WO2021235433A1 - Procédé de production de particules conductrices et particules conductrices - Google Patents

Procédé de production de particules conductrices et particules conductrices Download PDF

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WO2021235433A1
WO2021235433A1 PCT/JP2021/018784 JP2021018784W WO2021235433A1 WO 2021235433 A1 WO2021235433 A1 WO 2021235433A1 JP 2021018784 W JP2021018784 W JP 2021018784W WO 2021235433 A1 WO2021235433 A1 WO 2021235433A1
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Prior art keywords
conductive particles
group
particles
conductive
core material
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PCT/JP2021/018784
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English (en)
Japanese (ja)
Inventor
千紘 松本
哲 高橋
昭紘 久持
裕之 稲葉
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日本化学工業株式会社
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Priority claimed from JP2021006519A external-priority patent/JP7095127B2/ja
Application filed by 日本化学工業株式会社 filed Critical 日本化学工業株式会社
Priority to KR1020227040065A priority Critical patent/KR20230012495A/ko
Priority to CN202180036693.8A priority patent/CN115667579A/zh
Publication of WO2021235433A1 publication Critical patent/WO2021235433A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum

Definitions

  • the present invention relates to a method for producing conductive particles and conductive particles.
  • the conductive particles used as the conductive material of the anisotropic conductive material such as the anisotropic conductive film and the anisotropic conductive paste
  • those in which a conductive layer made of metal is formed on the surface of the core material particles are generally known.
  • This conductive layer provides an electrical connection between the electrodes and wiring.
  • a nickel plating film obtained by an electroless plating method is often used.
  • the nickel plating film by the electroless plating method contains phosphorus precipitated from the reducing agent as an impurity, it forms a film containing a large amount of amorphous material. Therefore, a technique for crystallizing a nickel plating film by heat-treating conductive particles to improve various properties of the conductive layer is disclosed.
  • Patent Document 1 the powder on which the nickel coat layer is formed is heat-treated in an inert gas atmosphere or a slightly reducing atmosphere at 300 to 600 ° C. to adjust the crystallite diameter of the nickel structure constituting the nickel coat layer. It is stated that the adhesion stability with the gold-coated layer performed after this step is enhanced, whereby the conductor obtained by using the nickel- and gold two-layer coated particle powder has a low electrical resistance value. It is disclosed that it will be.
  • Patent Document 2 describes conductive particles having a conductive portion having a crystallite size of 50 nm or more, in which hydrogen atoms in the conductive portion are reduced by annealing the conductive particles at 200 ° C. or higher. As this effect, it is disclosed that the cracking of the conductive portion is suppressed and the acid resistance is enhanced, so that the connection reliability is excellent.
  • an object of the present invention is to provide a method for producing conductive particles, which has little influence on the quality of the conductive particles and suppresses the production cost.
  • the present inventor has made that the conductive particles are heated under a high vacuum when the conductive particles are heat-treated, so that the metal of the conductive layer is crystallized while the conductive particles are heated.
  • the present invention has been completed by finding that it is low and has excellent connection reliability.
  • the present invention provides a method for producing conductive particles having a step of heating the conductive particles having a conductive layer on the surface of the core material particles at a temperature of 200 to 600 ° C. under a vacuum of 1000 Pa or less.
  • the withstand current value per conductive particle when the compression ratio is 30% is 200 mA or more. Is to provide.
  • the present invention it is possible to provide conductive particles having excellent current resistance, low connection resistance, and excellent connection reliability, and a method for producing the conductive particles.
  • FIG. 1 is an SEM image of the conductive particles obtained in Example 1.
  • the method for producing conductive particles of the present invention includes a vacuum heating step of heating the conductive particles having a conductive layer on the surface of the core material particles at a temperature of 200 to 600 ° C. under a vacuum of 1000 Pa or less.
  • the conductive particles having a conductive layer on the surface of the core material particles to be subjected to the vacuum heating step will be described.
  • the conductive particles are formed by forming a conductive layer on the surface of the core material particles.
  • the core material particles may be inorganic or organic as long as they are in the form of particles, and can be used without particular limitation.
  • the inorganic core particles include metal particles such as gold, silver, copper, nickel, palladium, and solder, alloys, glass, ceramics, silica, metal or non-metal oxides (including hydrous), and aluminosilicates. Examples thereof include metal silicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, metal phosphates, metal sulfides, metal acid salts, metal halides and carbons.
  • examples of the organic core particles include thermoplastics such as natural fibers, natural resins, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polybutene, polyamide, polyacrylic acid ester, polyacrylic nitrile, polyacetal, ionomer, and polyester.
  • thermosetting resins such as resins, alkyd resins, phenol resins, urea resins, benzoguanamine resins, melamine resins, xylene resins, silicone resins, epoxy resins and diallyl phthalate resins. These may be used alone or in combination of two or more.
  • the core material particles may be composed of a material composed of both an inorganic substance and an organic substance, instead of the material composed of either the above-mentioned inorganic substance or the organic substance.
  • the existence mode of the inorganic substance and the organic substance in the core material particles is, for example, a core made of the inorganic substance and an inorganic substance covering the surface of the core. Examples thereof include a core-shell type configuration including a mode including a shell, or a mode including a core made of an organic substance and a shell made of an inorganic substance covering the surface of the core.
  • a blend type structure in which an inorganic substance and an organic substance are mixed or randomly fused in one core material particle can be mentioned.
  • the core material particles are preferably made of an organic substance or a material made of both an inorganic substance and an organic substance, and more preferably made of a material made of both an inorganic substance and an organic substance.
  • the inorganic substances include glass, ceramics, silica, metal or non-metal oxides (including hydrous), metal silicates including aluminosilicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, and metal phosphorus.
  • metal silicates including aluminosilicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, and metal phosphorus.
  • acid salts metal sulfides, metal acid salts, metal halides and carbons.
  • the organic substance is preferably a thermoplastic resin such as natural fiber, natural resin, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polybutene, polyamide, polyacrylic acid ester, polyacrylic nitrile, polyacetal, ionomer, polyester and the like.
  • a core material made of such a material it is possible to improve the dispersion stability between particles, and it is possible to develop appropriate elasticity and enhance continuity at the time of electrical connection of an electronic circuit. ..
  • the fact that the core material particles do not have a glass transition temperature or the glass transition temperature exceeds 100 ° C. makes it easy to maintain the shape of the core material particles and the core in the process of forming a metal film. It is preferable because it is easy to maintain the shape of the material particles.
  • the glass transition temperature can be determined, for example, as the intersection of the tangents of the original baseline and the inflection in the baseline shift portion of the DSC curve obtained by differential scanning calorimetry (DSC).
  • the core material particles When an organic substance is used as the core material particles and the organic substance is a highly crosslinked resin, almost no baseline shift is observed even if the glass transition temperature is measured up to 200 ° C. by the above method.
  • such particles are also referred to as particles having no glass transition temperature, and in the present invention, such core material particles may be used.
  • the core material having no glass transition temperature it can be obtained by copolymerizing the monomer constituting the organic substance exemplified above in combination with the crosslinkable monomer.
  • crosslinkable monomer examples 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, and tetraethylene oxide.
  • Examples thereof include silane-containing monomers, triallyl isocyanurates, diallyl phthalates, diallyl acrylamides, diallyl ethers and the like.
  • silane-containing monomers triallyl isocyanurates, diallyl phthalates, diallyl acrylamides, diallyl ethers and the like.
  • core material particles made of such a hard organic material are often used.
  • the core material particles are spherical.
  • the core material particles may have a shape other than a spherical shape, for example, a fibrous shape, a hollow shape, a plate shape, or a needle shape, and may have a large number of protrusions on the surface thereof or an amorphous shape.
  • spherical core material particles are preferable in terms of excellent filling property and easy coating with metal.
  • the conductive layer formed on the surface of the core material particles is made of a conductive metal.
