WO2018207627A1 - 被覆粒子及びその製造方法 - Google Patents

被覆粒子及びその製造方法 Download PDF

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Publication number
WO2018207627A1
WO2018207627A1 PCT/JP2018/016879 JP2018016879W WO2018207627A1 WO 2018207627 A1 WO2018207627 A1 WO 2018207627A1 JP 2018016879 W JP2018016879 W JP 2018016879W WO 2018207627 A1 WO2018207627 A1 WO 2018207627A1
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Prior art keywords
particles
coated
metal
fine particles
coated particles
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PCT/JP2018/016879
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English (en)
French (fr)
Japanese (ja)
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智真 成橋
夏博 佐野
恵里 古井
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日本化学工業株式会社
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Priority to JP2019517556A priority Critical patent/JP7160801B2/ja
Priority to CN201880026556.4A priority patent/CN110574126A/zh
Priority to KR1020197031934A priority patent/KR102528599B1/ko
Publication of WO2018207627A1 publication Critical patent/WO2018207627A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors

Definitions

  • the present invention relates to coated particles in which conductive particles are coated on an insulating layer and a method for producing the same.
  • Conductive particles in which a metal such as nickel or gold is formed on the surface of resin particles are used as conductive materials such as conductive adhesives, anisotropic conductive films, and anisotropic conductive adhesives.
  • conductive adhesives such as nickel or gold
  • anisotropic conductive films such as anisotropic conductive films
  • anisotropic conductive adhesives such as gold, silver, copper, silver, copper, and zinc.
  • the circuit width and pitch of electronic circuits have become increasingly smaller. Accordingly, as the conductive particles used in the above-described conductive adhesive, anisotropic conductive film, anisotropic conductive adhesive and the like, those having a small particle size are required. When conductive particles having such a small particle diameter are used, the blending amount of the conductive particles must be increased in order to improve the connectivity.
  • insulating coated conductive particles are used in which the surfaces of the conductive particles are coated with an insulating material to prevent contact between the metal layers of the conductive particles.
  • Patent Document 1 a particle having a surface made of a conductive metal is used as a nucleus, and the surface is partially modified by an organic particle made of an organic compound containing a functional group having a binding property to the metal. It is described that the organic compound has a positive or negative charge.
  • Patent Document 2 describes the same coated particles as Patent Document 1. In this document, the coated particle is chemically bonded to a particle having a surface made of a conductive metal through a functional group in which the insulating particle has a binding property to the metal, thereby forming a single-layer coating layer.
  • the coated particles having such a structure are formed by exposing the metal surface of the metal-coated particles by melting, deforming, or peeling the insulating particles by thermocompression bonding of the coated particles between the electrodes. It is described that conduction between particle electrodes is possible and connectivity is obtained.
  • the surface of the metal-coated particle is obtained by applying insulating resin fine particles containing a hetero element or a functional group having a bonding force with a metal on the surface of the metal-coated particle, and then heating it. Describes that anisotropic insulating conductive particles having an insulating layer having no particle shape can be obtained.
  • Patent Document 4 describes that the adhesiveness of the resin particles to the conductive particles is improved by taking into consideration the glass transition temperature of the resin particles made of an insulating substance.
  • Patent Documents 5 and 6 the coating particles are easily deformed and melted by increasing the glass transition temperature of the shell layer of the core shell particles as insulating particles higher than the glass transition temperature of the core particles. It is described that the conductive connection between the two becomes easy.
  • the conventional coated particles coated with the insulating fine particles described in Patent Documents 1 and 2 do not have sufficient adhesion between the insulating fine particles and the metal-coated particles. Even when coated, there is a case where the film is peeled off from the surface of the conductive particles at the time of manufacturing the conductive material or at the time of thermocompression bonding of the device manufacturing.
  • the coated conductive particles described in Patent Document 3 heat the functional groups of the insulating fine particles in the metal-coated particles coated with the insulating fine particles that are intermediates before heating, and the insulating fine particles. Since the resulting film does not have a charge, it was difficult to obtain adhesion with the metal-coated particles.
  • the insulating particles can be attached to the surface of the metal-coated particles, the insulating fine particles are difficult to form a single layer on the surface of the metal-coated particles because the functional group does not have a charge. From these points, the coated particles obtained by heating the insulating fine particles have room for improvement in terms of connection reliability.
  • the resin particles described in Patent Document 4 also have the same problems as Patent Document 3 because they do not have a charge on the surface.
  • the insulating fine particles are composed of core-shell particles made of a shell having a relatively high glass transition temperature as described in Patent Documents 5 and 6, even if the glass transition temperature of the core particles is low, the shell particles are the core particles. Therefore, it is unlikely that the adhesion between the insulating fine particles and the metal-coated particles will be sufficient.
  • the object of the present invention is not only that the insulating fine particles are easily adhered to the metal-coated particles in a single layer, but also better adhesion between the insulating material and the conductive particles than before, conductive adhesive, anisotropic
  • An object of the present invention is to provide insulating coated conductive particles having better connection reliability than conventional conductive materials such as conductive films and anisotropic conductive adhesives.
  • an insulating layer having a charge on the surface as an insulating substance and having a specific glass transition point is a conventional insulating layer.
  • the present inventors have found that it is possible to have excellent connection reliability that has never been achieved as a coated conductive material.
  • the present invention is a coated particle comprising conductive metal-coated particles having a metal film formed on the surface of the core material particles, and an insulating layer made of a polymer that coats the metal-coated particles,
  • the insulating layer has a charge and provides coated particles having a glass transition temperature Tg of 40 ° C. or higher and 100 ° C. or lower.
