particles.
6. The coated particle according to any one of claims 1 to 5, wherein,
the insulating particles comprise a polymer.
7. The coated particle according to any one of claims 1 to 6, wherein,
the ratio of the thickness of the coating portion to the particle diameter of the insulating particles is 1/2 or less.
8. The coated particle according to any one of claims 1 to 7, wherein,
the area of the portion covered by the covering portion is 80% or more of 100% of the total surface area of the conductive particles with insulating particles.
9. A method for producing the coated particle according to any one of claims 1 to 8, wherein the method comprises:
polymerizing the material of the coating portion in a dispersion liquid in which the conductive particles with insulating particles are dispersed in a dispersion medium,
and forming the coating portion on the surface of the conductive portion of the conductive particle and the surface of the insulating particle to obtain a coated particle.
10. The method for producing coated particles according to claim 9, comprising:
a step of disposing the conductive portions on the surfaces of the base particles to obtain conductive particles; and
and a step of disposing a plurality of insulating particles on the surface of the conductive portion of the conductive particles to obtain conductive particles with insulating particles.
11. A resin composition comprising:
the coated particle according to any one of claims 1 to 8, and
and (3) a binder resin.
12. A connection structure is provided with:
a first connection object member having a first electrode on a surface thereof;
a second connection object member having a second electrode on a surface thereof; and
a connection portion for connecting the first connection object member and the second connection object member,
The material of the connecting portion comprising the coated particles according to any one of claims 1 to 8,
the first electrode and the second electrode are electrically connected by the conductive particles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021098103 | 2021-06-11 | ||
| JP2021-098103 | 2021-06-11 | ||
| PCT/JP2022/023409 WO2022260159A1 (en) | 2021-06-11 | 2022-06-10 | Coated particles, coated particle production method, resin composition, and connection structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117461095A true CN117461095A (en) | 2024-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280041129.XA Pending CN117461095A (en) | 2021-06-11 | 2022-06-10 | Coated particle, method for producing coated particle, resin composition, and connection structure |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2022260159A1 (en) |
| KR (1) | KR20240019751A (en) |
| CN (1) | CN117461095A (en) |
| WO (1) | WO2022260159A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268303A (en) * | 1995-03-13 | 1995-10-17 | Soken Kagaku Kk | Anisotropic electrically-conductive adhesive composition |
| JP5476168B2 (en) | 2010-03-09 | 2014-04-23 | 積水化学工業株式会社 | Conductive particles, anisotropic conductive materials, and connection structures |
| JP5899063B2 (en) * | 2011-06-22 | 2016-04-06 | 積水化学工業株式会社 | Conductive particles with insulating particles, anisotropic conductive material, and connection structure |
| JP6564302B2 (en) | 2014-10-28 | 2019-08-21 | 積水化学工業株式会社 | Conductive particles with insulating particles, method for producing conductive particles with insulating particles, conductive material, and connection structure |
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2022
- 2022-06-10 JP JP2022538342A patent/JPWO2022260159A1/ja active Pending
- 2022-06-10 WO PCT/JP2022/023409 patent/WO2022260159A1/en active Application Filing
- 2022-06-10 KR KR1020237029689A patent/KR20240019751A/en unknown
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| Publication number | Publication date |
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| WO2022260159A1 (en) | 2022-12-15 |
| KR20240019751A (en) | 2024-02-14 |
| JPWO2022260159A1 (en) | 2022-12-15 |
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