  • the metal constituting the conductive layer include gold, platinum, silver, copper, iron, zinc, nickel, tin, lead, antimony, bismuth, cobalt, indium, titanium, germanium, aluminum, chromium, palladium, tungsten and molybdenum. , Calcium, magnesium, rhodium, sodium, iridium, beryllium, ruthenium, potassium, cadmium, osmium, lithium, rubidium, gallium, tarium, tantalum, cesium, thorium, strontium, polonium, zirconium, barium, manganese and other metals or theirs.
  • metal compounds such as ITO and solder can be mentioned.
  • gold, silver, copper, nickel, palladium, rhodium or solder is preferable because of its low electrical resistance, and nickel, gold, nickel alloy or gold alloy is particularly preferably used.
  • the metal may be one kind, or two or more kinds may be used in combination.
  • the conductive layer may have a single layer structure or a laminated structure composed of a plurality of layers.
  • the outermost layer may be at least one selected from nickel, gold, silver, copper, palladium, nickel alloy, gold alloy, silver alloy, copper alloy and palladium alloy. preferable.
  • the conductive layer may not cover the entire surface of the core material particles, or may cover only a part thereof.
  • the coated portions may be continuous, for example, may be discontinuously covered in an island shape.
  • the thickness of the conductive layer is preferably 0.1 nm or more and 2000 nm or less, and more preferably 1 nm or more and 1500 nm or less.
  • the conductive particles have excellent electrical characteristics.
  • the conductive particles have protrusions described later, the height of the protrusions is not included in the thickness of the conductive layer referred to here.
  • the thickness of the conductive layer can be measured by cutting the particles to be measured into two pieces and observing the cross section of the cut end with a scanning electron microscope (SEM).
  • the average particle size of the conductive particles is preferably 0.1 ⁇ m or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m or less.
  • the average particle size of the conductive particles is a value measured by SEM observation. Specifically, the average particle size of the conductive particles is measured by the method described in Examples.
  • the particle diameter is the diameter of a circular conductive particle image. When the conductive particles are not spherical, the particle diameter refers to the largest length (maximum length) of the line segments traversing the conductive particle image.
  • the height of the protrusions is preferably 20 nm or more and 1000 nm or less, and more preferably 50 nm 800 nm or less.
  • the number of protrusions depends on the particle size of the conductive particles, but the number of protrusions is preferably 1 or more and 20000 or less, and more preferably 5 or more and 5000 or less per conductive particle. It is advantageous in that the conductivity is further improved.
  • the length of the base of the protrusion is preferably 5 nm or more and 1000 nm or less, and more preferably 10 nm or more and 800 nm or less.
  • the length of the base of the protrusion refers to the length along the surface of the conductive particle at the site where the protrusion is formed when the cross section of the particle is observed by SEM, and the height of the protrusion is from the base of the protrusion to the protrusion apex. The shortest distance to. When one protrusion has a plurality of vertices, the highest vertex is the height of the protrusion.
  • the length of the base of the protrusion and the height of the protrusion shall be the arithmetic mean of the values measured for 20 different particles observed by an electron microscope.
  • the shape of the conductive particles depends on the shape of the core material particles, but is not particularly limited.
  • it may be fibrous, hollow, plate-shaped or needle-shaped, and may have a large number of protrusions on its surface or may be amorphous.
  • the shape is spherical or has a large number of protrusions on the outer surface in terms of excellent filling property and connectivity.
  • a dry method using a vapor deposition method, a sputtering method, a mechanochemical method, a hybridization method, etc., an electrolytic plating method, a wet method using an electroless plating method, etc. are used.
  • a conductive layer may be formed on the surface of the core material particles by combining these methods.
  • the conductive particles it is preferable to form a conductive layer on the surface of the core material particles by an electroless plating method because it is easy to obtain conductive particles having desired particle characteristics.
  • the conductive particles it is preferable that the conductive particles have an electroless nickel-phosphorus plating layer formed as a conductive layer on the surface of the core material particles.
  • the core material particles are surface-modified so that the surface has the ability to capture noble metal ions or has the ability to capture noble metal ions.
  • the noble metal ion is preferably a palladium or silver ion. Having the ability to capture noble metal ions means that the noble metal ions can be captured as a chelate or a salt.
  • the surface of the core material particles has an ability to capture noble metal ions.
  • the surface is modified so as to have the ability to capture noble metal ions, for example, the method described in JP-A-61-64882 can be used.
  • Such core material particles are used to support a precious metal on the surface thereof.
  • the core material particles are dispersed in a dilute acidic aqueous solution of a precious metal salt such as palladium chloride or silver nitrate. This causes the noble metal ions to be captured on the surface of the particles.
  • the concentration of the noble metal salt is sufficient in the range of 1 ⁇ 10 -7 to 1 ⁇ 10 ⁇ 2 mol per 1 m 2 of the surface area of the particles.
  • the core material particles in which the noble metal ions are captured are separated from the system and washed with water. Subsequently, the core material particles are suspended in water, and a reducing agent is added thereto to reduce the noble metal ions.
  • the precious metal is carried on the surface of the core material particles.
  • the reducing agent for example, sodium hypophosphite, sodium borohydride, potassium borohydride, dimethylamine borane, hydrazine, formalin and the like are used, and the reducing agent is selected from these based on the constituent material of the target conductive layer. It is preferable to be done.
  • a sensitization treatment for adsorbing tin ions on the surface of the particles may be performed.
  • the surface-modified core material particles may be put into an aqueous solution of stannous chloride and stirred for a predetermined time.
  • the conductive layer is formed on the core material particles that have been pretreated in this way.
  • a treatment for forming a conductive layer having protrusions will be described.
  • the first step is an electroless nickel plating step of mixing an aqueous slurry of core material particles with an electroless nickel plating bath containing a dispersant, a nickel salt, a reducing agent, a complexing agent and the like.
  • self-decomposition of the plating bath occurs at the same time as the formation of the conductive layer on the core material particles. Since this autolysis occurs in the vicinity of the core material particles, the autolyzed material is trapped on the surface of the core material particles when the conductive layer is formed, so that the nuclei of microprojections are generated, and at the same time, the conductive layer is formed. Will be done.
  • the protrusion grows from the nucleus of the generated microprotrusion as a base point.
  • the above-mentioned core material particles are sufficiently dispersed in water in the range of preferably 0.1 to 500 g / L, more preferably 1 to 300 g / L to prepare an aqueous slurry.
  • the dispersion operation can be carried out by normal stirring, high speed stirring or by using a shear dispersion device such as a colloid mill or a homogenizer. Further, ultrasonic waves may be used in combination with the dispersion operation. If necessary, a dispersant such as a surfactant may be added in the dispersion operation.
  • the aqueous slurry of the core material particles subjected to the dispersion operation is added to the electroless nickel plating bath containing the nickel salt, the reducing agent, the complexing agent, various additives and the like, and the first step of the electroless plating is performed.
  • Examples of the above-mentioned dispersant include nonionic surfactants, zwitterionic surfactants and / or water-soluble polymers.
  • a nonionic surfactant a polyoxyalkylene ether-based surfactant such as polyethylene glycol, polyoxyethylene alkyl ether, or polyoxyethylene alkyl phenyl ether can be used.
  • a betaine-based surfactant such as alkyldimethylacetate betaine, alkyldimethylcarboxymethyl acetate betaine, and alkyldimethylaminoacetate betaine can be used.
  • the water-soluble polymer polyvinyl alcohol, polyvinylpyrrolidinone, hydroxyethyl cellulose and the like can be used. These dispersants can be used alone or in combination of two or more.
  • the amount of the dispersant used depends on the type, but is generally 0.5 to 30 g / L with respect to the volume of the liquid (electroless nickel plating bath). In particular, when the amount of the dispersant used is in the range of 1 to 10 g / L with respect to the volume of the liquid (electroless nickel plating bath), it is preferable from the viewpoint of further improving the adhesion of the conductive layer.