  • the present invention is a method for producing coated particles in which metal-coated particles in which metal is formed on the surface of core material particles are coated with an insulating layer made of a polymer, Insulating fine particles obtained by polymerizing a polymerizable composition comprising a polymerizable compound having a charge and a polymerizable compound having an ester bond, having a charge on the surface and having a glass transition temperature Tg of 40 ° C. or higher and 100 ° C. or lower. And obtaining A process comprising: mixing a dispersion containing insulating fine particles and metal-coated particles under a temperature condition of Tg-30 ° C. or higher and Tg + 30 ° C. to adhere the insulating fine particles to the surface of the metal-coated particles.
  • Tg is the glass transition temperature of the insulating fine particles
  • FIG. 1 is a photograph of the insulating fine particles obtained in Production Example 1 observed with a scanning electron microscope (SEM).
  • FIG. 2 is a photograph of the insulating fine particles obtained in Production Example 2 observed with an SEM.
  • FIG. 3 is a photograph of the coated particles obtained in Example 1 observed with an SEM.
  • FIG. 4 is a photograph of the coated particles obtained in Example 2 observed with an SEM.
  • FIG. 5 is a photograph of the coated particles obtained in Example 3 observed with an SEM.
  • FIG. 6 is a photograph of the coated particles obtained in Comparative Example 1 observed with an SEM.
  • FIG. 7 is a photograph of the coated particles obtained in Comparative Example 2 observed with an SEM.
  • the coated particles of the present embodiment are coated particles in which conductive metal-coated particles having a metal film formed on the surface of core material particles are coated with an insulating layer made of a polymer, The insulating layer has a charge, and the glass transition temperature Tg is lower than the glass transition temperature of the core particle.
  • the core material in the metal-coated particles is particulate and can be used without particular limitation whether it is an inorganic material or an organic material.
  • Inorganic core particles include metal particles such as gold, silver, copper, nickel, palladium, solder, alloys, glass, ceramics, silica, metal or non-metal oxides (including hydrates), and aluminosilicates. Examples thereof include metal silicate, metal carbide, metal nitride, metal carbonate, metal sulfate, metal phosphate, metal sulfide, metal acid salt, metal halide and carbon.
  • organic core particles for example, natural fibers, natural resins, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polybutene, polyamide, polyacrylic ester, polyacrylonitrile, polyacetal, ionomer, polyester, etc.
  • examples include resins, alkyd resins, phenol resins, urea resins, benzoguanamine resins, melamine resins, xylene resins, silicone resins, epoxy resins, diallyl phthalate resins, and the like. These may be used alone or in combination of two or more.
  • the core particles made of a resin material are preferable in that the specific gravity is small compared to the core particles made of metal and hardly settles, the dispersion stability is excellent, and the electrical connection is easily maintained due to the elasticity of the resin. .
  • the core material particles When an organic substance is used as the core material particles, it does not have a glass transition temperature, or the glass transition temperature is higher than 100 ° C., and the shape of the core material particles is easily maintained in the anisotropic conductive connection process. This is preferable because the shape of the core particles can be easily maintained in the step of forming the film.
  • the glass transition temperature when the core particles have a glass transition temperature, the glass transition temperature is 200 ° C. or less. In the anisotropic conductive connection, the conductive particles tend to soften, and the contact area becomes large so that conduction can be easily obtained.
  • the glass transition temperature is more preferably more than 100 ° C. and not more than 180 ° C., and particularly preferably more than 100 ° C. and not more than 160 ° C.
  • the glass transition temperature can be measured by the method described in Examples described later.
  • the glass transition temperature is hardly observed even when measurement is attempted up to 200 ° C. by the method described in the following examples.
  • such particles are also referred to as particles having no glass transition temperature, and such core material particles may be used in the present invention.
  • the core particle material having no such glass transition temperature can be obtained by copolymerizing a monomer constituting the organic substance exemplified above in combination with a crosslinkable monomer. .
  • Crosslinkable monomers include tetramethylene di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide di (meth) acrylate, tetraethylene oxide (Meth) acrylate, 1,6-hexanedi (meth) acrylate, neopentylglycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane di ( (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, dipentaerythritol pent
  • the shape of the core particle is not particularly limited.
  • the core particles are spherical.
  • the core particles may have a shape other than a spherical shape, for example, a fiber shape, a hollow shape, a plate shape, or a needle shape, and may have a number of protrusions on its surface or an indefinite shape.
  • spherical core particles are preferable from the viewpoint of excellent filling properties.
  • the shape of the metal-coated particles is not particularly limited, although it depends on the shape of the core particles. For example, it may be in the form of a fiber, hollow, plate, or needle, and may have a number of protrusions on its surface or an indefinite shape. In the present invention, a spherical shape or a shape having a large number of protrusions is preferable in terms of excellent filling properties and connectivity.
  • the metal film in the metal-coated particles has conductivity, and examples of the constituent metal include gold, platinum, silver, copper, iron, zinc, nickel, tin, lead, antimony, bismuth, cobalt, indium,
  • metal compounds such as ITO and solder can be used.
  • gold, silver, copper, nickel, palladium or solder is preferable because of low resistance, and in particular, nickel, gold, nickel alloy or gold alloy is preferable because it has low resistance and high bonding with insulating fine particles. It is done.
  • the metals in the metal-coated particles can be used alone or in combination of two or more.
  • the metal film may have a single layer structure or a multilayer structure composed of a plurality of layers.
