WO2013094637A1 - 導電性粒子、導電材料及び接続構造体 - Google Patents
導電性粒子、導電材料及び接続構造体 Download PDFInfo
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- WO2013094637A1 WO2013094637A1 PCT/JP2012/082911 JP2012082911W WO2013094637A1 WO 2013094637 A1 WO2013094637 A1 WO 2013094637A1 JP 2012082911 W JP2012082911 W JP 2012082911W WO 2013094637 A1 WO2013094637 A1 WO 2013094637A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
Definitions
- the present invention relates to conductive particles in which a conductive layer is disposed on the surface of base particles, and more particularly to conductive particles that can be used for electrical connection between electrodes, for example.
- the present invention also relates to a conductive material and a connection structure using the conductive particles.
- Anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are widely known.
- anisotropic conductive material conductive particles are dispersed in a binder resin.
- the anisotropic conductive material is used for connection between an IC chip and a flexible printed circuit board, connection between an IC chip and a circuit board having an ITO electrode, and the like. For example, after disposing an anisotropic conductive material between the electrode of the IC chip and the electrode of the circuit board, these electrodes can be electrically connected by heating and pressing.
- Patent Document 1 discloses a conductive material in which a nickel conductive layer or a nickel alloy conductive layer is formed on the surface of spherical base particles having an average particle diameter of 1 to 20 ⁇ m by an electroless plating method. Sex particles are disclosed. The conductive particles have minute protrusions of 0.05 to 4 ⁇ m on the outermost layer of the conductive layer. The conductive layer and the protrusion are substantially continuously connected.
- connection resistance between the electrodes may increase.
- a conductive layer containing nickel and phosphorus is formed.
- an oxide film is formed on the surfaces of the electrodes connected by the conductive particles and the conductive layer of the conductive particles.
- the conductive layer containing nickel and phosphorus is relatively soft. It may not be sufficiently eliminated, and the connection resistance may increase.
- connection target member or the substrate may be damaged by the conductive particles.
- connection structure in which the electrodes are connected by the conductive particles may be exposed to high temperature and high humidity.
- the conductive layer may be modified under the influence of acid or the like under high temperature and high humidity, and the connection resistance between the electrodes may be increased. That is, when the connection structure is exposed to high temperature and high humidity, the connection resistance between the electrodes may increase, and the low connection resistance may not be maintained for a long time.
- An object of the present invention is to provide a conductive particle capable of reducing the connection resistance between electrodes when the electrodes are connected to obtain a connection structure, and further suppressing an increase in connection resistance under high temperature and high humidity. And providing a conductive material and a connection structure using the conductive particles.
- the substrate has a base particle and a conductive layer disposed on the surface of the base particle, and the conductive layer is at least one of nickel, tungsten, and molybdenum.
- a conductive layer portion 100 having a thickness of 5 nm from the outer surface of the conductive layer toward the inside in the thickness direction. Conductive particles are provided in which the total content of tungsten and molybdenum exceeds 5% by weight.
- the total content of tungsten and molybdenum is 10% in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer. % By weight or more.
- nickel and at least one metal component of tungsten and molybdenum are unevenly distributed in the thickness direction of the conductive layer, and the outside of the conductive layer.
- the portion contains more metal component than the inner portion of the conductive layer.
- the total content of tungsten and molybdenum exceeds 5% by weight in 100% by weight of the entire conductive layer.
- the concentration of nickel ions eluted is 100 ppm / cm per unit surface area of the conductive particles. It is preferable that it is 2 or less.
- the conductive layer is formed by electroless nickel plating using a reducing agent, and the conductive layer does not include a component derived from the reducing agent, Or content of the component derived from the said reducing agent in the 100 weight% of the whole of the said conductive layer containing the component derived from the said reducing agent is 5 weight% or less.
- the conductive layer includes boron.
- the boron content is preferably 0.05% by weight or more and 4% by weight or less in 100% by weight of the entire conductive layer.
- the conductive layer does not contain phosphorus, or the conductive layer contains phosphorus, and the content of phosphorus in 100% by weight of the entire conductive layer is 0. Less than 5% by weight.
- the conductive layer has a protrusion on the outer surface.
- the conductive material according to the present invention includes the above-described conductive particles and a binder resin.
- connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection
- the part is formed of the above-described conductive particles, or is formed of a conductive material containing the conductive particles and a binder resin.
- a conductive layer is disposed on the surface of the base particle, and the conductive layer contains nickel and at least one metal component of tungsten and molybdenum, In 100% by weight of the entire layer, the nickel content is 60% by weight or more, and in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer, tungsten and molybdenum Since total content exceeds 5 weight%, when connecting between electrodes using the electroconductive particle which concerns on this invention and obtaining a connection structure, the connection resistance between electrodes can be made low. Furthermore, even when the connection structure is exposed to high temperature and high humidity, the connection resistance is unlikely to increase.
- FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
- FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
- FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
- the conductive particles according to the present invention have base particles and a conductive layer disposed on the surface of the base particles.
- the conductive layer includes nickel and at least one metal component of tungsten and molybdenum. In 100% by weight of the entire conductive layer, the nickel content is 60% by weight or more. The total content of tungsten and molybdenum exceeds 5% by weight in 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer.
- the conductive layer has a specific composition
- the connection resistance between the electrodes can be lowered.
- the conductive layer having the specific composition is relatively hard. Therefore, the connection resistance between the electrodes can be reduced by effectively eliminating the oxide film on the surfaces of the electrodes and the conductive particles when connecting the electrodes.
- the total content of tungsten and molybdenum in the vicinity of the outer surface is relatively large. For this reason, for example, the acid resistance of the conductive layer is increased. Therefore, even if the connection structure is exposed to high temperature and high humidity, the influence of acid or the like is reduced. As a result, the connection resistance between the electrodes hardly increases, and a low connection resistance can be maintained over a long period of time.
- the total content of tungsten and molybdenum is preferably 10% by weight or more, more preferably 15% by weight in 100% by weight of the conductive layer portion having a thickness of 5 nm inward from the outer surface of the conductive layer. More preferably, it is 20% by weight or more, particularly preferably 25% by weight or more, and most preferably 30% by weight or more.
- the total content of tungsten and molybdenum is preferably 100% by weight of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer. 60% by weight or less, more preferably 50% by weight or less, and still more preferably 40% by weight or less.
- the outer portion of the conductive layer has the metal component more than the inner portion of the conductive layer. It is preferable to include many. In this case, it is possible to effectively reduce the initial connection resistance between the electrodes and further effectively suppress the increase in the connection resistance under high temperature and high humidity.
- the outer portion of the conductive layer is preferably a conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer toward the inner side in the thickness direction.
- the inner portion of the conductive layer is preferably an inner portion of the conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer.
- content of the said metal component does not need to have a concentration gradient in the whole electroconductive layer.
- the content of the metal component may be substantially uniform throughout the conductive layer. Therefore, the total content of tungsten and molybdenum may exceed 5% by weight in all the conductive layer portions.
- the concentration of nickel ions eluted is 100 ppm / cm per unit surface area of the conductive particles. It is preferable that it is 2 or less. In this case, the connection resistance between the electrodes is effectively reduced, and the current capacity that the conductive particles in contact with the electrodes can withstand is further increased.
- the conductive layer is formed by electroless nickel plating using a reducing agent, and the conductive layer does not include a component derived from the reducing agent or includes a component derived from the reducing agent and
- the content of the component derived from the reducing agent in 100% by weight as a whole is preferably 5% by weight or less. In this case, it is possible to effectively reduce the connection resistance between the electrodes and further effectively suppress the increase in the connection resistance under high temperature and high humidity.
- the content of the component derived from the reducing agent in 100% by weight of the entire conductive layer is more preferably 4% by weight or less, still more preferably 3% by weight or less, still more preferably 1% by weight or less, particularly preferably. Is 0.3% by weight or less, most preferably 0.1% by weight or less.
- Examples of the component derived from the reducing agent include phosphorus and boron.
- the reducing agent is preferably a phosphorus-containing reducing agent or a boron-containing reducing agent, and more preferably a boron-containing reducing agent.
- the component derived from the reducing agent is preferably phosphorus or boron, and more preferably boron.
- FIG. 1 is a cross-sectional view showing conductive particles according to the first embodiment of the present invention.
- the conductive particle 1 includes a base particle 2, a conductive layer 3, a plurality of core substances 4, and a plurality of insulating substances 5.
- the conductive layer 3 is disposed on the surface of the base particle 2.
- the conductive particle 1 is a coated particle in which the surface of the base particle 2 is coated with the conductive layer 3.
- the conductive particle 1 has a plurality of protrusions 1a on the surface.
- the conductive layer 3 has a plurality of protrusions 3a on the outer surface.