  • the nickel salt for example, nickel chloride, nickel sulfate, nickel acetate or the like is used, and the concentration thereof is preferably in the range of 0.1 to 50 g / L.
  • the reducing agent for example, the same one as that used for the reduction of the noble metal ion described above can be used, and the reducing agent is selected based on the constituent material of the target base film.
  • the concentration thereof is preferably in the range of 0.1 to 50 g / L.
  • the complexing agent examples include citric acid, hydroxyacetic acid, tartaric acid, malic acid, lactic acid, gluconic acid or carboxylic acids (salts) such as alkali metal salts and ammonium salts thereof, amino acids such as glycine, and amines such as ethylenediamine and alkylamine. Acids and other compounds that have a complexing effect on nickel ions, such as ammonium, EDTA or pyrophosphate (salt), are used. These can be used alone or in combination of two or more.
  • the concentration is preferably in the range of 1 to 100 g / L, more preferably 5 to 50 g / L.
  • the pH of the preferred electroless nickel plating bath at this stage is in the range of 3-14.
  • the electroless nickel plating reaction starts promptly when an aqueous slurry of core particles is added, and is accompanied by the generation of hydrogen gas. The first step is terminated when the generation of hydrogen gas is completely no longer recognized.
  • a first aqueous solution containing one of a nickel salt, a reducing agent and an alkali, and a second aqueous solution containing the remaining two are added. Either used, or (ii) a first aqueous solution containing a nickel salt, a second aqueous solution containing a reducing agent, and a third aqueous solution containing an alkali are used, and these aqueous solutions are used simultaneously and over time, respectively.
  • Electroless nickel plating is performed by adding to the liquid of one step. When these liquids are added, the plating reaction starts again, and the conductive layer formed can be controlled to a desired film thickness by adjusting the addition amount. After the addition of the electroless nickel plating solution is completed, after the generation of hydrogen gas is completely no longer observed, stirring is continued while maintaining the liquid temperature for a while to complete the reaction.
  • first aqueous solution containing a nickel salt and a second aqueous solution containing a reducing agent and an alkali it is preferable to use a first aqueous solution containing a nickel salt and a second aqueous solution containing a reducing agent and an alkali, but the combination is not limited to this.
  • the first aqueous solution does not contain the reducing agent and the alkali
  • the second aqueous solution does not contain the nickel salt.
  • the nickel salt and the reducing agent those described above can be used.
  • alkali for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide can be used. The same applies to the case of (ii) above.
  • the first to third aqueous solutions contain nickel salts, reducing agents and alkalis, respectively, and each aqueous solution does not contain any other two components other than the components.
  • the concentration of the nickel salt in the aqueous solution is preferably 10 to 1000 g / L, particularly preferably 50 to 500 g / L.
  • the concentration of the reducing agent is preferably 100 to 1000 g / L, particularly preferably 100 to 800 g / L.
  • a boron compound is used as the reducing agent, it is preferably 5 to 200 g / L, particularly preferably 10 to 100 g / L.
  • hydrazine or a derivative thereof is used as the reducing agent, it is preferably 5 to 200 g / L, particularly preferably 10 to 100 g / L.
  • the alkali concentration is preferably 5 to 500 g / L, particularly preferably 10 to 200 g / L.
  • the second step is continuously performed after the completion of the first step, but instead of this, the first step and the second step may be performed intermittently.
  • the core material particles and the plating solution are separated by a method such as filtration, and the core material particles are newly dispersed in water to prepare an aqueous slurry, and a complexing agent is prepared therein.
  • the dispersant is preferably 0.5 to 30 g / L, more preferably 1 to 10 g / L.
  • the formation of the conductive layer having a smooth surface can be performed by reducing the concentration of the nickel salt in the electroless nickel plating bath in the first step of the treatment for forming the conductive layer having the protrusions. That is, as the nickel salt, for example, nickel chloride, nickel sulfate, nickel acetate or the like is used, and the concentration thereof is preferably in the range of 0.01 to 0.5 g / L.
  • a conductive layer having a smooth surface can be formed by the method of performing the first step and the second step other than reducing the concentration of the nickel salt in the electroless nickel plating bath. In this way, conductive particles to be used in the vacuum heating step of the present invention can be obtained.
  • the degree of vacuum in the vacuum heating step in the present invention is 1000 Pa or less, preferably 0.01 to 900 Pa, and particularly preferably 0.01 to 500 Pa. By setting the degree of vacuum within this range, the residual components of the reaction solution used when forming the conductive layer are successfully removed, so that the metal of the conductive layer is less likely to cause side reactions even at high temperatures, and connection reliability is improved. Conductive particles with excellent desired properties can be obtained.
  • This vacuum heating step may be carried out at a constant degree of vacuum or may be carried out by changing the degree of vacuum as long as the above effects are not impaired. This change in the degree of vacuum can be performed, for example, by purging an inert gas such as nitrogen or argon when the degree of vacuum is lowered. Further, when increasing the degree of vacuum, it can be done by increasing the output of the vacuum pump.
  • the degree of vacuum in the present invention is an absolute pressure, that is, a value when the absolute vacuum is 0.
  • the heating temperature of the vacuum heating step in the present invention is 200 to 600 ° C, preferably 250 to 500 ° C, and particularly preferably 300 to 450 ° C. By setting the heating temperature in this range, the crystallization of the metal of the conductive layer proceeds, so that the electric resistance becomes low and the electrical conductivity becomes excellent.
  • the heating rate from room temperature to the heating temperature in the vacuum heating step in the present invention is preferably 0.1 to 50 ° C./min, and more preferably 0.1 to 30 ° C./min. By adopting this rate of temperature rise, the crystallization of the metal in the conductive portion proceeds successfully, so that the electric resistance becomes low and the electrical conductivity becomes excellent.
  • the temperature lowering rate of the vacuum heating step in the present invention is preferably 0.02 to 50 ° C./min, more preferably 0.02 to 30 ° C./min. It is preferable to set the temperature lowering rate up to at least 50 ° C. in this range.
  • the temperature lowering rate can be controlled by purging with room temperature or cooled gas, or by cooling the heating furnace housing with cooling water or the like. By adopting this temperature lowering rate, the denaturation of the core material particles and the conductive layer due to the heat history can be suppressed, and the influence on the quality can be reduced.
  • the treatment time of the vacuum heating step in the present invention is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours.
  • this processing time indicates the time for heating within the above-mentioned heating temperature range.
  • the vacuum heating step in the present invention may be performed in a state where the conductive particles are allowed to stand still, or may be performed while stirring.
  • the vacuum heating step is performed in a state where the conductive particles are allowed to stand still, it is preferable to leave the conductive particles stationary to a thickness of 0.1 mm to 100 mm.
  • the container containing the conductive particles is evacuated and then heated in a stationary state or with stirring.
  • the gas phase portion of the container containing the conductive particles may be replaced with an inert gas such as nitrogen and then evacuated, or may be evacuated as it is.
  • the vacuum heating step in the present invention may be repeated a plurality of times as needed.
  • the conductive particles of the present invention have a withstand current value of 200 mA or more per conductive particle, particularly preferably 300 mA or more.
  • the withstand current value per conductive particle is within the above range, the connection resistance is low and the connection reliability is excellent.
  • a large withstand current value is considered to mean that the conductive layer has few defects and high uniformity, and therefore, it is considered that not only the electrical characteristics of the conductive layer but also the mechanical characteristics are excellent.
  • the conductive particles of the present invention can be suitably produced by the above-mentioned production method of the present invention.
  • the withstand current value in the present invention is the withstand current per conductive particle when the compression ratio is 30% using a conductive fine particle electrical property measuring device (hereinafter, also referred to as a VI device). It is a measurement of the value. When the electrodes are connected under pressure, it is necessary to compress and deform the conductive particles to increase the contact area with the electrodes. Therefore, it is important that the withstand current value in the compressed state is large.