  • the outermost layer is preferably nickel, gold, a nickel alloy or a gold alloy.
  • the metal film may not cover the entire surface of the core particle, or may cover only a part thereof.
  • the coated portion may be continuous, for example, it may be discontinuously coated in an island shape.
  • the thickness of the metal film is preferably 0.001 ⁇ m or more and 2 ⁇ m or less.
  • the average particle diameter of the metal-coated particles is preferably from 0.1 ⁇ m to 50 ⁇ m, more preferably from 1 ⁇ m to 30 ⁇ m.
  • the average particle diameter of the metal-coated particles is a value measured using a scanning electron microscope (Scanning Electron Microscope: SEM). Specifically, the average particle diameter of the metal-coated particles is measured by the method described in the examples.
  • the particle diameter is the diameter of a circular metal-coated particle image.
  • the particle diameter refers to the largest length (maximum length) of line segments that cross the metal-coated particle image.
  • a method of forming a metal film on the surface of the core particle there are a dry method using a vapor deposition method, a sputtering method, a mechanochemical method, a hybridization method, a wet method using an electroplating method, an electroless plating method, etc. Can be mentioned. Moreover, you may form a metal membrane
  • the insulating layer that coats the metal-coated particles is made of a polymer and has a charge.
  • the insulating layer include a plurality of insulating fine particles, and the fine particles have a charge on the surface, or the insulating layer is a continuous film having a charge.
  • the term “continuous film” means that the material constituting the insulating layer is present in the form of dots. The continuous film does not need to be completely coated, and when a part of the surface of the metal-coated particle is coated, the coating part of the film may be continuous, for example, discontinuous in an island shape. May be coated.
  • the insulating layer is an insulating fine particle made of a polymer
  • the metal in the portion where the insulating fine particles are melted, deformed, peeled off or moved on the surface of the metal-coated particles by thermocompression bonding of the coated particles between the electrodes The metal surface of the coated particles is exposed, thereby allowing conduction between the electrodes and providing connectivity.
  • the surface portion of the coated particle that faces in a direction other than the thermocompression bonding direction generally maintains the state of the metal surface covered with the insulating fine particles, so that conduction in a direction other than the thermocompression bonding direction is prevented.
  • the coated particles are thermocompression bonded between the electrodes, so that the coating melts, deforms, or peels to expose the metal surface of the metal-coated particles, thereby enabling conduction between the electrodes. Sex is obtained.
  • the metal surface is often exposed by tearing the coated particles by thermocompression bonding between electrodes.
  • the coated state of the metal surface by the coating is generally maintained at the surface portion of the coated particle that faces in a direction different from the thermocompression bonding direction, conduction in directions other than the thermocompression bonding direction is prevented.
  • the glass transition temperature Tg is 100 ° C. or lower.
  • the adhesiveness between the insulating fine particles and film and the metal-coated particles can be easily increased.
  • the contact area between the insulating fine particle and the metal-coated particle, which has conventionally been a point-to-point contact is increased, and adhesion between the two is facilitated as a surface-to-surface contact.
  • the adhesion between the fine particles can be easily increased on the surface of one metal-coated particle.
  • the glass transition temperature Tg of the insulating fine particles and the film is 40 ° C. or more, so that the shape stability during storage of the coated particles and the ease of synthesis of the insulating fine particles and the film can be obtained.
  • the glass transition temperature Tg of the insulating fine particles and the coating is preferably lower than the glass transition temperature of the core material of the metal-coated particles, from the viewpoint of obtaining coated particles with higher connection reliability.
  • the adhesion between the insulating layer that is a fine particle or film and the metal-coated particle can be further improved.
  • the insulating layer is a fine particle
  • the fine particle has a charge on the surface, so that it can be adhered to the metal-coated particle of the insulating fine particle as a single layer while preventing aggregation.
  • the metal-coated particles can be coated with a single layer and a layer of insulating fine particles having a high coverage. For the above reasons, according to the coated particles of the present invention, it is easy to obtain suitable insulation in the lateral direction and reliable conductive connectivity between the counter electrodes, and the connection reliability can be improved.
  • the glass transition temperature Tg of the insulating layer which is a fine particle or a film is more preferably 95 ° C. or less, and particularly preferably 90 ° C. or less.
  • the glass transition temperature Tg of the insulating layer is more preferably 45 ° C. or higher, and particularly preferably 50 ° C. or higher.
  • the glass transition temperature can be measured by the method described in Examples described later.
  • the difference between the glass transition temperature Tg of the insulating layer and the glass transition temperature of the core material of the metal-coated particles is preferably 160 ° C. or less. It is more preferable that the temperature is not higher than ° C, and particularly preferable that the temperature is not higher than 100 ° C.
  • the difference between the glass transition temperature of the insulating layer and the glass transition temperature of the core material of the metal-coated particles is preferably 5 ° C. or higher, and more preferably 10 ° C. or higher.
  • Examples of the method for measuring the glass transition temperature include the following methods. Using a differential scanning calorimeter “STAR SYSTEM” (manufactured by METTLER TOLEDO), 0.04 to 0.06 g of the sample was heated to 120 ° C. and cooled to 25 ° C. at a rate of temperature decrease of 5 ° C./min. did. Next, the sample was heated at a heating rate of 5 ° C./min, and the heat quantity was measured. When a peak is observed, the temperature of the peak is measured. When a step is observed without a peak being observed, a tangent indicating the maximum slope of the curve of the step and an extension of the baseline on the high temperature side of the step The temperature at the intersection of these was the glass transition temperature.