- a plurality of core substances 4 are arranged on the surface of the base particle 2.
- a plurality of core materials 4 are embedded in the conductive layer 3.
- the core substance 4 is disposed inside the protrusions 1a and 3a.
- the conductive layer 3 covers a plurality of core materials 4.
- the outer surface of the conductive layer 3 is raised by the plurality of core materials 4 to form protrusions 1a and 3a.
- the conductive particles 1 have an insulating material 5 disposed on the outer surface of the conductive layer 3. At least a part of the outer surface of the conductive layer 3 is covered with the insulating material 5.
- the insulating substance 5 is made of an insulating material and is an insulating particle.
- the electroconductive particle which concerns on this invention may have the insulating substance arrange
- the conductive particles according to the present invention do not necessarily have an insulating material.
- FIG. 2 is a cross-sectional view showing conductive particles according to the second embodiment of the present invention.
- the conductive particles 11 shown in FIG. 2 include base material particles 2, a second conductive layer 12 (another conductive layer), a conductive layer 13 (first conductive layer), a plurality of core substances 4, and a plurality of And an insulating material 5.
- the conductive particles 1 and the conductive particles 11 are different only in the conductive layer. That is, the conductive particle 1 has a single-layered conductive layer, whereas the conductive particle 11 has a two-layered second conductive layer 12 and conductive layer 13.
- the conductive layer 13 is disposed on the surface of the base particle 2.
- a second conductive layer 12 (another conductive layer) is disposed between the base particle 2 and the conductive layer 13. Therefore, the second conductive layer 12 is disposed on the surface of the base particle 2, and the conductive layer 13 is disposed on the surface of the second conductive layer 12.
- the conductive layer 13 has a plurality of protrusions 13a on the outer surface.
- the conductive particles 11 have a plurality of protrusions 11a on the surface.
- FIG. 3 is a cross-sectional view showing conductive particles according to the third embodiment of the present invention.
- the conductive particle 21 shown in FIG. 3 has the base particle 2 and the conductive layer 22.
- the conductive layer 22 is disposed on the surface of the base particle 2.
- the conductive particles 21 do not have a core substance.
- the conductive particles 21 do not have protrusions on the surface.
- the conductive particles 21 are spherical.
- the conductive layer 22 has no protrusion on the surface.
- the electroconductive particle which concerns on this invention does not need to have a litigation
- the conductive particles 21 do not have an insulating material.
- the conductive particles 21 may have an insulating material disposed on the surface of the conductive layer 22.
- Examples of the substrate particles include resin particles, inorganic particles excluding metals, organic-inorganic hybrid particles, and metal particles.
- the substrate particles are preferably substrate particles excluding metal particles, and more preferably resin particles, inorganic particles excluding metal, or organic-inorganic hybrid particles.
- the base material particles are preferably resin particles formed of a resin.
- the said electroconductive particle is compressed by crimping
- the substrate particles are resin particles, the conductive particles are easily deformed during the pressure bonding, and the contact area between the conductive particles and the electrode is increased. For this reason, the conduction
- the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate.
- polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyisobutylene, and polybutadiene
- acrylic resins such as polymethyl methacrylate and polymethyl acrylate.
- Resin for forming the resin particles can be designed and synthesized, and the hardness of the base particles can be easily controlled within a suitable range, which is suitable for conductive materials and having physical properties at the time of compression.
- the monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer. And so on.
- non-crosslinkable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (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 ( Alkyl (meth) acrylates such as meth) acrylate and isobornyl (meth) acrylate; acids such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate and glycidyl (meth) acrylate Atom
- crosslinkable monomer examples include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, (poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate; triallyl (iso) cyanurate, tri Lil
- the resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group by a known method. Examples of this method include a method of suspension polymerization in the presence of a radical polymerization initiator, and a method of polymerizing by swelling a monomer together with a radical polymerization initiator using non-crosslinked seed particles.
- the substrate particles are inorganic particles or organic-inorganic hybrid particles excluding metal particles
- examples of the inorganic material for forming the substrate particles include silica and carbon black. Although it does not specifically limit as the particle
- grains obtained by performing are mentioned.
- examples of the organic / inorganic hybrid particles include organic / inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
- the substrate particles are metal particles
- examples of the metal for forming the metal particles include silver, copper, nickel, silicon, gold, and titanium.
- the substrate particles are preferably not metal particles.
- the particle diameter of the substrate particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, still more preferably 1.5 ⁇ m or more, particularly preferably 2 ⁇ m or more, preferably 1000 ⁇ m or less, More preferably, it is 500 ⁇ m or less, still more preferably 300 ⁇ m or less, still more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, particularly preferably 5 ⁇ m or less, and most preferably 3 ⁇ m or less.
- the particle diameter of the substrate particles When the particle diameter of the substrate particles is equal to or greater than the above lower limit, the contact area between the conductive particles and the electrodes is increased, so that the conduction reliability between the electrodes is further increased, and the electrodes are connected via the conductive particles. The connection resistance between them becomes even lower. Further, when forming the conductive layer on the surface of the base particle by electroless plating, it becomes difficult to aggregate and the aggregated conductive particles are hardly formed. When the particle diameter is not more than the above upper limit, the conductive particles are easily compressed, the connection resistance between the electrodes is further reduced, and the distance between the electrodes is further reduced.
- the particle diameter of the base particle indicates a diameter when the base particle is a true sphere, and indicates a maximum diameter when the base particle is not a true sphere.
- the particle diameter of the substrate particles is particularly preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
- the particle diameter of the substrate particles is in the range of 0.1 to 5 ⁇ m, even when the distance between the electrodes is small and the thickness of the conductive layer is increased, small conductive particles can be obtained.
- the particle diameter of the substrate particles is preferably 0.5 ⁇ m or more. More preferably, it is 2 ⁇ m or more, preferably 3 ⁇ m or less.
- the electroconductive particle which concerns on this invention has the electroconductive layer arrange
- the conductive layer includes nickel and at least one metal component of tungsten and molybdenum.
- a conductive layer containing nickel and at least one metal component of tungsten and molybdenum may be referred to as a conductive layer X.
- the nickel content is 60 weight% or more.
- the total content of tungsten and molybdenum exceeds 5% by weight in 100% by weight of the conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer X toward the inside in the thickness direction.
- the conductive layer X may be directly laminated on the surface of the base particle, or may be disposed on the surface of the base particle via another conductive layer or the like. Furthermore, another conductive layer may be disposed on the surface of the conductive layer X.
- the outer surface of the conductive particles is preferably the conductive layer X.
- the content of the nickel in the entire 100 wt% of the conductive layer X is larger. Therefore, the content of nickel is preferably 65% by weight or more, more preferably 70% by weight or more, still more preferably 75% by weight or more, and further preferably 80% by weight or more in the total 100% by weight of the conductive layer X. Even more preferably, it is 85% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.
- the content of nickel in 100% by weight of the entire conductive layer X may be 97% by weight or more, 97.5% by weight or more, or 98% by weight or more.
- the upper limit of the nickel content can be appropriately changed depending on the contents of tungsten, molybdenum, boron, and the like.
- the content of nickel in 100% by weight of the entire conductive layer X is preferably 99.85% by weight or less, more preferably 99.7% by weight or less, and still more preferably less than 99.45% by weight.
- the connection resistance between the electrodes is further reduced.
- there are few oxide films in the surface of an electrode or a conductive layer there exists a tendency for the connection resistance between electrodes to become low, so that there is much content of the said nickel.
- the conductive layer X contains at least one metal component of tungsten and molybdenum in addition to nickel. That is, the conductive layer X is a nickel-tungsten / molybdenum conductive layer containing nickel and at least one metal component of tungsten and molybdenum. In the conductive layer X, nickel and at least one metal component of tungsten and molybdenum may be alloyed. In the conductive layer X, chromium or seaborgium may be used in addition to tungsten and molybdenum.
- the nickel conductive layer that does not contain both tungsten and molybdenum tends to have a relatively low hardness in the initial stage of compression. For this reason, at the time of connection between electrodes, the effect which excludes the oxide film on the surface of an electrode and electroconductive particle becomes small, and there exists a tendency for connection resistance to become low.
- the thickness of the nickel conductive layer that does not contain both tungsten and molybdenum is increased in order to obtain the effect of lowering the connection resistance further, or to be suitable for applications in which a large current flows, conductive objects may cause connection.
- the member or the substrate tends to be easily damaged. As a result, the conduction reliability between the electrodes in the connection structure tends to be low.
- connection resistance between the electrodes is effectively reduced. Moreover, it is easy to cause a moderate crack in the conductive layer X. When cracks occur when compressed appropriately, damage to the electrodes is less likely to occur, and therefore the connection resistance between the electrodes is further reduced.