  • the VI device may be a device capable of measuring voltage-current characteristics and / or current capacity while maintaining a constant compressibility of conductive fine particles. For example, Japanese Patent Application Laid-Open No. 10-221388. The described device can be used.
  • the withstand current value in the present invention is a value obtained by measuring one conductive particle. As for the withstand current value in this measurement, it is preferable that the compressibility of the conductive particles to be measured is 30% from the viewpoint of measurement under conditions closer to those at the time of mounting.
  • the surface thereof can be further coated with an insulating resin in order to prevent the occurrence of short circuits between the conductive particles. ..
  • the coating of the insulating resin is destroyed by the heat and pressure applied when the two electrodes are bonded together with a conductive adhesive so that the surface of the conductive particles is not exposed as much as possible when no pressure is applied. , At least the protrusions on the surface of the conductive particles are exposed.
  • the thickness of the insulating resin can be about 0.1 to 0.5 ⁇ m.
  • the insulating resin may cover the entire surface of the conductive particles, or may cover only a part of the surface of the conductive particles.
  • insulating resin those known in the technical field can be widely used.
  • a chemical method such as a core selvation method, an interfacial polymerization method, an insitu polymerization method and a liquid curing coating method, a spray drying method, and an aerial suspension coating method are used.
  • a physico-mechanical method such as a vacuum vapor deposition coating method, a dry blend method, a hybridization method, an electrostatic coalescence method, a melting dispersion cooling method and an inorganic encapsulation method, and a physicochemical method such as an interfacial precipitation method.
  • the organic polymer constituting the insulating resin may contain a compound containing an ionic group as a monomer component in the structure of the polymer, provided that it is non-conductive.
  • the compound containing an ionic group may be a crosslinkable monomer or a non-crosslinkable monomer. That is, it is preferable that the organic polymer is formed by using a compound in which at least one of the crosslinkable monomer and the non-crosslinkable monomer has an ionic group.
  • the "monomer component" refers to a structure derived from a monomer in an organic polymer, and is a component derived from the monomer. By subjecting the monomer to polymerization, an organic polymer containing the monomer component as a constituent unit is formed.
  • the ionic group is preferably present at the interface of the organic polymer constituting the insulating resin. Further, it is preferable that the ionic group is chemically bonded to the monomer component constituting the organic polymer. Whether or not the ionic group is present at the interface of the organic polymer is determined by the scanning electron microscope observation when the insulating resin containing the organic polymer having the ionic group is formed on the surface of the conductive particles. It can be determined by whether or not it adheres to the surface of the particles. It was
  • the ionic group examples include onium-based functional groups such as a phosphonium group, an ammonium group and a sulfonium group.
  • onium-based functional groups such as a phosphonium group, an ammonium group and a sulfonium group.
  • ammonium groups or phosphonium groups are preferable from the viewpoint of enhancing the adhesiveness of the conductive particles and the insulating resin to form conductive particles having both insulating properties and conduction reliability at a high level. It is more preferably a phosphonium group.
  • onium-based functional group those represented by the following general formula (1) are preferably mentioned.
  • X is a phosphorus atom, a nitrogen atom, or a sulfur atom
  • R may be the same or different, 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 and a phosphorus atom, and 0 when X is a sulfur atom. * Is a bond.
  • Examples of the counterion for the ionic group include halide ions.
  • Examples of halide ions include Cl ⁇ , F ⁇ , Br ⁇ , and I ⁇ .
  • examples of the linear alkyl group represented by R include a linear alkyl group having 1 or more and 20 or less carbon atoms, and specifically, a methyl group, an ethyl group, or n ⁇ .
  • examples of the branched alkyl group represented by R include a branched alkyl group having 3 or more carbon atoms and 8 or less carbon atoms, and specifically, an isopropyl group, an isobutyl group, or s-.
  • examples thereof include a butyl group, a t-butyl group, an isopentyl group, an s-pentyl group, a t-pentyl group, an isohexyl group, an s-hexyl group, a t-hexyl group and an ethylhexyl group.
  • examples of the cyclic alkyl group represented by R include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclooctadecyl group. ..
  • examples of the aryl group represented by R include a phenyl group, a benzyl group, a tolyl group, an o-kisilyl group and the like.
  • R is preferably an alkyl group having 1 or more and 12 or less carbon atoms, more preferably an alkyl group having 1 or more and 10 or less carbon atoms, and an alkyl group having 1 or more and 8 or less carbon atoms. Is more preferable. Further, in the general formula (1), it is further preferable that R is a linear alkyl group.
  • the organic polymer having an ionic group constituting the insulating resin is represented by the following general formula (2) or general formula (3). It is preferable to have a structural unit represented.
  • X, R and n are synonymous with the general formula (1).
  • M is an integer of 0 or more and 5 or less .
  • An ⁇ indicates a monovalent anion.
  • X, R and n are synonymous with the general formula (1).
  • An ⁇ represents a monovalent anion.
  • M 1 is an integer of 1 or more and 5 or less.
  • R 5 is a hydrogen atom or It is a methyl group.
  • R in the formula (2) and the formula (3) the description of the functional group of R in the general formula (1) described above is appropriately applied.
  • the ionic group may be bonded to any of the para-position, the ortho-position, and the meta-position with respect to the CH group of the benzene ring of the formula (2), and is preferably bonded to the para-position.
  • a halide ion is preferably mentioned as the monovalent An ⁇ . Examples of halide ions include Cl ⁇ , F ⁇ , Br ⁇ , and I ⁇ .
  • m is preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and particularly preferably 1.
  • m 1 is preferably 1 or more and 3 or less, more preferably 1 or 2, and most preferably 2.
  • the organic polymer having an ionic group is preferably composed, for example, containing a monomer component having an onium-based functional group and an ethylenically unsaturated bond. From the viewpoint of facilitating the acquisition of the monomer and the synthesis of the polymer and increasing the production efficiency of the insulating resin, the organic polymer having an ionic group preferably contains a non-crosslinkable monomer component.
  • non-crosslinkable monomer having an onium-based functional group and an ethylenically unsaturated bond examples include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropylacrylamide, N, N, N-trimethyl.
  • -N-2-Armium group-containing monomer such as methacryloyloxyethylammonium chloride; Monomer having a sulfonium group such as phenyldimethylsulfonate sulfonatemethylsulfate; 4- (vinylbenzyl) triethylphosphonium chloride, 4- (vinylbenzyl) trimethyl Phosphonium chloride, 4- (vinylbenzyl) tributylphosphonium chloride, 4- (vinylbenzyl) trioctylphosphonium chloride, 4- (vinylbenzyl) triphenylphosphonium chloride, 2- (methacloyloxyethyl) trimethylphosphonium chloride, 2-( Phosphonium groups such as metachlorooxyethyl) triethylphosphonium chloride, 2- (methacloyloxyethyl) tributylphosphonium chloride, 2- (methacloyloxyethyl)
  • an ionic group may be bonded to all of the monomer components, or an ionic group may be bonded to a part of all the constituent units of the organic polymer. good.
  • the ratio of the monomer component to which the ionic group is bonded is preferably 0.01 mol% or more and 99 mol% or less, and is 0. More preferably, it is 0.02 mol% or more and 95 mol% or less.
  • the number of monomer components in the organic polymer counts the structure derived from one ethylenically unsaturated bond as a constituent unit of one monomer.
  • the ionic group is contained in both the crosslinkable monomer and the non-crosslinkable monomer, the ratio of the monomer components is the total amount.
  • Examples of the form of coating with the insulating resin include a form in which a plurality of insulating fine particles are arranged in a layer, or an insulating continuous film.
  • the insulating fine particles are melted, deformed, peeled off, or moved on the surface of the conductive particles by heat-bonding the conductive particles coated with the insulating fine particles between the electrodes to generate heat.