  • STAR SYSTEM manufactured by METTLER TOLEDO
  • the glass transition temperature Tg of the insulating layer As a method for setting the glass transition temperature Tg of the insulating layer within the above-described range, it is preferable to use a polymer having at least one ester unit in the structure as a polymer constituting the insulating fine particles. Thereby, there is an advantage that the glass transition temperature of the polymer can be suitably lowered and the desired physical properties can be easily controlled.
  • Examples of the structural unit having an ester bond include those derived from a polymerizable compound having an ethylenically unsaturated bond and an ester bond.
  • Examples of such a polymerizable compound include esters.
  • Esters include vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth ) Amyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, ( Of (meth) acrylic acid such as 2-phenoxyethyl (meth) acrylate, 3-phenylpropyl (meth
  • the polymerizable compound having an ethylenically unsaturated bond and an ester bond may have only one ester bond or two or more in the structure.
  • the polymerizable compound having both an ethylenically unsaturated bond and an ester bond in the structure is represented by —COOR 1 or —OCOR 2 (where R 1 and R 2 are alkyl groups, and — is a bond).
  • these groups are represented by H 2 C ⁇ CH *, or H 2 C ⁇ C (CH 3 ) * (* is represented by the above-mentioned —COOR 1 or —OCOR 2
  • the compound bonded to the bond destination of the bond in the group is preferable.
  • R 1 and R 2 a linear or branched alkyl group is preferable, the number of carbon atoms is preferably 1 or more and 12 or less, and more preferably 2 or more and 10 or less. These can be used alone or in combination of two or more.
  • the polymer constituting the insulating layer preferably has a structural unit having no ester bond in addition to a structural unit having an ester bond in the structure.
  • the structural unit having no ester bond include those derived from the polymerizable compound having an ethylenically unsaturated bond, such as styrenes, olefins, ⁇ , ⁇ unsaturated carboxylic acids, amides, and nitriles.
  • styrenes examples include styrene, o, m, p-methyl styrene, dimethyl styrene, ethyl styrene, styrene derivatives such as chlorostyrene, and styrene derivatives such as ⁇ -methyl styrene, ⁇ -chloro styrene, and ⁇ -chloro styrene.
  • olefins examples include ethylene and propylene.
  • ⁇ , ⁇ unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like.
  • these salts of ⁇ , ⁇ unsaturated carboxylic acids are also included in the ⁇ , ⁇ unsaturated carboxylic acids.
  • amides include acrylamide and methacrylamide.
  • nitriles include acrylonitrile. These may be further substituted, and examples of the substituent include a functional group having a charge described later.
  • the polymer constituting the insulating layer is preferably at least one polymer selected from styrenes and nitriles from the viewpoint of high polymerization rate and easy spheroidization. These monomers can be used alone or in combination of two or more.
  • the existence mode of these structural units in the polymer may be random, alternating, or block.
  • the polymer constituting the insulating layer may be cross-linked or non-cross-linked.
  • the proportion of the structural unit having an ester bond in the structure in all the structural units is preferably 0.1 mol% or more from the viewpoint of suitably reducing the glass transition temperature Tg, 30 mol% or less is preferable from the viewpoint of preventing the insulating fine particles and the film from being deformed during storage of the coated particles.
  • the proportion of the structural unit having an ester bond in the structure in all the structural units is more preferably 0.2 mol% or more and 28 mol% or less, and 0.3 mol% or more and 25 mol% or less. It is particularly preferred.
  • the number of structural units in the polymer counts a structure derived from one unsaturated bond as one structural unit.
  • the shape of the insulating fine particles is not particularly limited, and may be spherical or other than spherical. Examples of the shape other than the spherical shape include a fiber shape, a hollow shape, a plate shape, and a needle shape.
  • the insulating fine particles may have a large number of protrusions on the surface or may be indefinite. Spherical insulating fine particles are preferred from the viewpoint of adhesion to metal-coated particles and ease of synthesis.
  • the insulating fine particles themselves preferably have no core-shell structure in which shell particles are attached to the surface of the core particles.
  • the insulating fine particles have a charge on the surface.
  • the coated particles of the present invention have higher adhesion to the metal coated particles than the coated particles having insulating fine particles having no charge on the surface.
  • the insulating fine particles having the same charge on the surface repel each other, so that aggregates of the insulating fine particles are not easily generated, and a single layer of insulating fine particles is easily formed on the surface of the metal-coated particles. .
  • the insulating fine particles have an electric charge and the insulating fine particles are attached to the surface of the metal-coated particle by observation with a scanning electron microscope, “the insulating fine particles have an electric charge on the surface”. This is true.
  • the term “insulating fine particles have a charge” as used herein means that the insulating fine particles themselves have a charge before being attached to the metal-coated particles.
  • the insulating fine particles preferably have a functional group having a charge on the surface as an example of a form having a charge on the surface.
  • the functional group preferably forms a part of the chemical structure of the substance as a part of the substance constituting the insulating fine particles.
  • the functional group is preferably contained in at least one structure of a polymer constituent unit constituting the insulating fine particles.
  • the functional group is preferably chemically bonded to the polymer constituting the insulating fine particles, more preferably bonded to the side chain of the polymer.
  • the insulating fine particles have a functional group having an electric charge and the insulating fine particles are attached to the surface of the metal-coated particle by observation with a scanning electron microscope, “the insulating fine particles are charged. It corresponds to “having a functional group having on the surface”.
  • Preferred examples of the functional group include a phosphonium group, an ammonium group, a sulfonium group, and an amino group as positively charged functional groups.
