WO2010032854A1 - Particules électroconductrices et matériau électroconducteur anisotrope utilisant ces particules - Google Patents

Particules électroconductrices et matériau électroconducteur anisotrope utilisant ces particules Download PDF

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WO2010032854A1
WO2010032854A1 PCT/JP2009/066455 JP2009066455W WO2010032854A1 WO 2010032854 A1 WO2010032854 A1 WO 2010032854A1 JP 2009066455 W JP2009066455 W JP 2009066455W WO 2010032854 A1 WO2010032854 A1 WO 2010032854A1
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particles
fine particles
base
parts
conductive fine
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PCT/JP2009/066455
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English (en)
Japanese (ja)
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令晋 佐々木
和明 松本
純子 木太
勇人 池田
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株式会社日本触媒
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Priority to KR1020117006494A priority Critical patent/KR101368836B1/ko
Priority to CN2009801367693A priority patent/CN102160125B/zh
Priority to JP2010529829A priority patent/JP5539887B2/ja
Publication of WO2010032854A1 publication Critical patent/WO2010032854A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • 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
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0221—Insulating particles having an electrically conductive coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to conductive fine particles and an anisotropic conductive material using the conductive fine particles.
  • liquid crystal display panel ITO electrodes and drive LSI connections, LSI chip and circuit board connections, and fine pattern electrode terminals For the electrical connection between minute parts of electronic devices such as the connection between them, the application of the electrical connection using the anisotropic conductive material containing the conductive fine particles is expanding from the conventional connection by the solder or the connector.
  • Conductive fine particles are widely used as the main constituent material of anisotropic conductive materials, and are generally mixed in a binder resin and the like, and are anisotropic conductive films, anisotropic conductive pastes, conductive adhesives, conductive Processed into a form such as a pressure-sensitive adhesive.
  • metal particles such as gold, silver, and nickel have been used as conductive fine particles.
  • these metal particles have a large specific gravity and the shape thereof is not constant, so it may be difficult to uniformly disperse in the binder resin. This is a cause of unevenness in the conductivity of the conductive material.
  • conductive fine particles there are conductive fine particles in which inorganic fine particles or organic resin fine particles having a uniform particle diameter are used as base particles and the surface of the base particles is coated with a metal such as nickel by an electroless plating method.
  • Patent Documents 1 to 4 Patent Documents 1 to 4.
  • the base particles are degreased and fine irregularities are formed on the base particle surfaces prior to the electroless plating.
  • a pretreatment process such as an etching treatment or a catalyst treatment for supporting the catalyst on the surface of the substrate particles is performed.
  • a resin coating layer containing a functional group having a binding ability with metal ions is provided on the surface of the base material particles.
  • a technique of using a dispersion stabilizer having at least one functional group selected from a carboxyl group and a sulfone group at the time of polymerization of particles, or using a polymerizable monomer having the above-mentioned functional group as a raw material for base particles has also been proposed (Patent Documents 5 and 6).
  • the base particle obtained by the above technique can form a plating film without performing an etching treatment, it is not sufficient in terms of adhesion between the base particle and the metal layer, and the plating film is also cracked. It could not be completely eliminated.
  • Patent Document 7 discloses that when a conductive metal layer is formed on the surface of the polymer fine particles, a peroxide group and / or a hydroxyl group is selectively introduced into the surface of the polymer fine particles by low-temperature plasma treatment to selectively hydrophilize. Then, a method of forming a conductive metal coating layer is disclosed.
  • agglomeration of the base particles during the plating treatment can be prevented to some extent, and the occurrence of defects in the plating film derived from the agglomeration of the base particles can be suppressed.
  • the effects of only peroxide groups and / or hydroxyl groups introduced to the particle surface are insufficient, and further, degreasing treatment, chromic acid, It was necessary to form an anchor on the surface of the substrate particles by performing an etching process or the like.
  • the present invention has been made by paying attention to the above situation, and can greatly simplify the conventional conductive metal layer application step, and at the same time, uniformly coat the surface of the substrate particles with the conductive layer.
  • the present invention provides conductive fine particles that are excellent in adhesion between base particles and conductive metal layers, have very few defects such as cracks in the conductive metal layers, and anisotropic conductive materials using the conductive fine particles. That was the issue.
  • the conductive fine particles of the present invention are conductive fine particles having base particles and a conductive metal layer covering the surface of the base particles, and the base particles are vinyl having a mass average particle diameter of 1000 ⁇ m or less.
  • the total number of alkali metal and nitrogen atoms relative to the number of carbon atoms measured by X-ray photoelectron spectroscopy (ESCA) after the base particles are treated with sodium adsorption by the following method. It is characterized in that the ratio M / C (number ratio) of the amount is 0.5 ⁇ 10 ⁇ 2 or more and the degree of hydrophobicity is less than 2%.