  • the metal surface of the conductive particles in the crimped portion is exposed, which enables conduction between the electrodes and provides connectivity.
  • the surface portion of the conductive particles facing a direction other than the thermocompression bonding direction is generally maintained in a state of being covered with the insulating fine particles on the surface of the conductive particles, conduction in a direction other than the thermocompression bonding direction is prevented. ..
  • the insulating fine particles can easily adhere to the conductive particles, whereby the ratio of the insulating fine particles covered with the insulating fine particles on the surface of the conductive particles can be made sufficient, and the insulating fine particles are conductive.
  • the peeling of insulating fine particles from the particles is effectively prevented. Therefore, the effect of preventing a short circuit in a direction different from that between the counter electrodes by the insulating fine particles is likely to be exhibited, and improvement in the insulating property in that direction can be expected.
  • the shape of the insulating fine particles is not particularly limited and may be spherical or may be a shape other than spherical.
  • Examples of the shape other than the spherical shape include a fibrous 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 thereof or may have an amorphous shape. Spherical insulating fine particles are preferable in terms of adhesion to conductive particles and ease of synthesis.
  • the average particle size (D) of the insulating fine particles 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 average particle size of the insulating fine particles is within the above range, it is easy to secure conduction between the counter electrodes without causing a short circuit in the obtained coated particles in a direction different from that between the counter electrodes.
  • the average particle size of the insulating fine particles is a value measured by observation using a scanning electron microscope, and specifically, it is measured by the method described in Examples described later.
  • the particle size distribution of the insulating fine particles measured by the above method varies.
  • the width of the particle size distribution of the powder is represented by the coefficient of variation (hereinafter also referred to as “CV”) represented by the following formula (1).
  • C. V. (%) (Standard deviation / average particle size) x 100 ... (1)
  • the coated particles of this embodiment are C.I. V. It is preferable to use insulating fine particles of 0.1% or more and 20% or less, more preferably 0.5% or more and 15% or less, and most preferably 1% or more and 10% or less. C. V. However, there is an advantage that the thickness of the coating layer made of the insulating fine particles can be made uniform.
  • the insulating resin may be a continuous film made of a polymer and having an ionic group instead of the above-mentioned insulating fine particles.
  • the insulating resin is a continuous film having an ionic group
  • the conductive particles are thermally pressure-bonded between the electrodes to melt, deform or peel off the continuous film, and the metal surface of the conductive particles is exposed. This enables continuity between the electrodes and provides connectivity.
  • the metal surface is often exposed by tearing the continuous film by thermocompression bonding the conductive particles between the electrodes.
  • the coating state of the conductive particles by the continuous film is generally maintained, so that conduction in a direction other than the thermocompression bonding direction is prevented. It is preferable that the continuous film also has an ionic group on the surface.
  • the thickness of the continuous film is preferably 10 nm or more from the viewpoint of improving the insulating property in a direction different from that between the counter electrodes, and 3,000 nm or less is preferable from the viewpoint of ease of conduction between the counter electrodes. Is preferable. From this point of view, the thickness of the continuous 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 ionic group in the continuous film, preferably forms a part of the chemical structure of the substance as a part of the substance constituting the continuous film.
  • the ionic group is preferably contained in at least one structure of the constituent unit of the polymer constituting the continuous film.
  • the ionic group is preferably chemically bonded to the polymer constituting the continuous film, and more preferably bonded to the side chain of the polymer.
  • the insulating particles are a continuous film obtained by coating the conductive particles with insulating fine particles having an ionic group on the surface and then heating the insulating fine particles.
  • it is preferably a continuous film obtained by dissolving the insulating fine particles with an organic solvent.
  • the insulating fine particles having an ionic group easily adhere to the conductive particles, whereby the ratio of being covered with the insulating fine particles on the surface of the conductive particles becomes sufficient, and the conductive particles are covered with the insulating fine particles. It becomes easy to prevent the peeling of the insulating fine particles from. Therefore, the continuous film obtained by heating or dissolving the insulating fine particles that coat the conductive particles can have a uniform thickness and a high coating ratio on the surface of the conductive particles.
  • the conductive particles of the present invention may be treated with a surface treatment agent for the purpose of increasing the affinity with the insulating resin and improving the adhesion.
  • a surface treatment agent examples include benzotriazole-based compounds, titanium-based compounds, higher fatty acids or derivatives thereof, phosphoric acid esters, phosphite esters and the like. These may be used alone or in combination of two or more as needed.
  • the surface treatment agent may or may not be chemically bonded to the metal on the surface of the conductive particles.
  • the surface treatment agent may be present on the surface of the conductive particles, and in that case, it may be present on the entire surface of the conductive particles, or may be present only on a part of the surface.
  • triazole-based compound examples include compounds having a nitrogen-containing heterocyclic structure having three nitrogen atoms in a 5-membered ring.
  • Examples of the triazole-based compound include a compound having a triazole monocyclic structure that is not condensed with another ring, and a compound having a ring structure in which a triazole ring and another ring are condensed.
  • Examples of other rings include a benzene ring and a naphthalene ring.
  • a compound having a ring structure in which a triazole ring and another ring are condensed is preferable because of its excellent adhesion to an insulating resin
  • a benzotriazole compound which is a compound having a structure in which a triazole ring and a benzene ring are condensed is particularly preferable.
  • the benzotriazole-based compound include those represented by the following general formula (I).
  • R 11 is a negative charge, a hydrogen atom, an alkali metal, an optionally substituted alkyl group, an amino group, a formyl group, a hydroxyl group, an alkoxy group, a sulfonic acid group or a silyl group, and R 12 ,.
  • R 13 , R 14 and R 15 are independently hydrogen atoms, halogen atoms, optionally substituted alkyl groups, carboxyl groups, hydroxyl groups or nitro groups.
  • Examples of the alkali metal represented by R 11 in the formula (I) include lithium, sodium, potassium and the like.
  • the alkali metal represented by R 11 is an alkali metal cation, and when R 11 in the formula (I) is an alkali metal, the bond between R 11 and the nitrogen atom may be an ionic bond.
  • Examples of the alkyl group represented by R 11 , R 12 , R 13 , R 14 and R 15 in the formula (I) include those having 1 to 20 carbon atoms, and 1 to 12 carbon atoms are particularly preferable.
  • the alkyl group may be substituted, and the substituents include an amino group, an alkoxy group, a carboxyl group, a hydroxyl group, an aldehyde group, a nitro group, a sulfonic acid group, a quaternary ammonium group, a sulfonium group and a sulfonyl group.
  • substituents include an amino group, an alkoxy group, a carboxyl group, a hydroxyl group, an aldehyde group, a nitro group, a sulfonic acid group, a quaternary ammonium group, a sulfonium group and a sulfonyl group.
  • Examples include a phosphonium group, a cyano group, a fluoroalkyl group, a mercapto group, and a halogen atom.
  • the alkoxy group represented by R 11 those having 1 to 12 carbon atoms are preferably mentioned.
  • the number of carbon atoms of the alkoxy group as a substituent of the alkyl group represented by R 12 , R 13 , R 14 and R 15 is preferably 1 to 12.
  • the halogen atom represented by R 12 , R 13 , R 14 and R 15 in the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • triazole-based compounds include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, and 5 as compounds having a triazole monocyclic structure.
  • -Mercapto-1H-1,2,3-triazole sodium 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole
  • benzotriazole having a ring structure in which a triazole ring and another ring are condensed, 1-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 4 -Carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 5-ethyl-1H-benzotriazole, 5-propyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, 1-aminobenzo Tri
  • the titanium-based compound for example, when a compound having a structure represented by the general formula (II) is present on the surface of conductive particles, an affinity between the insulating resin and the conductive particles can be easily obtained and a solvent. It is particularly preferable because it is easy to disperse in the particle and the surface of the conductive particles can be uniformly treated.
  • R 21 is a divalent or trivalent group
  • Examples of the aliphatic hydrocarbon group having 4 or more and 28 or less carbon atoms represented by R 22 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group.