  • Preferred examples of the functional group having a negative charge include a carboxyl group, a hydroxyl group, a thiol group, a sulfonic acid group, and a phosphoric acid group.
  • an onium-based functional group such as a phosphonium group, an ammonium group, or a sulfonium group is particularly preferable in terms of further improving the binding property to the metal-coated particle surface.
  • X is a nitrogen atom, a phosphorus atom or a sulfur atom
  • R may be the same or different from each other, and is a hydrogen atom, a linear, branched or cyclic alkyl group, or an aryl group.
  • N is 1 when X is a nitrogen atom or phosphorus atom, and is 0 when X is a sulfur atom. * Is a bond.
  • Examples of the linear alkyl group represented by R include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, Examples thereof include n-nonadecyl group and n-icosyl group.
  • Examples of the branched alkyl group represented by R include isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, s-pentyl group, t-pentyl group, isohexyl group, and s-hexyl group. , T-hexyl group, ethylhexyl group and the like.
  • Examples of the cyclic alkyl group represented by R include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group.
  • a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group.
  • Examples of the aryl group represented by R include a phenyl group, a benzyl group, a tolyl group, and an o-xylyl group.
  • the alkyl group represented by R increases the adhesion between the metal-coated particles and the insulating fine particles, or the insulating fine particles are detached from the metal-coated particles when thermocompression bonded inside the anisotropic conductive film. From the point that conduction is easily secured, the number of carbon atoms is preferably 1 or more and 12 or less, more preferably 1 or more and 10 or less, and most preferably 1 or more and 8 or less. Moreover, it is also preferable that the alkyl group represented by R is linear because the insulating fine particles are easy to come close to and adhere to the metal-coated particles.
  • the insulating fine particles are composed of a polymer of a polymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond having a functional group. Is preferred.
  • Examples of the polymerizable compound having an ethylenically unsaturated bond having a functional group include N, N-dimethylaminoethyl methacrylate and N, N—as polymerizable compounds having an ethylenically unsaturated bond having an onium-based functional group.
  • Ammonium group-containing monomers such as dimethylaminopropylacrylamide and N, N, N-trimethyl-N-2-methacryloyloxyethylammonium chloride; Monomers having a sulfonium group such as phenyldimethylsulfonium methylsulfate methacrylate; 4- (vinylbenzyl ) Triethylphosphonium chloride, 4- (vinylbenzyl) trimethylphosphonium chloride, 4- (vinylbenzyl) tributylphosphonium chloride, 4- (vinylbenzyl) trioctylphosphonium chloride, 4- Vinylbenzyl) triphenylphosphonium chloride, 2- (methacryloyloxyethyl) trimethylphosphonium chloride, 2- (methacryloyloxyethyl) triethylphosphonium chloride, 2- (methacryloyloxyethyl) tributylphosphonium chloride, 2-
  • the polymer constituting the insulating fine particles preferably has a structural unit composed of styrenes (styrene monomers) from the viewpoint of easy availability of the polymer and ease of polymer synthesis. It is preferable to have a monomer having a functional group attached thereto.
  • the functional group may be bonded to any of the para-position, ortho-position and meta-position with respect to the CH group of the benzene ring of styrenes, and is preferably bonded to the para-position.
  • a functional group of the above general formula (1) is bonded to the benzene ring of styrene (the bond represented by the functional group of the general formula (1) is bonded to the carbon atom of the benzene ring of styrene).
  • a halide ion is preferably used as a counter ion for a functional group having a positive charge. Examples of halide ions include Cl ⁇ , F ⁇ , Br ⁇ and I ⁇ .
  • the film is easily adhered to the metal-coated particles because the film has a charge.
  • the insulating fine particles serving as the precursor of the insulating layer can be uniformly arranged on the core material particles. This has the effect of making the film thickness uniform.
  • the film has an electric charge, so that the effect of preventing a short circuit in a direction different from that between the counter electrodes is easily exhibited, the insulation in the direction is improved, and the connection reliability is improved. Is expensive.
  • the film may cover the entire surface of the metal-coated particles, or may cover a part of the surface.
  • the thickness of the film is preferably 10 nm or more from the viewpoint of improvement of insulation in a direction different from that between the counter electrodes, and is preferably 3,000 nm or less from the viewpoint of easy conduction between the counter electrodes. Is preferable. From this viewpoint, the thickness of the film is preferably 10 nm or more and 3,000 nm or less, and more preferably 15 nm or more and 2,000 nm or less.
  • the charge in the film preferably forms part of the chemical structure of the substance as part of the substance constituting the film.
  • the electric charge is preferably contained in at least one structure of the structural units of the polymer constituting the film.
  • the electric charge is preferably chemically bonded to the polymer constituting the film, more preferably bonded to the side chain of the polymer. Examples of the type of charge that the film has and the method of making the film have the charge include the same kind of charge that the insulating fine particle has and the method of making the insulating fine particle have the charge.
  • the film is preferably a film obtained by coating the metal-coated particles with insulating fine particles having electric charges on the surface and then heating the insulating fine particles.
  • the insulating fine particles are likely to adhere to the metal-coated particles with respect to the metal-coated particles, whereby the ratio of the coating with the insulating fine particles on the surface of the metal-coated particles becomes sufficient and the metal coating is performed. Peeling of the insulating fine particles from the particles is easy to be prevented.
  • the insulating fine particles having a charge are easy to coat the metal-coated particles with a single layer. For these reasons, the coating obtained by heating the insulating fine particles that coat the metal-coated particles can have a uniform thickness and a high coating ratio on the surface of the metal-coated particles.