- the conductive layer X has an appropriate hardness, when the conductive particles are compressed to connect the electrodes, an appropriate indentation can be formed on the electrodes.
- the indentation formed on the electrode is a concave portion of the electrode formed by pressing the electrode with conductive particles.
- the total content of tungsten and molybdenum (content of metal component) in 100% by weight of the entire conductive layer X is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably. Is 0.2% by weight or more, more preferably 0.5% by weight or more, still more preferably 1% by weight or more, particularly preferably more than 5% by weight, most preferably 10% by weight or more.
- the hardness of the outer surface of the conductive layer is further increased.
- the oxide film on the surface of the electrode or the conductive layer when the oxide film is formed on the surface of the electrode or the conductive layer, the oxide film on the surface of the electrode and the conductive particles can be effectively eliminated, the connection resistance can be lowered, and the obtained connection The impact resistance of the structure can be increased. Furthermore, when the total content of tungsten and molybdenum is equal to or greater than the above lower limit, the magnetism of the outer surface of the conductive layer becomes weak, and a plurality of conductive particles are difficult to aggregate. For this reason, the short circuit between electrodes can be suppressed effectively.
- the upper limit of the total content of tungsten and molybdenum in 100% by weight of the entire conductive layer X can be appropriately changed depending on the contents of nickel, boron, and the like.
- the total content of tungsten and molybdenum in 100% by weight of the entire conductive layer X is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, and particularly preferably 20% by weight. It is as follows.
- the conductive layer X preferably contains boron in addition to nickel.
- the conductive layer X preferably contains nickel, at least one of tungsten and molybdenum, and boron. That is, the conductive layer X is preferably a nickel-tungsten / molybdenum-boron conductive layer containing at least one of nickel, tungsten, and molybdenum and boron.
- nickel and boron may be alloyed, or at least one of tungsten and molybdenum and boron may be alloyed.
- chromium or seaborgium may be used in addition to tungsten, molybdenum, and boron.
- the nickel conductive layer that does not contain boron is relatively soft at the initial stage of compression, and an oxide film on the surface of the electrode and the conductive particles is formed when the electrodes are connected.
- the effect of eliminating tends to be small, and the effect of reducing the connection resistance tends to be small.
- the conductive layer may contain phosphorus instead of boron.
- the effect of eliminating the oxide film on the surface of the electrode and the conductive particles tends to be small, and the effect of reducing the connection resistance tends to be small.
- the thickness of the conductive layer not containing boron or the thickness of the conductive layer containing nickel and phosphorus is increased in order to obtain the effect of lowering the connection resistance or to be suitable for applications in which a large current flows. If the thickness is increased, the connection target member or the substrate tends to be easily damaged by the conductive particles. As a result, the conduction reliability between the electrodes in the connection structure tends to be low.
- the conductive layer X contains boron
- the conductive layer has an appropriate hardness, so that the electrode is more unlikely to be damaged, and thus the connection resistance between the electrodes is further reduced.
- the conductive layer X is a nickel-tungsten / molybdenum-boron conductive layer
- the nickel-tungsten / molybdenum-boron conductive layer has an appropriate hardness.
- an appropriate indentation can be formed on the electrode.
- the indentation formed on the electrode is a concave portion of the electrode formed by pressing the electrode with conductive particles.
- the content of boron in 100% by weight of the conductive layer X is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, preferably 5% by weight. Below, more preferably 4% by weight or less, still more preferably 3% by weight or less, particularly preferably 2.5% by weight or less, and most preferably 2% by weight or less.
- the boron content is not less than the above lower limit, the conductive layer X becomes harder, the oxide film on the surface of the electrode and the conductive particles can be more effectively removed, and the connection resistance between the electrodes is further reduced. . If the boron content is less than or equal to the above upper limit, the contents of nickel, tungsten, molybdenum, and the like are relatively increased, so that the connection resistance between the electrodes is further reduced.
- the conductive layer X contains boron
- the conductive layer is considerably hardened. As a result, even when an impact is applied to the connection structure connecting the electrodes by the conductive particles, poor conduction is unlikely to occur. That is, the impact resistance of the connection structure can be increased.
- the surface of the conductive layer containing nickel and boron has high magnetism, and when the electrodes are electrically connected, the electrodes adjacent to each other in the lateral direction are connected due to the influence of the conductive particles aggregated by magnetism. It tends to be easy.
- the conductive layer X contains nickel, at least one of tungsten and molybdenum, and boron, the magnetic property of the surface of the conductive layer X is considerably reduced. For this reason, it can suppress that several electroconductive particle aggregates. Therefore, when the electrodes are electrically connected, it is possible to prevent the electrodes adjacent in the lateral direction from being connected by the aggregated conductive particles. That is, a short circuit between adjacent electrodes can be further prevented.
- the conductive layer X does not contain phosphorus, or the conductive layer X contains phosphorus, and the content of phosphorus in 100% by weight of the entire conductive layer X is less than 0.5% by weight.
- the content of phosphorus in the total 100% by weight of the conductive layer X is more preferably 0.3% by weight or less, and still more preferably 0.1% by weight or less. It is particularly preferable that the conductive layer X does not contain phosphorus.
- the method for measuring the contents of nickel, tungsten, molybdenum, boron and phosphorus in the conductive layer X is not particularly limited, and various known analysis methods can be used. Examples of this measuring method include absorption spectrometry or spectrum analysis. In the above-mentioned absorption analysis method, a flame absorptiometer, an electric heating furnace absorptiometer, or the like can be used. Examples of the spectrum analysis method include a plasma emission analysis method and a plasma ion source mass spectrometry method.
- ICP emission spectrometer When measuring the contents of nickel, tungsten, molybdenum, boron and phosphorus in the conductive layer X, it is preferable to use an ICP emission spectrometer.
- ICP emission analyzers include ICP emission analyzers manufactured by HORIBA.
- FE-TEM apparatus When measuring the contents of nickel, tungsten, molybdenum, boron and phosphorus in the thickness direction of the conductive layer X, it is preferable to use an FE-TEM apparatus.
- Examples of commercially available FE-TEM devices include JEM-2010 manufactured by JEOL Ltd.
- the metal for forming the other conductive layer is not particularly limited.
- the metal include gold, silver, copper, palladium, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, and tungsten. , Molybdenum, and alloys thereof.
- the metal include tin-doped indium oxide (ITO) and solder. Especially, since the connection resistance between electrodes becomes still lower, an alloy containing tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is more preferable.
- the metal constituting the conductive layer preferably contains nickel.
- the method for forming a conductive layer (another conductive layer and conductive layer X) on the surface of the substrate particle is not particularly limited.
- a method for forming the conductive layer for example, a method by electroless plating, a method by electroplating, a method by physical vapor deposition, and a paste containing metal powder or metal powder and a binder is used for base particles or other conductive layers.
- a method of coating the surface for example, since formation of a conductive layer is simple, the method by electroless plating is preferable.
- Examples of the method by physical vapor deposition include methods such as vacuum vapor deposition, ion plating, and ion sputtering.
- the particle diameter of the conductive particles is preferably 0.11 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 0.51 ⁇ m or more, particularly preferably 1 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 20 ⁇ m or less, and further Preferably it is 5.6 micrometers or less, Most preferably, it is 3.6 micrometers or less.
- the particle diameter of the conductive particles is not less than the above lower limit and not more than the above upper limit, the contact area between the conductive particles and the electrodes is sufficiently large when the electrodes are connected using the conductive particles, and the conductive layer When forming the conductive particles, it becomes difficult to form aggregated conductive particles. Further, the distance between the electrodes connected via the conductive particles does not become too large, and the conductive layer is difficult to peel from the surface of the base material particles.
- the particle diameter of the conductive particles indicates the diameter when the conductive particles are true spherical, and indicates the maximum diameter when the conductive particles are not true spherical.
- the thickness of the conductive layer X is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.3 ⁇ m or less.
- the thickness of the conductive layer X is not less than the above lower limit and not more than the above upper limit, sufficient conductivity can be obtained, and the conductive particles do not become too hard, and the conductive particles are sufficiently bonded at the time of connection between the electrodes. Deform.
- the thickness of the conductive layer X is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, preferably 0.5 ⁇ m or less. More preferably, it is 0.3 ⁇ m or less, and further preferably 0.1 ⁇ m or less.
- the thickness of the conductive layer X is not less than the above lower limit and not more than the above upper limit, the coating with the conductive layer X can be made uniform, and the connection resistance between the electrodes becomes sufficiently low.
- the total thickness of the conductive layer is preferably 0.001 ⁇ m or more, more preferably 0.01 ⁇ m or more, still more preferably 0.05 ⁇ m or more, and particularly preferably 0.1 ⁇ m.