  • the conductive fine particles of the present invention have base particles exhibiting an alkali metal content and a degree of hydrophobicity in the above-mentioned range, and the base particles have high hydrophilicity, so that the base particles and the surface thereof are covered. It is excellent in adhesiveness with the metal to be used, and the base particles are less likely to aggregate with each other.
  • the base particles preferably have an M / C ratio of 0.5 ⁇ 10 ⁇ 2 or more before sodium adsorption treatment.
  • the acid value of the base particle before the sodium adsorption treatment is preferably 0.05 mgKOH / g or more.
  • the alkali metal is preferably sodium.
  • the coefficient of variation of the particle diameter of the base particle is 15% or less, and the base particle has a carboxyl group and / or a carboxylate group (COOM, M is an alkali metal ion or an amine cation on the surface). It is desirable to have
  • the conductive fine particles of the present invention include those having an insulating resin layer on at least a part of its surface.
  • An anisotropic conductive material using the above conductive fine particles is a recommended embodiment of the present invention.
  • conductive fine particles having excellent adhesion between the base particles and the conductive metal layer can be obtained without performing pretreatment steps such as degreasing and etching. Can be greatly simplified, and at the same time, a conductive metal layer having excellent adhesion to the substrate particles can be uniformly formed on the surface of the substrate particles.
  • the conductive fine particles of the present invention are excellent in adhesion between the substrate particles and the conductive metal layer, the conductive metal layer hardly breaks or peels off, and an anisotropic conductive material using the conductive fine particle Is highly reliable so that the electrical connection between the electrode substrates can be maintained over a long period of time.
  • Example 6 is a SEM image of conductive fine particles obtained in Example 6.
  • 10 is a SEM image of conductive fine particles obtained in Example 9.
  • 7 is an FE-SEM image of conductive fine particles obtained in Example 9.
  • 10 is a graph showing the results of elemental analysis of conductive fine particles obtained in Example 9.
  • 6 is a cross-sectional FE-SEM image of conductive fine particles obtained in Example 9.
  • the conductive fine particles of the present invention are conductive fine particles having base particles and a conductive metal layer covering the surface of the base particles, and the base particles are vinyl having a mass average particle diameter of 1000 ⁇ m or less.
  • the ratio of the number of atoms of alkali metal and nitrogen to the number of atoms of carbon measured by X-ray photoelectron spectroscopy (ESCA) after the substrate particles are subjected to sodium adsorption treatment and M / C. (Atom ratio, M is the total number of atoms of alkali metal and nitrogen, C is the number of carbon atoms) is 0.5 ⁇ 10 ⁇ 2 or more and the degree of hydrophobicity is less than 2% It has the characteristic in that.
  • the base material particle according to the present invention is subjected to sodium adsorption treatment by the following method, and then the ratio M of the abundance of alkali metal element and nitrogen element to the abundance of carbon element measured by X-ray photoelectron spectroscopy (ESCA). / C is 0.5 ⁇ 10 ⁇ 2 or more.
  • the base particle according to the present invention has a carboxyl group as one of the acidic functional groups on the surface thereof, whereby the surface of the base particle is hydrophilized, and the base particle and the conductive particles are electrically conductive.
  • the adhesiveness with the conductive metal layer is good. However, the detailed reason is unclear by the study of the present inventors.
  • M / C is preferably 1.0 ⁇ 10 ⁇ 2 or more, and more preferably 1.5 ⁇ 10 ⁇ 2 or more.
  • the upper limit of M / C is not particularly limited, but is preferably 30 ⁇ 10 ⁇ 2 or less, more preferably 20 ⁇ 10 ⁇ 2 or less, still more preferably 13 ⁇ 10 ⁇ 2 or less, and further preferably 10 ⁇ . 10 ⁇ 2 or less, most preferably 8 ⁇ 10 ⁇ 2 or less.
  • the suspension is subjected to solid-liquid separation, and the base particles are washed with 100 parts by mass of ion-exchanged water, and further washed with 33 parts by mass of methanol to wash the base particles. After washing, the obtained base particles are vacuum-dried at 120 ° C. for 2 hours.
  • the base particles before the sodium adsorption treatment preferably have an M / C (atomic number ratio) measured by X-ray photoelectron spectroscopy (ESCA) of 0.5 ⁇ 10 ⁇ 2 or more. It is preferred that the alkali metal is adsorbed on the substrate particles or the alkali metal salt or amine salt of carboxylic acid is present on the surface of the substrate particles. That is, irrespective of the presence or absence of the sodium adsorption treatment, when the M / C is in the above range, the adhesion (plating property) of the conductive metal layer is improved. Therefore, the preferable range of M / C of the base particle before the sodium adsorption treatment is also the same range as the base particle M / C after the sodium adsorption treatment.
  • M / C atomic number ratio
  • M is the measured abundance of alkali metal atoms and nitrogen atoms on the surface of the substrate particles
  • C is the abundance of carbon atoms.