  • the structure and characteristics of the film obtained by subjecting the specific insulating fine particles to heat treatment are all measured using some means and directly specified in the present specification.
  • the structure or characteristics of other films related to the effects of the present invention could not be confirmed at the applicant's technical level. Even if all the factors are identified, it is necessary to establish and specify a new measurement method for the structure and characteristics of the coatings related to those factors, which requires significantly excessive economic expenditure and time. .
  • the applicant is manufactured by the above manufacturing method as one of the preferable features of the film of the present invention. It was described that there was.
  • the ratio of the structural unit to which the functional group is bonded is preferably 0.01 mol% or more and 5.0 mol% or less in all the structural units. % To 2.0 mol% is more preferable.
  • the number of structural units in the polymer counts a structure derived from one ethylenically unsaturated bond as one structural unit.
  • the average particle diameter (D) of the insulating fine particles is preferably 10 nm to 3,000 nm, more preferably 15 nm to 2,000 nm.
  • the average particle diameter of the insulating fine particles is a value measured by observation using a scanning electron microscope, and specifically, is measured by the method described in Examples described later.
  • the particle diameter is the diameter of the circular insulating fine particle image.
  • the particle diameter refers to the largest length (maximum length) of the line segments crossing the insulating fine particle image.
  • the width of the particle size distribution of the powder is represented by a coefficient of variation (hereinafter also referred to as “CV”) expressed by the following calculation formula (1).
  • C. V. (%) (Standard deviation / average particle diameter) ⁇ 100 (1)
  • This C.I. V. Large indicates that the particle size distribution has a width, while C.I. V. A small value indicates that the particle size distribution is sharp.
  • the coated particles of this embodiment are C.I. V. However, it is desirable to use insulating fine particles of 0.1% to 10%, more preferably 0.5% to 8%, and most preferably 1% to 6%. C. V. In this range, there is an advantage that the thickness of the coating layer made of insulating fine particles can be made uniform.
  • a polymerizable composition containing a polymerizable compound having a charge and a polymerizable compound having an ester bond is polymerized to have a charge on the surface and a glass transition temperature Tg of 40 ° C. or higher and 100 ° C. or lower.
  • a first step of obtaining insulating fine particles The second step of mixing the dispersion containing the insulating fine particles and the metal-coated particles under a temperature condition of Tg-30 ° C. or higher and Tg + 30 ° C. to adhere the insulating fine particles to the surface of the metal-coated particles (where Tg is an insulation) The glass transition temperature of the conductive fine particles).
  • the polymerizable compound having a charge and the polymerizable compound having an ester bond may be the same or different. That is, the polymerizable composition may contain only a compound having a charge and an ester bond as a polymerizable compound having a charge and a polymerizable compound having an ester bond. Examples of the polymerizable compound having a charge and the polymerizable compound having an ester bond include those described above. Moreover, what gives the preferable structural ratio of said structural unit as the structural ratio about the polymeric compound which has an electric charge in the whole ethylenic polymeric compound, and the polymeric compound which has an ester bond is mentioned.
  • Examples of the polymerization method include emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, suspension polymerization and the like. Any of them may be used, but in the case of soap-free emulsion polymerization, a monodisperse fine particle is used as a surfactant. It is preferable because it has an advantage that it can be manufactured without using it. In the case of soap-free emulsion polymerization, a water-soluble initiator is used as the polymerization initiator.
  • the polymerization is preferably performed in an inert atmosphere such as nitrogen or argon. As described above, insulating fine particles having a glass transition temperature Tg of 40 ° C. or more and 100 ° C. or less and having a functional group on the surface can be obtained.
  • the dispersion containing the insulating fine particles and the metal-coated particles are mixed under a temperature condition of Tg-30 ° C. or higher and Tg + 30 ° C. or lower to adhere the insulating fine particles to the surface of the metal-coated particles (provided that Tg is an insulating property). It is the glass transition temperature of fine particles).
  • Tg is an insulating property. It is the glass transition temperature of fine particles.
  • the liquid medium of the dispersion include water, an organic solvent, and a mixture thereof, and water is preferable.
  • the dispersion preferably contains an inorganic salt or an organic salt from the viewpoint of easily obtaining coated particles having a certain coverage.
  • the inorganic salt and organic salt those capable of dissociating anions are preferably used.
  • the anions include Cl ⁇ , F ⁇ , Br ⁇ , I ⁇ , SO 4 2 ⁇ , CO 3 2 ⁇ , NO 3. -, COO - and the like.
  • the inorganic salt for example NaCl, KCl, LiCl, MgCl 2 , BaCl 2, NaF, KF, LiF, MgF 2, BaF 2, NaBr, KBr, LiBr, MgBr 2, BaBr 2, NaI, KI, LiI, MgI 2 , BaI 2, Na 2 SO 4 , K 2 SO 4, Li 2 SO 4, MgSO 4, Na 2 CO 3, NaHCO 3, K 2 CO 3, KHCO 3, Li 2 CO 3, LiHCO 3, MgCO 3, NaNO 3 , KNO 3 , LiNO 3 , MgNO 3 , BaNO 3 and the like can be used.
  • the organic salt Na oxalate, Na acetate, Na citrate, Na tartrate and the like can be used.
  • the concentration of the preferred inorganic salt and organic salt varies depending on the extent to which the insulating fine particles occupy the surface area of the metal-coated particles, but in the dispersion after mixing the metal-coated particles, for example, 5 mmol / L or more and 100 mmol It is preferable for the concentration to be less than / L because it is easy to obtain coated particles having a suitable coverage and having a single layer of insulating fine particles. From this viewpoint, the concentration of the inorganic salt and the organic salt in the dispersion is more preferably 5 mmol / L or more and 100 mmol / L or less, and particularly preferably 10 mmol / L or more and 80 mmol / L or less.