- the thickness is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.3 ⁇ m or less, and still more preferably 0.1 ⁇ m or less.
- the thickness of the conductive layer X is particularly preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less.
- the particle diameter of the base particles is 0.1 ⁇ m or more (more preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more), 5 ⁇ m or less (more preferably 3 ⁇ m or less), and the thickness of the conductive layer X is It is particularly preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less.
- the total thickness of the conductive layer is particularly preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less.
- the particle diameter of the substrate particles is 0.1 ⁇ m or more (more preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more), 5 ⁇ m or less (more preferably 3 ⁇ m or less), and the thickness of the entire conductive layer is It is particularly preferably 0.05 ⁇ m or more and 0.3 ⁇ m or less.
- the conductive particles can be suitably used for applications in which a large current flows. Furthermore, when the conductive particles are compressed to connect the electrodes, it is possible to further suppress the electrodes from being damaged.
- the thickness of the conductive layer X and the thickness of the entire conductive layer can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).
- TEM transmission electron microscope
- Examples of a method for controlling the contents of nickel, tungsten, molybdenum and boron in the conductive layer X include, for example, a method for controlling the pH of a nickel plating solution when the conductive layer X is formed by electroless nickel plating.
- a method of adjusting the concentration of the boron-containing reducing agent, a method of adjusting the tungsten concentration in the nickel plating solution, a method of adjusting the molybdenum concentration in the nickel plating solution, and nickel plating Examples include a method of adjusting the nickel salt concentration in the liquid.
- the compounding amount of the compounding component containing nickel, tungsten, molybdenum or boron is adjusted depending on the formation time of the electroless nickel plating. And the like.
- a catalytic step and an electroless plating step are performed.
- an example of a method for forming an alloy plating layer containing at least one of nickel, tungsten, and molybdenum and boron on the surface of the resin particles by electroless plating will be described.
- a catalyst serving as a starting point for forming a plating layer by electroless plating is formed on the surface of the resin particles.
- the surface of the resin particles is activated with an acid solution or an alkali solution
- the reducing agent a boron-containing reducing agent is preferably used.
- a phosphorus-containing reducing agent such as sodium hypophosphite may be used as the reducing agent.
- a nickel plating bath containing a nickel salt, at least one of a tungsten-containing compound and a molybdenum-containing compound, and the boron-containing reducing agent is used.
- nickel By immersing the resin particles in the nickel plating bath, nickel can be deposited on the surface of the resin particles on which the catalyst is formed, and includes at least one of nickel, tungsten, and molybdenum and boron.
- a conductive layer can be formed.
- Examples of the tungsten-containing compound include tungsten boride and sodium tungstate.
- Examples of the molybdenum-containing compound include molybdenum boride and sodium molybdate.
- Examples of the boron-containing reducing agent include dimethylamine borane, sodium borohydride, potassium borohydride, and the like.
- the conductive particles according to the present invention preferably have protrusions on the surface.
- the conductive layer preferably has a protrusion on the outer surface.
- An oxide film is often formed on the surface of the electrode connected by the conductive particles.
- an oxide film is often formed on the surface of the conductive layer of the conductive particles.
- the conductive particles have an insulating material on the surface, or when the conductive particles are dispersed in the resin and used as a conductive material, the conductive particles and the electrodes are insulated by the protrusions of the conductive particles. Substances or resins can be effectively excluded. For this reason, the conduction
- the number of protrusions on the outer surface of the conductive layer per one conductive particle is preferably 3 or more, more preferably 5 or more.
- the upper limit of the number of protrusions is not particularly limited. The upper limit of the number of protrusions can be appropriately selected in consideration of the particle diameter of the conductive particles.
- the average height of the plurality of protrusions is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- the connection resistance between the electrodes can be effectively lowered.
- the core substance Since the core substance is embedded in the conductive layer, it is easy for the conductive layer to have a plurality of protrusions on the outer surface. However, in order to form protrusions on the surfaces of the conductive particles and the conductive layer, the core substance is not necessarily used.
- a core material is attached to the surface of the base particle, and then a conductive layer is formed by electroless plating, and a conductive layer is formed on the surface of the base particle by electroless plating. Thereafter, a method of attaching a core substance and further forming a conductive layer by electroless plating may be used.
- the core substance is added to the dispersion of the base particle, and the core substance is applied to the surface of the base particle, for example, van der Waals force.
- the method of making a core substance accumulate and adhere on the surface of the base particle in a dispersion liquid is preferable.
- the material constituting the core material there may be mentioned a conductive material and a non-conductive material.
- the conductive material include conductive non-metals such as metals, metal oxides, and graphite, and conductive polymers.
- the conductive polymer include polyacetylene.
- the non-conductive substance include silica, alumina, barium titanate, zirconia, and the like. Among them, metal is preferable because conductivity can be increased and connection resistance can be effectively reduced.
- the core substance is preferably metal particles.
- the metal examples include gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium and cadmium, and tin-lead.
- examples thereof include alloys composed of two or more metals such as alloys, tin-copper alloys, tin-silver alloys, tin-lead-silver alloys, and tungsten carbide. Of these, 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 layer.
- the metal constituting the core material preferably includes a metal constituting the conductive layer. It is preferable that the metal which comprises the said core substance contains nickel. It is preferable that the metal which comprises the said core substance contains nickel.
- the shape of the core substance is not particularly limited.
- the shape of the core substance is preferably a lump.
- Examples of the core substance include a particulate lump, an agglomerate in which a plurality of fine particles are aggregated, and an irregular lump.
- the average diameter (average particle diameter) of the core substance is preferably 0.001 ⁇ m or more, more preferably 0.05 ⁇ m or more, preferably 0.9 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- the connection resistance between the electrodes can be effectively reduced.
- the “average diameter (average particle diameter)” of the core substance indicates a number average diameter (number average particle diameter).
- the average diameter of the core material is obtained by observing 50 arbitrary core materials with an electron microscope or an optical microscope and calculating an average value.
- Inorganic particles may be disposed on the surface of the core substance. It is preferable that there are a plurality of inorganic particles arranged on the surface of the core substance. Inorganic particles may be attached to the surface of the core substance. You may use the composite particle provided with such an inorganic particle and a core substance.
- the size (average diameter) of the inorganic particles is preferably smaller than the size (average diameter) of the core substance, and the inorganic particles are preferably inorganic fine particles.
- Examples of the material of the inorganic particles arranged on the surface of the core substance include silica (silicon dioxide, Mohs hardness 6-7), zirconia (Mohs hardness 8-9), alumina (Mohs hardness 9), tungsten carbide (Mohs). Hardness 9), diamond (Mohs hardness 10), and the like.
- the inorganic particles are preferably silica, zirconia, alumina, tungsten carbide or diamond, and are also preferably silica, zirconia, alumina or diamond.
- the Mohs hardness of the inorganic particles is preferably 5 or more, more preferably 6 or more.
- the Mohs hardness of the inorganic particles is preferably larger than the Mohs hardness of the conductive layer.
- the Mohs hardness of the inorganic particles is preferably larger than the Mohs hardness of the second conductive layer.
- the absolute value of the difference between the Mohs hardness of the inorganic particles and the Mohs hardness of the conductive layer, and the absolute value of the difference between the Mohs hardness of the inorganic particles and the Mohs hardness of the second conductive layer are preferably 0.1. Above, more preferably 0.2 or more, still more preferably 0.5 or more, particularly preferably 1 or more.
- the inorganic particles are harder than all the metals constituting the plurality of layers, so that the effect of reducing the connection resistance is more effectively exhibited. Is done.
- the average particle size of the inorganic particles is preferably 0.0001 ⁇ m or more, more preferably 0.005 ⁇ m or more, preferably 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less.
- the connection resistance between the electrodes can be effectively reduced.
- the “average particle size” of the inorganic particles indicates the number average particle size.
- the average particle diameter of the inorganic particles is obtained by observing 50 arbitrary inorganic particles with an electron microscope or an optical microscope and calculating an average value.
- the average diameter of the composite particles is preferably 0.0012 ⁇ m or more, more preferably 0.0502 ⁇ m or more, preferably Is 1.9 ⁇ m or less, more preferably 1.2 ⁇ m or less.
- the average diameter of the composite particles is not less than the above lower limit and not more than the above upper limit, the connection resistance between the electrodes can be effectively reduced.
- the “average diameter (average particle diameter)” of the composite particles indicates a number average diameter (number average particle diameter).
- the average diameter of the composite particles is determined by observing 50 arbitrary composite particles with an electron microscope or an optical microscope and calculating an average value.
- the conductive particles according to the present invention preferably include an insulating material disposed on the surface of the conductive layer.
- an insulating material disposed on the surface of the conductive layer.
- an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between electrodes adjacent in the lateral direction instead of between the upper and lower electrodes.