  • Decyl group dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group and the like.
  • Examples of unsaturated aliphatic hydrocarbon groups include dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, nonadesenyl group, icosenyl group, eicosenyl group, henicosenyl group and docosenyl group as alkenyl groups. Be done.
  • Examples of the aryl group having 6 or more and 22 or less carbon atoms include a phenyl group, a tolyl group, a naphthyl group, an anthryl group and the like.
  • Examples of the arylalkyl group having 7 or more and 23 or less carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.
  • a linear or branched aliphatic hydrocarbon group is particularly preferable, and a linear aliphatic hydrocarbon group is particularly preferable.
  • the aliphatic hydrocarbon group as the hydrophobic group those having 4 or more and 28 or less carbon atoms are more preferable, and those having 6 or more and 24 or less are the most preferable, from the viewpoint of enhancing the affinity between the insulating resin and the conductive particles. preferable.
  • Examples of the divalent group represented by R 21 include -O-, -COO-, -OCO-, -OSO 2- and the like.
  • Examples of the trivalent group represented by R 21 include -P (OH) (O-) 2 , -OPO (OH) -OPO (O-) 2, and the like.
  • * is a bond, and the bond may be bonded to the metal film of the conductive particles, or may be bonded to another group or the like.
  • groups in that case include hydrocarbon groups, and specific examples thereof include alkyl groups having 1 or more and 12 or less carbon atoms.
  • the compound having the structure in which R 21 is a divalent group in the general formula (II) has the availability and the conductive property of the conductive particles. It is preferable in that it can be processed without damage.
  • the structure in which R 21 is a divalent group in the general formula (II) is represented by the following general formula (III).
  • R 21 is a group selected from -O-, -COO-, -OCO-, and -OSO 2- , and p, r and R 22 are synonymous with the general formula (II).
  • r is preferably 2 or 3, from the viewpoint of improving the adhesion between the insulating resin and the conductive layer, and r is most preferably 3.
  • titanate-based coupling agent used in the present invention examples include isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropyl (dioctylphosphite) titanate, and tetraisopropylbis.
  • titanate (Dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, Examples thereof include bis (dioctylpyrophosphate) ethylene titanate, and these can be used in one kind or two or more kinds.
  • These titanate-based coupling agents are commercially available, for example, from Ajinomoto Fine-Techno Co., Ltd.
  • the higher fatty acid is preferably a saturated or unsaturated linear or branched mono or polycarboxylic acid, more preferably a saturated or unsaturated linear or branched monocarboxylic acid. More preferably, it is a saturated or unsaturated linear monocarboxylic acid.
  • the fatty acid preferably has 7 or more carbon atoms.
  • the derivative refers to a salt or amide of the fatty acid.
  • the higher fatty acid or its derivative used in the present invention preferably has 7 to 23 carbon atoms, more preferably 10 to 20 carbon atoms.
  • Examples of such higher fatty acids or derivatives thereof include saturated fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid and stearic acid, unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and arachidonic acid, or these.
  • Metal salts or amides of the above can be mentioned.
  • the metal salt of the higher fatty acid examples include alkali metals, alkaline earth metals, transition metals such as Zr, Cr, Mn, Fe, Co, Ni, Cu and Ag, and metals other than transition metals such as Al and Zn. Examples thereof include polyvalent metal salts such as Al, Zn, W and V.
  • the higher fatty acid metal salt may be a mono-form, a di-form, a tri-form, a tetra-form or the like, depending on the valence of the metal.
  • the higher fatty acid metal salt may be any combination thereof.
  • the phosphoric acid ester and the phosphite ester those having an alkyl group having 6 to 22 carbon atoms are preferably used.
  • the phosphoric acid ester include phosphoric acid hexyl ester, phosphoric acid heptyl ester, phosphoric acid monooctyl ester, phosphoric acid monononyl ester, phosphoric acid monodecyl ester, phosphoric acid monoundecyl ester, phosphoric acid monododecyl ester, and phosphorus.
  • Examples thereof include acid monotridecyl ester, phosphoric acid monotetradecyl ester, and phosphoric acid monopentadecyl ester.
  • phosphite ester examples include succinic acid hexyl ester, succinic acid heptyl ester, sulphate monooctyl ester, sulphate monononyl ester, sulphate monodecyl ester, and sulphate monoundecyl ester.
  • examples thereof include phosphite monododecyl ester, sulphate monotridecyl ester, sulphate monotetradecyl ester, and sulphate monopentadecyl ester.
  • the surface treatment agent is preferably a triazole-based compound or a titanium-based compound, and is particularly benzotriazole or 4-carboxyl, because it has an excellent affinity with the insulating resin and has a high effect of increasing the coverage of the insulating resin.
  • Benzotriazole, isopropyltriisostearoyl titanate, and tetraisopropyl (dioctylphosphite) titanate are particularly preferred.
  • the method of treating the conductive particles with a surface treatment agent is obtained by dispersing the conductive particles in a solution of the surface treatment agent and then filtering the particles. Before the treatment with the surface treatment agent, the conductive particles may be treated with another treatment agent or may not be treated.
  • the concentration of the surface treatment agent in the solution of the surface treatment agent for dispersing the conductive particles (solution containing the conductive particles) is 0.01% by mass or more and 10.0% by mass or less.
  • the solvent in the solution of the surface treatment agent is water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, and other alcohols, acetone, and methyl.
  • Ketones such as isobutyl ketone, methyl ethyl ketone, methyl-n-butyl ketone, esters such as methyl acetate and ethyl acetate, ethers such as diethyl ether and ethylene glycol monoethyl ether, normal hexane, cyclohexanone, toluene, 1,4 -Dioxane, N, N-dimethylformamide, tetrahydrofuran and the like can be mentioned. It is preferable that the dispersed and filtered conductive particles after the surface treatment are dispersed in the solvent again to remove the excess surface treatment agent.
  • the surface treatment of the conductive particles with the surface treatment agent can be performed by mixing the conductive particles, the surface treatment agent and the solvent at room temperature.
  • the conductive particles and the surface treatment agent may be mixed in a solvent and then heated to accelerate the reaction.
  • the heating temperature is, for example, 30 ° C. or higher and 50 ° C. or lower.
  • the conductive particles of the present invention have low connection resistance and excellent connection reliability, for example, an anisotropic conductive film (ACF), a heat-sealed connector (HSC), and an LSI chip for driving an electrode of a liquid crystal display panel are used. It is suitably used as a conductive material for connecting to a circuit board of the above.
  • the conductive material include the use of the conductive particles of the present invention as they are, or the use of the conductive particles of the present invention dispersed in a binder resin.
  • Other forms of the conductive material are not particularly limited, and examples thereof include an anisotropic conductive paste, a conductive adhesive, and an anisotropic conductive ink.
  • binder resin examples include thermoplastic resins and thermosetting resins.
  • thermoplastic resin examples include acrylic resin, styrene resin, ethylene-vinyl acetate resin, styrene-butadiene block copolymer and the like
  • thermosetting resin examples include epoxy resin, phenol resin and urea resin. Examples thereof include polyester resin, urethane resin, and polyimide resin.
  • the conductive material includes a tackifier, a reactive aid, an epoxy resin curing agent, a metal oxide, a photoinitiator, a sensitizer, and curing, if necessary.
  • Agents, vulcanizers, deterioration inhibitors, heat resistant additives, heat conduction improvers, softeners, colorants, various coupling agents, metal deactivators and the like can be blended.
  • the amount of the conductive particles used may be appropriately determined according to the intended use, but from the viewpoint of facilitating electrical conduction without contacting the conductive particles, for example, 100 mass of the conductive material. It is preferably 0.01 parts by mass or more and 50 parts by mass or less, particularly preferably 0.03 parts by mass or more and 40 parts by mass or less.