  • the metal-coated particles to be mixed with the dispersion may be metal-coated particles themselves or a dispersion of metal-coated particles.
  • the insulating fine particles are preferably contained in the dispersion after mixing the metal-coated particles in an amount of 10 ppm to 50,000 ppm, more preferably 250 ppm to 10,000 ppm.
  • the metal-coated particles are preferably contained in an amount of 100 ppm or more and 100,000 ppm or less, more preferably 500 ppm or more and 80,000 ppm or less.
  • the temperature of the dispersion at the time of mixing with the metal-coated particles is 30 ° C. lower than the glass transition temperature Tg, so that the insulating fine particles adhere to the metal-coated particles and the insulating fine particles adhere to each other. Can be enhanced. Further, the temperature of the dispersion is Tg + 30 ° C. or lower, so that the shape of the insulating fine particles is maintained, and a suitable contact area is easily obtained between the insulating fine particles and the metal-coated particles. From these viewpoints, the temperature of the dispersion at the time of mixing with the metal-coated particles is more preferably Tg ⁇ 25 ° C. or more and Tg + 25 ° C. or less, and particularly preferably Tg ⁇ 15 ° C. or more and Tg + 15 ° C. or less.
  • the time for which the insulating fine particles are attached to the metal-coated particles is preferably 0.1 hours or more and 24 hours or less. During this time, it is preferable to stir the dispersion. Next, the solid content of the dispersion is washed and dried as necessary to obtain coated particles in which insulating fine particles having functional groups adhere to the surface of the metal-coated particles.
  • the surface of the metal-coated particles can be coated in a film state with the insulating fine particles in a molten state.
  • the insulating property becomes stronger.
  • a heating method a method of heating the dispersion liquid after the insulating fine particles are attached to the surface of the metal-coated particles, a method of heating the coated particles in a solvent such as water, and a gas phase such as air are used. The method etc. which heat inside are mentioned. As the heating temperature, it is easy to form a uniform film shape without the insulating fine particles falling off.
  • Tg being the glass transition temperature of the polymer constituting the insulating fine particles
  • Tg + 1 ° C. or higher and Tg + 60 ° C. The following is preferable, and Tg + 5 ° C. or higher and Tg + 50 ° C. or lower is more preferable.
  • the pressure condition can be performed under atmospheric pressure, reduced pressure or increased pressure.
  • the coated particles obtained by coating the surface of the metal-coated particles in a film shape may be subjected to an annealing treatment in order to further stabilize the coating.
  • the annealing treatment include a method of heating the coated particles in a gas phase such as an inert gas.
  • the heating temperature is preferably Tg + 1 ° C. or more and Tg + 60 ° C. or less, more preferably Tg + 5 ° C. or more and Tg + 50 ° C. or less, when Tg is the glass transition temperature of the polymer constituting the insulating fine particles.
  • the heating atmosphere is not particularly limited, and the heating atmosphere can be performed under any of atmospheric pressure, reduced pressure, or increased pressure in an inert gas atmosphere such as nitrogen or argon or an oxidizing atmosphere such as air.
  • coated particles of the present invention can be produced by other production methods.
  • insulating fine particles having no charge may be produced in advance by a polymerization reaction, and the resulting insulating fine particles may be reacted with a compound having a charge to introduce the charge onto the surface of the insulating fine particles.
  • the coated particles obtained as described above are conductive adhesives, taking advantage of the insulating properties between the coated particles due to the advantage of using the insulating fine particles having an electric charge and the insulating film and the connectivity between the counter electrodes, It is suitably used as a conductive material such as an anisotropic conductive film or an anisotropic conductive adhesive.
  • Average particle diameter 200 particles are arbitrarily extracted from a scanning electron microscope (SEM) photograph (magnification 100,000 times) to be measured, their particle diameters are measured, and the average value is averaged. The particle diameter was taken.
  • the dispersion of fine particles after polymerization was passed through a SUS sieve having an opening of 150 ⁇ m to remove aggregates. From the dispersion from which the aggregates had been removed, fine particles were allowed to settle under a condition of 20,000 rpm for 20 minutes using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CR-21N), and the supernatant was removed.
  • the obtained solid was washed with pure water to obtain spherical fine particles of poly (styrene / n-butyl acrylate / 4- (vinylbenzyl) triethylphosphonium chloride).
  • the average particle diameter of the obtained fine particles is 245 nm. V. was 3.6%.
  • the glass transition temperature was about 62 ° C.
  • An SEM photograph of the obtained insulating fine particles is shown in FIG.
  • Example 1 A fine particle dispersion was prepared by adding pure water and NaCl so that the solid content concentration of the fine particles obtained in Production Example 1 was 10,000 ppm by mass, the NaCl concentration was 25 mmol / L, and the total was 20 mL.
  • 50 mg of Ni-plated particles manufactured by Nippon Chemical Industry Co., Ltd.
  • the Ni plating particles are formed so that the surface of the spherical resin particles having a glass transition temperature of 120 ° C. made of a crosslinkable acrylic resin has a thickness within the range described as the thickness of the preferable metal film. It was spherical with nickel plating.