- the insulating substance between the conductive layer of the conductive particles and the electrodes can be easily excluded. Since the conductive particles have a plurality of protrusions on the outer surface of the conductive layer, the insulating material between the conductive layer of the conductive particles and the electrode can be easily excluded.
- the insulating material is an insulating particle because the insulating material can be more easily removed when the electrodes are crimped.
- thermoplastic resin examples include vinyl polymers and vinyl copolymers.
- thermosetting resin an epoxy resin, a phenol resin, a melamine resin, etc.
- water-soluble resin examples include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyethylene oxide, and methyl cellulose. Of these, water-soluble resins are preferable, and polyvinyl alcohol is more preferable.
- Examples of a method for disposing an insulating material on the surface of the conductive layer include a chemical method and a physical or mechanical method.
- Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method.
- Examples of the physical or mechanical method include spray drying, hybridization, electrostatic adhesion, spraying, dipping, and vacuum deposition. In particular, since the insulating substance is difficult to be detached, a method of disposing the insulating substance on the surface of the conductive layer through a chemical bond is preferable.
- the average diameter (average particle diameter) of the insulating material can be appropriately selected depending on the particle diameter of the conductive particles and the use of the conductive particles.
- the average diameter (average particle diameter) of the insulating material is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
- the average diameter of the insulating material is not less than the above lower limit, the conductive layers of the plurality of conductive particles are difficult to contact when the conductive particles are dispersed in the binder resin.
- the average diameter of the insulating particles is not more than the above upper limit, it is not necessary to make the pressure too high in order to eliminate the insulating material between the electrodes and the conductive particles when the electrodes are connected. There is no need for heating.
- the “average diameter (average particle diameter)” of the insulating material indicates a number average diameter (number average particle diameter).
- the average diameter of the insulating material is obtained using a particle size distribution measuring device or the like.
- the conductive material according to the present invention includes the conductive particles described above and a binder resin.
- the conductive particles are preferably dispersed in a binder resin and used as a conductive material.
- the conductive material is preferably an anisotropic conductive material.
- the binder resin is not particularly limited.
- As the binder resin a known insulating resin is used.
- binder resin examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers.
- vinyl resins examples include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers.
- the said binder resin only 1 type may be used and 2 or more types may be used together.
- Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin.
- examples of the thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin.
- examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin, and an unsaturated polyester resin.
- the curable resin may be a room temperature curable resin, a thermosetting resin, a photocurable resin, or a moisture curable resin.
- the curable resin may be used in combination with a curing agent.
- thermoplastic block copolymer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a styrene-isoprene. -Hydrogenated products of styrene block copolymers.
- the elastomer examples include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
- the conductive material includes, for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
- a filler for example, a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, and a light stabilizer.
- Various additives such as an agent, an ultraviolet absorber, a lubricant, an antistatic agent and a flame retardant may be contained.
- the method for dispersing the conductive particles in the binder resin is not particularly limited, and a conventionally known dispersion method can be used.
- Examples of a method for dispersing the conductive particles in the binder resin include a method in which the conductive particles are added to the binder resin and then kneaded and dispersed with a planetary mixer or the like. The conductive particles are dispersed in water. Alternatively, after uniformly dispersing in an organic solvent using a homogenizer or the like, it is added to the binder resin and kneaded with a planetary mixer or the like, and the binder resin is diluted with water or an organic solvent. Then, the method of adding the said electroconductive particle, kneading with a planetary mixer etc. and disperse
- distributing is mentioned.
- the conductive material according to the present invention can be used as a conductive paste and a conductive film.
- the conductive material according to the present invention is a conductive film
- a film that does not include conductive particles may be laminated on a conductive film that includes conductive particles.
- the conductive paste is preferably an anisotropic conductive paste.
- the conductive film is preferably an anisotropic conductive film.
- the content of the binder resin is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably 70% by weight or more, preferably 99.% or more. It is 99 weight% or less, More preferably, it is 99.9 weight% or less.
- the content of the binder resin is not less than the above lower limit and not more than the above upper limit, the conductive particles are efficiently arranged between the electrodes, and the connection reliability of the connection target member connected by the conductive material is further increased.
- the content of the conductive particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 40% by weight or less, more preferably 20% by weight or less, More preferably, it is 10 weight% or less.
- the content of the conductive particles is not less than the above lower limit and not more than the above upper limit, the conduction reliability between the electrodes is further enhanced.
- connection structure can be obtained by connecting the connection target members using the conductive particles of the present invention or using a conductive material containing the conductive particles and a binder resin.
- connection structure includes a first connection target member, a second connection target member, and a connection portion connecting the first and second connection target members, and the connection portion is a conductive member of the present invention.
- the connection structure is preferably formed of conductive particles or formed of a conductive material (such as an anisotropic conductive material) containing the conductive particles and a binder resin.
- the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.
- FIG. 4 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
- connection portion 54 includes a first connection target member 52, a second connection target member 53, and a connection portion 54 that connects the first and second connection target members 52 and 53.
- the connection portion 54 is formed by curing a conductive material including the conductive particles 1.
- the conductive particles 1 are schematically shown for convenience of illustration.
- the first connection target member 52 has a plurality of electrodes 52b on the upper surface 52a (front surface).
- the second connection target member 53 has a plurality of electrodes 53b on the lower surface 53a (front surface).
- the electrode 52 b and the electrode 53 b are electrically connected by one or a plurality of conductive particles 1. Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1.
- connection structure is not particularly limited.
- the conductive material is disposed between the first connection target member and the second connection target member to obtain a laminate, and then the laminate is heated and pressurized. Methods and the like.
- the pressurizing pressure is about 9.8 ⁇ 10 4 to 4.9 ⁇ 10 6 Pa.
- the heating temperature is about 120 to 220 ° C.
- connection target member examples include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as circuit boards such as printed boards, flexible printed boards, and glass boards.
- the connection target member is preferably an electronic component.
- the conductive particles are preferably used for electrical connection of electrodes in an electronic component.
- the electrode provided on the connection target member examples include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, and a tungsten electrode.
- the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode.
- the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode.
- the electrode formed only with aluminum may be sufficient and the electrode by which the aluminum layer was laminated
- the material for the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.
- Example 1 Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
- the resin particles were taken out by dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
- a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium tungstate was prepared. While stirring the obtained suspension at 60 ° C., the above nickel plating solution was gradually added dropwise to the suspension, and an electroless plating first step was performed.
- a plating solution pH 11.0 containing 0.92 mol / L of dimethylamine borane and 0.01 mol / L of sodium tungstate was gradually added dropwise, and an electroless plating late step was performed. Thereafter, the suspension is filtered to remove the particles, washed with water, and dried to obtain conductive particles having a nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) on the surface of the resin particles. It was.
- Example 2 A nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.12 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 3 A nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.23 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 4 A nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 5 In the first step and the second step, the resin particles were prepared in the same manner as in Example 1 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium tungstate concentration was changed to 0.35 mol / L. Conductive particles having a nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) on the surface were obtained.
- Example 6 Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Electroless nickel plating step In the same manner as in Example 1, conductive particles were obtained in which a nickel-tungsten-boron conductive layer (thickness: 0.1 ⁇ m) was disposed on the surface of the resin particles.
- Example 7 A nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 6 except that the sodium tungstate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 8 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 6 10 g of the conductive particles obtained in Example 6 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 9 A nickel-tungsten-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 1 except that the sodium tungstate concentration was changed to 0.46 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 10 A nickel-tungsten-boron conductive layer (thickness of about 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 3 except that the dimethylamine borane concentration was changed to 4.60 mol / L in the first and second steps. The electroconductive particle by which was arrange
- Comparative Example 2 A conductive layer (thickness 0) containing nickel and boron on the surface of the resin particles in the same manner as in Example 1 except that sodium tungstate 0.01 mol / L in the nickel plating solution was not used in the first step and the second step. .1 ⁇ m) was obtained.
- Divinylbenzene copolymer resin particles (“Micropearl SP-203” manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 ⁇ m were prepared.
- the resin particles were taken out by dispersing 10 parts by weight of the resin particles in 100 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst solution using an ultrasonic disperser, and then filtering the solution. Next, the resin particles were added to 100 parts by weight of a 1% by weight dimethylamine borane solution to activate the surface of the resin particles. The resin particles whose surface was activated were sufficiently washed with water, and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension.
- a nickel plating solution (pH 8.5) containing 0.23 mol / L of nickel sulfate, 0.92 mol / L of dimethylamine borane, 0.5 mol / L of sodium citrate and 0.01 mol / L of sodium molybdate was prepared.