  • the conductive particles of the present invention are particularly preferably used as a conductive filler for a conductive adhesive.
  • the conductive adhesive is disposed between two substrates on which a conductive substrate is formed, and is preferably used as an anisotropic conductive adhesive that adheres and conducts the conductive substrate by heating and pressurizing. ..
  • This anisotropic conductive adhesive contains the conductive particles of the present invention and an adhesive resin.
  • the adhesive resin can be used without particular limitation as long as it has an insulating property and is used as an adhesive resin. It may be either a thermoplastic resin or a thermosetting resin, and it is preferable that the adhesive performance is exhibited by heating.
  • Such adhesive resins include, for example, a thermoplastic type, a thermosetting type, an ultraviolet curable type and the like.
  • thermosetting type a composite type of a thermosetting type and an ultraviolet curable type, and the like, which show intermediate properties between a thermoplastic type and a thermosetting type.
  • adhesive resins can be appropriately selected according to the surface characteristics of the circuit board or the like to be adhered and the usage pattern.
  • an adhesive resin composed of a thermosetting resin is preferable because it has excellent material strength after bonding.
  • the adhesive resin examples include ethylene-vinyl acetate copolymer, carboxyl-modified ethylene-vinyl acetate copolymer, ethylene-isobutyl acrylate copolymer, polyamide, polyimide, polyester, polyvinyl ether, polyvinyl butyral, and polyurethane.
  • SBS block copolymer carboxyl-modified SBS copolymer, SIS copolymer, SEBS copolymer, maleic acid-modified SEBS copolymer, polybutadiene rubber, chloroprene rubber, carboxyl-modified chloroprene rubber, styrene-butadiene rubber, isobutylene- One or two selected from isoprene copolymer, acrylonitrile-butadiene rubber (hereinafter referred to as NBR), carboxyl-modified NBR, amine-modified NBR, epoxy resin, epoxy ester resin, acrylic resin, phenol resin, silicone resin and the like. Examples thereof include those prepared by using the one obtained by the above combination as the main agent.
  • thermoplastic resin styrene-butadiene rubber, SEBS, and the like are preferable as the thermoplastic resin because they have excellent reworkability.
  • thermosetting resin an epoxy resin is preferable. Of these, epoxy resin is most preferable because it has high adhesive strength, excellent heat resistance and electrical insulation, low melt viscosity, and can be connected at low pressure.
  • epoxy resin a commonly used epoxy resin can be used as long as it is a polyvalent epoxy resin having two or more epoxy groups in one molecule.
  • specific examples include novolak resins such as phenol novolac and cresol novolak, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, resorcin, and bishydroxydiphenyl ether, ethylene glycol, neopentyl glycol, glycerin, and trimethylolpropane.
  • Polyhydric alcohols such as polypropylene glycol, polyamino compounds such as ethylenediamine, triethylenetetramine, and aniline, polyhydric carboxy compounds such as adipic acid, phthalic acid, and isophthalic acid, etc., and epichlorhydrin or 2-methylepicrolhydrin.
  • a glycidyl type epoxy resin is exemplified. Examples thereof include aliphatic and alicyclic epoxy resins such as dicyclopentadiene epoxiside and butadiene dimer epoxiside. These can be used alone or in admixture of two or more.
  • the amount of the conductive particles used in the anisotropic conductive adhesive is usually 0.1 to 30 parts by mass, preferably 0.5 to 25 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the adhesive resin component. It is a department. When the amount of the conductive particles used is within this range, it is possible to suppress the increase in connection resistance and melt viscosity, improve the connection reliability, and sufficiently secure the anisotropy of the connection.
  • the above-mentioned anisotropic conductive adhesive may contain additives known in the art.
  • the blending amount may also be within the range known in the art.
  • Other additives include, for example, tackifiers, reactive aids, epoxy resin hardeners, metal oxides, photoinitiators, sensitizers, hardeners, vulcanizers, deterioration inhibitors, heat resistant additives, heat. Examples thereof include conduction improvers, softeners, colorants, various coupling agents, and metal deactivators.
  • tackifier examples include rosin, rosin derivative, terpene resin, terpene phenol resin, petroleum resin, kumaron-inden resin, styrene resin, isoprene resin, alkylphenol resin, xylene resin and the like.
  • reactive auxiliary agent examples include polyols, isocyanates, melamine resins, urea resins, utropines, amines, acid anhydrides, peroxides and the like.
  • the epoxy resin curing agent can be used without particular limitation as long as it has two or more active hydrogens in one minute.
  • polyamino compounds such as diethylenetriamine, triethylenetetramine, metaphenylenediamine, dicyandiamide and polyamideamine
  • organic acid anhydrides such as phthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and pyromellitic anhydride.
  • Novolac resins such as phenol novolac and cresol novolak can be mentioned. These can be used alone or in admixture of two or more. Further, a latent curing agent may be used if necessary.
  • latent curing agent examples include imidazole-based, hydrazide-based, boron trifluoride-amine complex, sulfonium salt, amineimide, polyamine salt, dicyandiamide and the like, and modified products thereof. These can be used alone or as a mixture of two or more.
  • the anisotropic conductive adhesive is manufactured by using a manufacturing apparatus usually used in the technical field. For example, conductive particles, an adhesive resin, and if necessary, a curing agent and various additives are blended, and if the adhesive resin is a thermosetting resin, it is mixed in an organic solvent, and if it is a thermoplastic resin, it is bonded. It is produced by melt-kneading at a temperature equal to or higher than the softening point of the agent resin, specifically preferably at about 50 to 130 ° C, more preferably about 60 to 110 ° C.
  • the anisotropic conductive adhesive thus obtained may be applied or may be applied in the form of a film.
  • connection structure can be obtained by connecting two circuit boards to each other using the conductive particles of the present invention or a conductive material containing the conductive particles.
  • Examples of the form of the connection structure include a connection structure between a flexible printed substrate and a glass substrate, a connection structure between a semiconductor chip and a flexible printed substrate, a connection structure between a semiconductor chip and a glass substrate, and the like.
  • the characteristics in the example were measured by the following method.
  • Average particle size 200 particles are arbitrarily extracted from a scanning electron microscope (SEM) photograph to be measured, the particle size is measured at a magnification of 10,000 times, and the arithmetic average value is the average particle. The diameter was set.
  • Thickness of the conductive layer The conductive particles were cut into two pieces, and the cross section of the cut end was observed and measured with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • Withstand current value Using a conductive fine particle electrical characteristic device (VI device, a device made by oneself with reference to the device described in JP-A No. 10-221388), the compressibility of the conductive particles is 30%. The current value (mA) that sometimes flows was measured.
  • VI device a conductive fine particle electrical characteristic device
  • Example 1 Pretreatment Spherical styrene-acrylate-silica composite resin particles having an average particle diameter of 3.0 ⁇ m were used as core particles. 9 g of the solution was added to a 200 mL aqueous conditioner solution (“Cleaner Conditioner 231” manufactured by Roam & Haas Electronic Materials) with stirring. The concentration of the aqueous conditioner solution was 40 mL / L. Subsequently, the surface of the core material particles was modified and dispersed by stirring for 30 minutes while applying ultrasonic waves at a liquid temperature of 60 ° C. This aqueous solution was filtered, and the core material particles washed once with ripulp water were made into a 200 mL slurry.
  • aqueous conditioner solution (“Cleaner Conditioner 231” manufactured by Roam & Haas Electronic Materials) with stirring. The concentration of the aqueous conditioner solution was 40 mL / L.
  • the surface of the core material particles was modified and dispersed by stirring for 30 minutes while
  • stannous chloride 0.1 g was added to this slurry. After stirring at room temperature for 5 minutes, a sensitization treatment was performed in which tin ions were adsorbed on the surface of the core material particles. Subsequently, this aqueous solution was filtered, and the core material particles washed once with ripulp water were made into a 200 mL slurry and maintained at 60 ° C. 1.5 mL of a 0.11 mol / L palladium chloride aqueous solution was added to this slurry. The mixture was stirred at 60 ° C. for 5 minutes to perform an activation treatment in which palladium ions were captured on the surface of the core material particles.