  • Solid matter is separated from the dispersion after stirring by a membrane filter having an opening of 10 ⁇ m, washed with pure water and dried, and the surface is poly (styrene / n-butyl acrylate / 4- (vinylbenzyl) triethylphosphonium chloride). Coated particles coated with a single layer with fine particles were obtained. An SEM photograph of the obtained coated particles is shown in FIG.
  • Example 2 A fine particle dispersion was prepared by adding pure water and NaCl so that the solid content concentration of the fine particles obtained in Production Example 1 was 10,000 ppm by mass, the NaCl concentration was 25 mmol / L, and the total was 20 mL.
  • 50 mg of Au plated particles manufactured by Nippon Chemical Industry Co., Ltd.
  • the Au plating particles are gold plated so that the surface of the spherical resin particles made of a crosslinkable acrylic resin having a glass transition temperature of 120 ° C. has a thickness within the range described as the thickness of the preferred metal coating.
  • Example 3 50 mg of the coated particles obtained in Example 1 was put into 20 mL of pure water and stirred at 80 ° C. for 6 hours. After completion of the stirring, the solid matter was separated by a membrane filter having an opening of 10 ⁇ m and dried to obtain coated particles in which the entire surface of the metal-coated particles was coated with a film having a thickness of 150 nm. An SEM photograph of the obtained coated particles is shown in FIG. The thickness of the film was measured by the following method.
  • ⁇ Measurement method of film thickness > 200 diameters of the metal-coated particles after film formation were measured by SEM, and the average value was calculated. Similarly, 200 diameters of the metal-coated particles before attaching the insulating fine particles were measured with an SEM, and the average value was calculated. Half of the difference between the average values of these diameters was taken as the film thickness.
  • Example 1 A fine particle dispersion was prepared by adding pure water and NaCl so that the solid content concentration of the fine particles obtained in Production Example 2 was 10,000 ppm by mass, the NaCl concentration was 25 mmol / L, and the total was 20 mL. To this dispersion, 50 mg of Ni-plated particles (manufactured by Nippon Chemical Industry Co., Ltd.) having a particle size of 20 ⁇ m was added and stirred at room temperature for 15 hours. The Ni plating particles were the same as those used in Example 1.
  • Example 2 A fine particle dispersion was prepared by adding pure water and NaCl so that the solid content concentration of the fine particles obtained in Production Example 2 was 10,000 ppm by mass, the NaCl concentration was 25 mmol / L, and the total was 20 mL. To this dispersion, 50 mg of Au plated particles (manufactured by Nippon Chemical Industry Co., Ltd.) having a particle size of 20 ⁇ m was added and stirred at room temperature for 15 hours. The Au plating particles were the same as those used in Example 2.
  • FIGS. 6 and 7 show scanning electron microscope images of the coated particles obtained in Examples 1 and 2 and Comparative Examples 1 and 2, respectively.
  • the adhesion with the insulating fine particles to the metal-coated particles is higher than in Comparative Examples 1 and 2, and the coverage of the insulating fine particles on the surface of the metal-coated particles is high. high.
  • the coated particles of the present invention are those in which the insulating layer is hardly peeled off from the metal coated particles and has excellent connection reliability, and the coated particles can be produced industrially advantageously.
  • the coated particles of the present invention are not only capable of coating the metal coated particles with a single layer due to the charge of the insulating layer, but also due to the low glass transition temperature of the insulating layer. Is more difficult to peel off from the metal-coated particles and has excellent connection reliability. Moreover, the manufacturing method of the coated particle of this invention can manufacture the coated particle of this invention by an industrially advantageous method.

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PCT/JP2018/016879 2017-05-08 2018-04-25 被覆粒子及びその製造方法 WO2018207627A1 (ja)

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WO2002035555A1 (fr) * 2000-10-23 2002-05-02 Sekisui Chemical Co., Ltd. Particule enrobee
WO2003025955A1 (fr) * 2001-09-14 2003-03-27 Sekisui Chemical Co., Ltd. Particule conductrice revetue, procede de fabrication d'une particule conductrice revetue, materiau conducteur anisotrope et structure de connexion electrique
JP2005149764A (ja) * 2003-11-11 2005-06-09 Sekisui Chem Co Ltd 被覆導電粒子、異方性導電材料及び導電接続構造体
JP2007537572A (ja) * 2004-05-12 2007-12-20 マイクログローブ コープ カンパニー リミテッド 異方性導電接続用の絶縁導電性粒子及びその製造方法並びにこれを用いた異方性導電接続材料

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JP5498907B2 (ja) 2010-09-29 2014-05-21 株式会社日本触媒 樹脂粒子およびこれを用いた絶縁化導電性粒子並びに異方性導電材料
JP5672022B2 (ja) 2011-01-25 2015-02-18 日立化成株式会社 絶縁被覆導電粒子、異方導電性材料及び接続構造体
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Publication number Priority date Publication date Assignee Title
WO2002035555A1 (fr) * 2000-10-23 2002-05-02 Sekisui Chemical Co., Ltd. Particule enrobee
WO2003025955A1 (fr) * 2001-09-14 2003-03-27 Sekisui Chemical Co., Ltd. Particule conductrice revetue, procede de fabrication d'une particule conductrice revetue, materiau conducteur anisotrope et structure de connexion electrique
JP2005149764A (ja) * 2003-11-11 2005-06-09 Sekisui Chem Co Ltd 被覆導電粒子、異方性導電材料及び導電接続構造体
JP2007537572A (ja) * 2004-05-12 2007-12-20 マイクログローブ コープ カンパニー リミテッド 異方性導電接続用の絶縁導電性粒子及びその製造方法並びにこれを用いた異方性導電接続材料

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