- a plating solution pH 11.0 containing 0.92 mol / L of dimethylamine borane and 0.01 mol / L of sodium molybdate was gradually added dropwise to carry out the latter stage of electroless plating. Thereafter, the suspension is filtered to take out the particles, washed with water, and dried to obtain conductive particles having a nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) disposed on the surface of the resin particles. It was.
- Example 12 A nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.12 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 13 A nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.23 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 14 A nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 15 Resin particles were prepared in the same manner as in Example 11 except that the dimethylamine borane concentration was changed to 2.76 mol / L and the sodium molybdate concentration was changed to 0.35 mol / L in the first and second steps. Conductive particles having a nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) disposed on the surface were obtained.
- Example 16 (1) Palladium adhesion process Divinylbenzene resin particles (“Micropearl SP-205” manufactured by Sekisui Chemical Co., Ltd.) having a particle diameter of 5.0 ⁇ m were prepared. The resin particles were etched and washed with water. Next, resin particles were added to 100 mL of a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- a palladium-catalyzed solution containing 8% by weight of a palladium catalyst and stirred. Then, it filtered and wash
- Electroless nickel plating step In the same manner as in Example 11, conductive particles having a nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) disposed on the surface of resin particles were obtained.
- Example 17 A nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 16 except that the sodium molybdate concentration was changed to 0.35 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 18 (1) Preparation of insulating particles Into a 1000 mL separable flask equipped with a four-neck separable cover, stirring blade, three-way cock, cooling tube and temperature probe, 100 mmol of methyl methacrylate and N, N, N-trimethyl Ion-exchanged water containing a monomer composition containing 1 mmol of —N-2-methacryloyloxyethylammonium chloride and 1 mmol of 2,2′-azobis (2-amidinopropane) dihydrochloride so that the solid content is 5% by weight. Then, the mixture was stirred at 200 rpm and polymerized at 70 ° C. for 24 hours under a nitrogen atmosphere. After completion of the reaction, it was freeze-dried to obtain insulating particles having an ammonium group on the surface, an average particle size of 220 nm, and a CV value of 10%.
- the insulating particles were dispersed in ion exchange water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.
- Example 16 10 g of the conductive particles obtained in Example 16 were dispersed in 500 mL of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. After filtration through a 3 ⁇ m mesh filter, the particles were further washed with methanol and dried to obtain conductive particles having insulating particles attached thereto.
- Example 19 A nickel-molybdenum-boron conductive layer (thickness 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 11 except that the sodium molybdate concentration was changed to 0.46 mol / L in the first and second steps. Arranged conductive particles were obtained.
- Example 20 A nickel-molybdenum-boron conductive layer (thickness: about 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 13 except that the dimethylamine borane concentration was changed to 4.60 mol / L in the first and second steps. The electroconductive particle by which was arrange
- Example 21 A nickel-tungsten-molybdenum-boron conductive layer (thickness of about 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Example 6 except that 0.01 mol / L of sodium molybdate was added in the first and second steps. The electroconductive particle by which was arrange
- Comparative Example 4 A nickel-tungsten-molybdenum-boron conductive layer (thickness of about 0.1 ⁇ m) was formed on the surface of the resin particles in the same manner as in Comparative Example 1 except that sodium molybdate 0.01 mol / L was added in the first and second steps. The electroconductive particle by which was arrange
- the distribution of the content of each component in the thickness direction of the conductive layer (the content of each component in the conductive layer portion having a thickness of 5 nm from the outer surface of the conductive layer toward the inside in the thickness direction) is evaluated as follows. did.
- a thin film section of the obtained conductive particles was prepared using a focused ion beam.
- JEM-2010FEF transmission electron microscope
- EDS energy dispersive X-ray analyzer
- the plating state of 50 conductive particles obtained was observed with a scanning electron microscope. The presence or absence of plating unevenness such as plating cracking or plating peeling was observed. The case where the number of conductive particles in which plating unevenness was confirmed was 4 or less was judged as “good”, and the case where the number of conductive particles in which plating unevenness was confirmed was 5 or more was judged as “bad”.
- the obtained anisotropic conductive material was stored at 25 ° C. for 72 hours. After storage, it was evaluated whether or not the conductive particles aggregated in the anisotropic conductive material were settled. The case where the aggregated conductive particles were not settled was determined as “good”, and the case where the aggregated conductive particles were sedimented was determined as “bad”.
- connection structure 10 parts by weight of bisphenol A type epoxy resin (“Epicoat 1009” manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of acrylic rubber (weight average molecular weight of about 800,000), 200 parts by weight of methyl ethyl ketone, and a microcapsule type curing agent (Asahi Kasei Chemicals) "HX3941HP” manufactured by HX3941) and 2 parts by weight of a silane coupling agent ("SH6040" manufactured by Toray Dow Corning Silicone Co., Ltd.) are mixed, and the conductive particles are added so that the content is 3% by weight.
- a resin composition was obtained by dispersing.
- the obtained resin composition was applied to a 50 ⁇ m-thick PET (polyethylene terephthalate) film whose one surface was release-treated, and dried with hot air at 70 ° C. for 5 minutes to produce an anisotropic conductive film.
- the thickness of the obtained anisotropic conductive film was 12 ⁇ m.
- the obtained anisotropic conductive film was cut into a size of 5 mm ⁇ 5 mm.
- a two-layer flexible printed board (width 2 cm, length 1 cm) having the same aluminum electrode was aligned and aligned so that the electrodes overlapped.
- the laminated body of the glass substrate and the two-layer flexible printed circuit board was thermocompression bonded under pressure bonding conditions of 10 N, 180 ° C., and 20 seconds to obtain a connection structure.
- a two-layer flexible printed board in which an aluminum electrode is directly formed on a polyimide film was used.
- connection resistance measurement The connection resistance between the opposing electrodes of the obtained connection structure was measured by the 4-terminal method. The initial connection resistance was determined according to the following criteria.
- Connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
- connection resistance after high-temperature and high-humidity test The connection structure obtained by the above (6) evaluation of the initial connection resistance was allowed to stand for 100 hours under the conditions of 85 ° C. and 85% humidity. The connection resistance between the electrodes of the connection structure after being allowed to stand was measured by the four-terminal method, and the obtained measured value was used as the connection resistance after the high temperature and high humidity test. Moreover, the connection resistance after a high temperature, high humidity test was determined according to the following criteria.
- connection resistance is 2.0 ⁇ or less ⁇ : Connection resistance exceeds 2.0 ⁇ , 3.0 ⁇ or less ⁇ : Connection resistance exceeds 3.0 ⁇ , 5.0 ⁇ or less ⁇ : Connection resistance exceeds 5.0 ⁇
- Impact resistance was evaluated by dropping the connection structure obtained in the above (6) evaluation of the initial connection resistance from a position having a height of 70 cm and confirming conduction. The case where the rate of increase in resistance value from the initial resistance value was 50% or less was determined as “good”, and the case where the rate of increase in resistance value from the initial resistance value exceeded 50% was determined as “bad”.
- the 5 nm conductive layer portion indicates a conductive layer portion having a thickness of 5 nm inward in the thickness direction from the outer surface of the conductive layer.
- the eluted nickel ion concentration indicates the eluted nickel ion concentration per unit surface area of the conductive particles.