  • this aqueous solution was filtered, and the core material particles washed once with hot water were made into a 100 mL slurry, 10 mL of 0.5 g / L dimethylamine borane aqueous solution was added, and the mixture was stirred for 2 minutes while applying ultrasonic waves to pretreated the core material. A slurry of particles was obtained.
  • the obtained conductive particles were placed in a square container so as to have a thickness of 5 mm. This is placed in a vacuum heating furnace (KDF-75, manufactured by Denken Hydental) and heated from room temperature to 390 ° C at a heating rate of 5 ° C / min under a vacuum of 10 Pa, and then heat-treated at this temperature for 2 hours. Was done.
  • KDF-75 manufactured by Denken Hydental
  • the pressure was increased to atmospheric pressure by nitrogen purging, and then the particles were cooled to room temperature at a temperature lowering rate of 3 ° C./min by blowing nitrogen gas to obtain heat-treated conductive particles.
  • the average particle size of the obtained conductive particles was 3.22 ⁇ m, the thickness of the conductive layer was 110 nm, and the conductive particles had protrusions.
  • Table 1 shows the results of measuring the withstand current value of the obtained conductive particles.
  • Example 2 The vacuum heat treatment (4) in Example 1 was carried out by the following operation.
  • the conductive particles obtained by the (3) electroless plating treatment of Example 1 were placed in a square container so as to have a thickness of 5 mm. This is placed in a heating furnace (KDF-75, manufactured by Denken Hydental) and heated from room temperature to 390 ° C at a heating rate of 5 ° C / min under a vacuum of 100 Pa, and then heat-treated at this temperature for 2 hours. went.
  • the pressure was increased to atmospheric pressure by nitrogen purging, and then the particles were cooled to room temperature at a temperature lowering rate of 3 ° C./min by blowing nitrogen gas to obtain heat-treated conductive particles.
  • the average particle size of the obtained conductive particles was 3.22 ⁇ m, the thickness of the conductive layer was 110 nm, and the conductive particles had protrusions. Table 1 shows the results of measuring the withstand current value of the obtained conductive particles.
  • Example 3 The vacuum heat treatment (4) in Example 1 was carried out by the following operation.
  • the conductive particles obtained by the (3) electroless plating treatment of Example 1 were placed in a square container so as to have a thickness of 5 mm. This is placed in a heating furnace (KDF-75 manufactured by Denken Hydental Co., Ltd.) and heated from room temperature to 320 ° C. at a heating rate of 5 ° C./min under a vacuum of 10 Pa, and then heat-treated at this temperature for 2 hours. went.
  • the pressure was increased to atmospheric pressure by nitrogen purging, and then the particles were cooled to room temperature at a temperature lowering rate of 3 ° C./min by blowing nitrogen gas to obtain heat-treated conductive particles.
  • the average particle size of the obtained conductive particles was 3.22 ⁇ m, the thickness of the conductive layer was 110 nm, and the conductive particles had protrusions. Table 1 shows the results of measuring the withstand current value of the obtained conductive particles.
  • Comparative Example 1 The conductive particles obtained by the (3) electroless plating treatment of Example 1 were used as the conductive particles of Comparative Example 1. Table 1 shows the results of measuring the withstand current value of the conductive particles.
  • Example 2 The following operation was performed instead of (4) vacuum heat treatment in Example 1.
  • the conductive particles obtained by the (3) electroless plating treatment of Example 1 were placed in a square container so as to have a thickness of 5 mm. This was placed in a heating furnace (KDF-75, manufactured by Denken Hydental Co., Ltd.) and heat-treated at 260 ° C. for 2 hours under normal pressure in a nitrogen atmosphere. After the heat treatment, the particles were allowed to cool to room temperature to obtain heat-treated conductive particles.
  • the average particle size of the obtained conductive particles was 3.22 ⁇ m, the thickness of the conductive layer was 110 nm, and the conductive particles had protrusions. Table 1 shows the results of measuring the withstand current value of the obtained conductive particles.
  • Example 3 The following operation was performed instead of (4) vacuum heat treatment in Example 1.
  • the conductive particles obtained by the (3) electroless plating treatment of Example 1 were placed in a square container so as to have a thickness of 5 mm. This was placed in a heating furnace (KDF-75, manufactured by Denken Hydental Co., Ltd.) and heat-treated at 390 ° C. for 2 hours under normal pressure in a nitrogen atmosphere. After the heat treatment, the particles were allowed to cool to room temperature to obtain heat-treated conductive particles.
  • the average particle size of the obtained conductive particles was 3.22 ⁇ m, the thickness of the conductive layer was 110 nm, and the conductive particles had protrusions. Table 1 shows the results of measuring the withstand current value of the obtained conductive particles.
  • connection resistance and connection reliability were evaluated by the following methods. 1.0 g of the conductive particles obtained in Examples and Comparative Examples were placed in a vertically standing resin cylinder having an inner diameter of 10 mm, and a load of 2 kN was applied at room temperature (25 ° C., 50% RH). The electrical resistance between the upper and lower electrodes was measured, and the initial volume resistance value was obtained. It can be evaluated that the lower the initial volume resistance value, the lower the connection resistance of the conductive particles. Furthermore, the resistance value after holding for 24 hours under the conditions of 85 ° C. and 85% RH was also measured. It can be evaluated that the smaller the difference from the connection resistance value at room temperature, the better the connection reliability of the conductive particles.
  • the conductive particles obtained in the examples have a lower initial volume resistance value and lower connection resistance than the conductive particles obtained in the comparative example. Further, the conductive particles obtained in the examples had a smaller difference between the initial volume resistance value and the resistance value after 24 hours at 85 ° C. and 85% RH as compared with the conductive particles obtained in the comparative example. It can be seen that the connection reliability is high. In particular, when the conductive particles obtained in Examples 1 and 2 and the conductive particles obtained in Comparative Example 3 are compared, the connection resistance is low and the connection reliability is excellent by heating under a vacuum. It can be seen that conductive particles can be obtained.

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Abstract

L'invention concerne un procédé de production de particules conductrices, lequel influence peu la qualité des particules conductrices tout en permettant de limiter les coûts de production. Plus spécifiquement, ce procédé de production de particules conductrices comporte une étape au cours de laquelle des particules conductrices présentant une couche conductrice sur la surface d'une particule de coeur sont chauffées à une température comprise entre 200 et 600℃ sous un vide de degré inférieur ou égal à 1000 Pa. De préférence, le temps de chauffage est compris entre 0,1 et 10 heures. De préférence, la particule de coeur est formée d'une substance organique ou à la fois d'une substance inorganique et d'une substance organique, et de préférence, la couche conductrice est au moins un élément choisi dans le groupe contenant nickel, or, alliage de nickel et alliage d'or.
PCT/JP2021/018784 2020-05-20 2021-05-18 Procédé de production de particules conductrices et particules conductrices WO2021235433A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63153280A (ja) * 1986-12-17 1988-06-25 Nippon Shirika Kogyo Kk 導電性無機珪酸質材料の製造方法
JP2000243132A (ja) * 1999-02-22 2000-09-08 Nippon Chem Ind Co Ltd 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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200728A (ja) 2004-01-16 2005-07-28 Mitsui Mining & Smelting Co Ltd 二層コート粒子粉末の製造方法及びその製造方法で得られた二層コート粒子粉末
JP6777405B2 (ja) 2015-03-03 2020-10-28 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、導電材料及び接続構造体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63153280A (ja) * 1986-12-17 1988-06-25 Nippon Shirika Kogyo Kk 導電性無機珪酸質材料の製造方法
JP2000243132A (ja) * 1999-02-22 2000-09-08 Nippon Chem Ind Co Ltd 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

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