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Abstract
Description
上記基材粒子としては、樹脂粒子、金属を除く無機粒子、有機無機ハイブリッド粒子及び金属粒子等が挙げられる。上記基材粒子は、金属粒子を除く基材粒子であることが好ましく、樹脂粒子、金属を除く無機粒子又は有機無機ハイブリッド粒子であることがより好ましい。
本発明に係る導電性粒子は、基材粒子の表面上に配置されている導電層を有する。上記導電層は、ニッケルと、タングステン及びモリブデンの内の少なくとも1種の金属成分とを含む。以下、ニッケルと、タングステン及びモリブデンの内の少なくとも1種の金属成分とを含む導電層を、導電層Xと記載することがある。上記導電層Xの全体100重量%中、ニッケルの含有量は60重量%以上である。上記導電層Xの外表面から厚み方向に内側に向かって5nmの厚みの導電層部分100重量%中、タングステン及びモリブデンの合計の含有量は5重量%を超える。
上記芯物質が上記導電層中に埋め込まれていることによって、上記導電層が外表面に複数の突起を有するようにすることが容易である。但し、導電性粒子及び導電層の表面に突起を形成するために、芯物質を必ずしも用いなくてもよい。
本発明に係る導電性粒子は、上記導電層の表面上に配置された絶縁物質を備えることが好ましい。この場合には、導電性粒子を電極間の接続に用いると、隣接する電極間の短絡を防止できる。具体的には、複数の導電性粒子が接触したときに、複数の電極間に絶縁物質が存在するので、上下の電極間ではなく横方向に隣り合う電極間の短絡を防止できる。なお、電極間の接続の際に、2つの電極で導電性粒子を加圧することにより、導電性粒子の導電層と電極との間の絶縁物質を容易に排除できる。導電性粒子が導電層の外表面に複数の突起を有するので、導電性粒子の導電層と電極との間の絶縁物質を容易に排除できる。
本発明に係る導電材料は、上述した導電性粒子と、バインダー樹脂とを含む。上記導電性粒子は、バインダー樹脂中に分散され、導電材料として用いられることが好ましい。上記導電材料は、異方性導電材料であることが好ましい。
本発明の導電性粒子を用いて、又は該導電性粒子とバインダー樹脂とを含む導電材料を用いて、接続対象部材を接続することにより、接続構造体を得ることができる。
粒子径が3.0μmであるジビニルベンゼン共重合体樹脂粒子(積水化学工業社製「ミクロパールSP-203」)を用意した。
前期工程及び後期工程において、タングステン酸ナトリウム濃度を0.12mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、タングステン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、タングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、ジメチルアミンボラン濃度を2.76mol/Lに変更したこと、並びにタングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)パラジウム付着工程
粒子径が5.0μmであるジビニルベンゼン樹脂粒子(積水化学工業社製「ミクロパールSP-205」)を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
パラジウムが付着された樹脂粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒子径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
実施例1と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、タングステン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例6と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径220nm及びCV値10%の絶縁性粒子を得た。
前期工程及び後期工程において、タングステン酸ナトリウム濃度を0.46mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、ジメチルアミンボラン濃度を4.60mol/Lに変更したこと以外は実施例3と同様にして、樹脂粒子の表面にニッケル-タングステン-ボロン導電層(厚み約0.1μm)が配置された導電性粒子を得た。
前期工程において、ニッケルめっき液におけるジメチルアミンボラン0.92mol/Lを、次亜リン酸ナトリウム0.5mol/Lに変更したこと以外は実施例1と同様にして、樹脂粒子の表面にニッケルとタングステンとリンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、ニッケルめっき液におけるタングステン酸ナトリウム0.01mol/Lを用いなかったこと以外は実施例1と同様にして、樹脂粒子の表面にニッケルとボロンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。
粒子径が3.0μmであるジビニルベンゼン共重合体樹脂粒子(積水化学工業社製「ミクロパールSP-203」)を用意した。
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を0.12mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を0.23mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、ジメチルアミンボラン濃度を2.76mol/Lに変更したこと、並びにモリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)パラジウム付着工程
粒子径が5.0μmであるジビニルベンゼン樹脂粒子(積水化学工業社製「ミクロパールSP-205」)を用意した。この樹脂粒子をエッチングし、水洗した。次に、パラジウム触媒を8重量%含むパラジウム触媒化液100mL中に樹脂粒子を添加し、攪拌した。その後、ろ過し、洗浄した。pH6の0.5重量%ジメチルアミンボラン液に樹脂粒子を添加し、パラジウムが付着された樹脂粒子を得た。
パラジウムが付着された樹脂粒子をイオン交換水300mL中で3分間攪拌し、分散させ、分散液を得た。次に、金属ニッケル粒子スラリー(平均粒子径100nm)1gを3分間かけて上記分散液に添加し、芯物質が付着された樹脂粒子を得た。
実施例11と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を0.35mol/Lに変更したこと以外は実施例16と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
(1)絶縁性粒子の作製
4ツ口セパラブルカバー、攪拌翼、三方コック、冷却管及び温度プローブが取り付けられた1000mLのセパラブルフラスコに、メタクリル酸メチル100mmolと、N,N,N-トリメチル-N-2-メタクリロイルオキシエチルアンモニウムクロライド1mmolと、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩1mmolとを含むモノマー組成物を固形分率が5重量%となるようにイオン交換水に秤取した後、200rpmで攪拌し、窒素雰囲気下70℃で24時間重合を行った。反応終了後、凍結乾燥して、表面にアンモニウム基を有し、平均粒子径220nm及びCV値10%の絶縁性粒子を得た。
前期工程及び後期工程において、モリブデン酸ナトリウム濃度を0.46mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、ジメチルアミンボラン濃度を4.60mol/Lに変更したこと以外は実施例13と同様にして、樹脂粒子の表面にニッケル-モリブデン-ボロン導電層(厚み約0.1μm)が配置された導電性粒子を得た。
ニッケルめっき液におけるジメチルアミンボラン0.92mol/Lを、次亜リン酸ナトリウム0.5mol/Lに変更したこと以外は実施例11と同様にして、樹脂粒子の表面にニッケルとモリブデンとリンとを含む導電層(厚み0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、モリブデン酸ナトリウム0.01mol/Lを追加したこと以外は実施例6と同様にして、樹脂粒子の表面にニッケル-タングステン-モリブデン-ボロン導電層(厚み約0.1μm)が配置された導電性粒子を得た。
前期工程及び後期工程において、モリブデン酸ナトリウム0.01mol/Lを追加したこと以外は比較例1と同様にして、樹脂粒子の表面にニッケル-タングステン-モリブデン-ボロン導電層(厚み約0.1μm)が配置された導電性粒子を得た。
(1)導電層の全体100重量%中のニッケル、ボロン、タングステン及びモリブデンの含有量
60%硝酸5mLと37%塩酸10mLとの混合液に、導電性粒子5gを加え、導電層を完全に溶解させ、溶液を得た。得られた溶液を用いて、ニッケル、ボロン、タングステン及びモリブデンの含有量をICP-MS分析器(日立製作所社製)により分析した。なお、実施例の導電性粒子における導電層はリンを含んでいなかった。
導電層の厚み方向における各成分の含有量の分布を測定した。導電層の外表面から厚み方向に内側に向かって5nmの厚みの導電層部分において、ニッケル、ボロン、タングステン及びモリブデンの各含有量を評価した。
複数の導電性粒子10重量部を5重量%クエン酸水溶液100重量部に25℃で1分間浸漬した。ICP発光分析装置(HORIBA社製「ULTIMA2」)を用いて、浸漬後の液中に溶出したニッケルイオン濃度を測定した。導電性粒子の単位表面積当たりの溶出したニッケルイオン濃度(ppm/cm2)を求めた。
得られた導電性粒子50個のめっき状態を、走査型電子顕微鏡により観察した。めっき割れ又はめっき剥がれ等のめっきむらの有無を観察した。めっきむらが確認された導電性粒子が4個以下の場合を「良好」、めっきむらが確認された導電性粒子が5個以上の場合を「不良」と判定した。
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成ケミカルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、異方性導電材料を得た。
接続構造体の作製:
ビスフェノールA型エポキシ樹脂(三菱化学社製「エピコート1009」)10重量部と、アクリルゴム(重量平均分子量約80万)40重量部と、メチルエチルケトン200重量部と、マイクロカプセル型硬化剤(旭化成ケミカルズ社製「HX3941HP」)50重量部と、シランカップリング剤(東レダウコーニングシリコーン社製「SH6040」)2重量部とを混合し、導電性粒子を含有量が3重量%となるように添加し、分散させ、樹脂組成物を得た。
得られた接続構造体の対向する電極間の接続抵抗を4端子法により測定した。また、初期の接続抵抗を下記の基準で判定した。
○○:接続抵抗が2.0Ω以下
○:接続抵抗が2.0Ωを超え、3.0Ω以下
△:接続抵抗が3.0Ωを超え、5.0Ω以下
×:接続抵抗が5.0Ωを超える
上記(6)初期の接続抵抗の評価で得られた接続構造体を、85℃及び湿度85%の条件で100時間放置した。放置後の接続構造体の電極間の接続抵抗を四端子法により測定し、得られた測定値を高温高湿試験後の接続抵抗とした。また、高温高湿試験後の接続抵抗を下記の基準で判定した。
○○:接続抵抗が2.0Ω以下
○:接続抵抗が2.0Ωを超え、3.0Ω以下
△:接続抵抗が3.0Ωを超え、5.0Ω以下
×:接続抵抗が5.0Ωを超える
上記(6)初期の接続抵抗の評価で得られた接続構造体を高さ70cmの位置から落下させ、導通を確認することにより耐衝撃性の評価を行った。初期抵抗値からの抵抗値の上昇率が50%以下の場合を「良好」、初期抵抗値からの抵抗値の上昇率が50%を超える場合を「不良」と判定した。
微分干渉顕微鏡を用いて、上記(6)の評価の接続構造体の作製で得られた接続構造体のガラス基板側から、ガラス基板に設けられた電極を観察し、導電性粒子が接触した電極の圧痕の形成の有無を下記の判定基準で評価した。なお、電極の圧痕の形成の有無について、電極面積が0.02mm2となるように、微分干渉顕微鏡にて観察し、電極0.02mm2あたりの圧痕の個数を算出した。任意の10箇所を微分干渉顕微鏡にて観察し、電極0.02mm2あたりの圧痕の個数の平均値を算出した。
○○:電極0.02mm2あたりの圧痕が25個以上
○:電極0.02mm2あたりの圧痕が20個以上、25個未満
△:電極0.02mm2あたりの圧痕が5個以上、20個未満
×:電極0.02mm2あたりの圧痕が5個未満
1a…突起
2…基材粒子
3…導電層
3a…突起
4…芯物質
5…絶縁物質
11…導電性粒子
11a…突起
12…第2の導電層
13…導電層
13a…突起
21…導電性粒子
22…導電層
51…接続構造体
52…第1の接続対象部材
52a…上面
52b…電極
53…第2の接続対象部材
53a…下面
53b…電極
54…接続部
Claims (12)
- 基材粒子と、該基材粒子の表面上に配置された導電層とを有し、
前記導電層が、ニッケルと、タングステン及びモリブデンの内の少なくとも1種の金属成分とを含み、
前記導電層の全体100重量%中、ニッケルの含有量が60重量%以上であり、
前記導電層の外表面から厚み方向に内側に向かって5nmの厚みの導電層部分100重量%中、タングステン及びモリブデンの合計の含有量が5重量%を超える、導電性粒子。 - 前記導電層の外表面から厚み方向に内側に向かって5nmの厚みの導電層部分100重量%中、タングステン及びモリブデンの合計の含有量が10重量%以上である、請求項1に記載の導電性粒子。
- 前記導電層の厚み方向で、ニッケルと、タングステン及びモリブデンの内の少なくとも1種の前記金属成分が偏在しており、
前記導電層の外側部分が、前記導電層の内側部分よりも前記金属成分を多く含む、請求項1又は2に記載の導電性粒子。 - 前記導電層の全体100重量%中、タングステン及びモリブデンの合計の含有量が5重量%を超える、請求項1~3のいずれか1項に記載の導電性粒子。
- 複数の導電性粒子10重量部を5重量%クエン酸水溶液100重量部に25℃で1分間浸漬したときに、溶出するニッケルイオン濃度が、導電性粒子の単位表面積当たり100ppm/cm2以下である、請求項1~4のいずれか1項に記載の導電性粒子。
- 前記導電層は、還元剤を用いる無電解ニッケルめっきにより形成されており、
前記導電層が前記還元剤に由来する成分を含まないか、又は前記還元剤に由来する成分を含みかつ前記導電層の全体100重量%中の前記還元剤に由来する成分の含有量が5重量%以下である、請求項1~5のいずれか1項に記載の導電性粒子。 - 前記導電層がボロンを含む、請求項1~6のいずれか1項に記載の導電性粒子。
- 前記導電層の全体100重量%中、ボロンの含有量が0.05重量%以上、4重量%以下である、請求項7に記載の導電性粒子。
- 前記導電層がリンを含まないか、又は前記導電層がリンを含みかつ前記導電層の全体100重量%中のリンの含有量が0.5重量%未満である、請求項1~8のいずれか1項に記載の導電性粒子。
- 前記導電層が外表面に突起を有する、請求項1~9のいずれか1項に記載の導電性粒子。
- 請求項1~10のいずれか1項に記載の導電性粒子と、バインダー樹脂とを含む、導電材料。
- 第1の接続対象部材と、第2の接続対象部材と、該第1,第2の接続対象部材を接続している接続部とを備え、
前記接続部が、請求項1~10のいずれか1項に記載の導電性粒子により形成されているか、又は該導電性粒子とバインダー樹脂とを含む導電材料により形成されている、接続構造体。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015109267A (ja) * | 2013-10-21 | 2015-06-11 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP2015118933A (ja) * | 2013-11-18 | 2015-06-25 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
KR20210014917A (ko) * | 2019-07-31 | 2021-02-10 | 덕산하이메탈(주) | 도전입자, 도전재료 및 접속 구조체 |
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TWI740807B (zh) * | 2014-10-29 | 2021-10-01 | 日商迪睿合股份有限公司 | 導電材料、連接構造體、及連接構造體之製造方法 |
CN111508635B (zh) * | 2016-02-08 | 2021-12-28 | 积水化学工业株式会社 | 导电性粒子、导电材料及连接结构体 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07207185A (ja) * | 1994-01-21 | 1995-08-08 | Kawazumi Gijutsu Kenkyusho:Kk | 被覆パラジウム微粉末および導電性ペースト |
JP2002075057A (ja) * | 2000-08-30 | 2002-03-15 | Mitsui Mining & Smelting Co Ltd | 被覆銅粉 |
JP2009224059A (ja) * | 2008-03-13 | 2009-10-01 | Sekisui Chem Co Ltd | 導電性微粒子、異方性導電材料、及び、接続構造体 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3696429B2 (ja) | 1999-02-22 | 2005-09-21 | 日本化学工業株式会社 | 導電性無電解めっき粉体とその製造方法並びに該めっき粉体からなる導電性材料 |
JP2002275511A (ja) * | 2001-03-15 | 2002-09-25 | Murata Mfg Co Ltd | 金属粉末の製造方法、金属粉末、導電性ペーストならびに積層セラミック電子部品 |
JP4017903B2 (ja) * | 2002-04-01 | 2007-12-05 | 宇部日東化成株式会社 | 導電性粒子およびその製造方法 |
JP4962706B2 (ja) * | 2006-09-29 | 2012-06-27 | 日本化学工業株式会社 | 導電性粒子およびその製造方法 |
JP4737177B2 (ja) * | 2006-10-31 | 2011-07-27 | 日立化成工業株式会社 | 回路接続構造体 |
CN101210305B (zh) * | 2006-12-31 | 2011-09-28 | 成都深嘉机械制造有限公司 | 钨合金复合镀层材料及制造方法 |
JP5139002B2 (ja) * | 2007-08-10 | 2013-02-06 | 株式会社東芝 | 微粒子担持方法および微粒子担持装置 |
JP4714719B2 (ja) * | 2007-09-07 | 2011-06-29 | 積水化学工業株式会社 | 導電性微粒子の製造方法 |
JP5430093B2 (ja) * | 2008-07-24 | 2014-02-26 | デクセリアルズ株式会社 | 導電性粒子、異方性導電フィルム、及び接合体、並びに、接続方法 |
TWI467065B (zh) * | 2009-06-17 | 2015-01-01 | Enthone | 含奈米粒子之金屬基複合塗層之電解澱積 |
JP4957838B2 (ja) * | 2009-08-06 | 2012-06-20 | 日立化成工業株式会社 | 導電性微粒子及び異方性導電材料 |
JP4752986B1 (ja) * | 2010-01-08 | 2011-08-17 | 日立化成工業株式会社 | 回路接続用接着フィルム及び回路接続構造体 |
JP5586682B2 (ja) * | 2010-03-01 | 2014-09-10 | 新日鉄住金化学株式会社 | 金属微粒子複合体及びその製造方法 |
JP5534891B2 (ja) * | 2010-03-26 | 2014-07-02 | 積水化学工業株式会社 | 導電性粒子、導電性粒子の製造方法、異方性導電材料及び接続構造体 |
JP2012164454A (ja) * | 2011-02-04 | 2012-08-30 | Sony Chemical & Information Device Corp | 導電性粒子及びこれを用いた異方性導電材料 |
JP5216165B1 (ja) * | 2011-07-28 | 2013-06-19 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP5952553B2 (ja) * | 2011-12-14 | 2016-07-13 | 株式会社日本触媒 | 導電性微粒子及びこれを含む異方性導電材料 |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07207185A (ja) * | 1994-01-21 | 1995-08-08 | Kawazumi Gijutsu Kenkyusho:Kk | 被覆パラジウム微粉末および導電性ペースト |
JP2002075057A (ja) * | 2000-08-30 | 2002-03-15 | Mitsui Mining & Smelting Co Ltd | 被覆銅粉 |
JP2009224059A (ja) * | 2008-03-13 | 2009-10-01 | Sekisui Chem Co Ltd | 導電性微粒子、異方性導電材料、及び、接続構造体 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015109267A (ja) * | 2013-10-21 | 2015-06-11 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP2015118933A (ja) * | 2013-11-18 | 2015-06-25 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
JP2019021635A (ja) * | 2013-11-18 | 2019-02-07 | 積水化学工業株式会社 | 導電性粒子、導電材料及び接続構造体 |
KR20210014917A (ko) * | 2019-07-31 | 2021-02-10 | 덕산하이메탈(주) | 도전입자, 도전재료 및 접속 구조체 |
KR102222105B1 (ko) | 2019-07-31 | 2021-03-03 | 덕산하이메탈(주) | 도전입자, 도전재료 및 접속 구조체 |
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