  • the nitrogen atom is a component derived from an amine salt.
  • the alkali metal to be measured includes lithium, potassium, rubidium, cesium and the like in addition to sodium used in the sodium adsorption treatment, but sodium is preferable.
  • the degree of hydrophilicity of the base particles can be expressed by the degree of hydrophobicity or the acid value described later.
  • the degree of hydrophobicity of the substrate particles according to the present invention is preferably less than 2%, more preferably 1% or less, still more preferably 0.5% or less, and most preferably 0%. .
  • the degree of hydrophobicity can be determined as follows.
  • the degree of hydrophobicity was determined to be 0%.
  • the conductive fine particles of the present invention have a conductive metal layer that covers the surface of the substrate particles.
  • the metal constituting the conductive metal layer is not particularly limited.
  • gold, silver, copper, platinum, iron, lead, aluminum, chromium, palladium, nickel, rhodium, ruthenium, antimony, bismuth, germanium, tin examples thereof include metals such as cobalt, indium, nickel-phosphorus, and nickel-boron, metal compounds, and alloys thereof.
  • nickel, gold, silver, and copper are preferable because they are excellent in conductivity and industrially inexpensive.
  • the thickness of the conductive metal layer is preferably 10 nm to 500 nm. More preferably, it is 20 nm to 400 nm, and further preferably 50 nm to 300 nm.
  • the thickness of the conductive metal layer is too thin, there is a tendency that it is difficult to maintain a stable electrical connection when the conductive fine particles are used as the anisotropic conductive material.
  • the conductive metal layer is too thick, the surface hardness of the conductive fine particles becomes too high, and there is a possibility that the mechanical properties of the substrate particles such as the recovery rate cannot be fully utilized.
  • the conductive metal layer has no substantial cracks or a surface on which the conductive metal layer is not formed.
  • a surface on which a substantial crack or a conductive metal layer is not formed means that the surface of any 10,000 conductive fine particles is observed using an electron microscope (1000 times magnification). It means that the crack of the metal layer and the exposure of the surface of the base material particle are not substantially visually observed. A detailed evaluation method will be described later.
  • the conductive fine particles of the present invention may further have an insulating resin layer on the surface of the conductive metal layer.
  • the insulating resin layer is not particularly limited as long as the insulating property between the particles of the conductive fine particles can be ensured, and the insulating resin layer can be easily collapsed or peeled off by a certain pressure and / or heating.
  • polyolefins such as polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer; polymethyl (meth) acrylate, polyethyl (meth) acrylate, as well as resins similar to vinyl polymer fine particles described later (Meth) acrylate polymers and copolymers such as polybutyl (meth) acrylate; polystyrene, styrene-acrylate copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer and Block polymers such as these hydrogenated compounds; Thermoplastic resins such as ethylene-based polymers and copolymers, and particularly crosslinked products thereof; Thermosetting resins such as epoxy resins, phenol resins, melamine resins; polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, poly(vin
  • the insulating resin layer is too hard compared to the vinyl polymer fine particles, the base material particles themselves may be destroyed before the insulating resin layer is destroyed. Therefore, it is preferable to use an uncrosslinked or relatively low degree of crosslinking resin for the insulating resin layer.
  • the insulating resin layer may be a single layer or a plurality of layers.
  • a single or a plurality of film-like layers may be formed, or particles having insulating particles, spheres, lumps, scales or other shapes attached to the surface of conductive fine particles, Furthermore, it may be formed by chemically modifying the surface of the conductive fine particles, or a combination of these.
  • the thickness of the insulating resin layer is preferably 0.01 ⁇ m to 1 ⁇ m. More preferably, it is 0.1 ⁇ m to 0.5 ⁇ m. When the thickness of the insulating resin layer is too thin, the electrical insulation becomes insufficient. On the other hand, when the thickness is too thick, the conduction characteristics may be deteriorated.
  • the substrate particles according to the present invention are obtained by subjecting a vinyl polymer fine particle to contact with a mixed gas containing a fluorine gas and a gas containing a compound containing oxygen atoms. It is desirable that it is made hydrophilic. By the said process, the surface of a base particle is hydrophilized and it has a specific acid value. The above processing will be described in detail later.
  • the amount of acidic functional groups on the surface of the substrate particles may be grasped based on the acid value, and this may be used as an index of the degree of hydrophilicity.
  • the acid value of the base particles is preferably 0.05 mgKOH / g or more, more preferably 0.1 mgKOH / g or more, and further preferably 1.0 mgKOH / g or more.
  • the acid value is too low, the hydrophilicity of the particles becomes insufficient, and when the conductive metal layer is coated by electroless plating treatment, the dispersibility of the particles in the aqueous medium is reduced. There is also a possibility that the adhesiveness between the conductive metal layer and the base material particles may be lowered.
  • the acid value is a value calculated from the measurement result of the KOH neutralization amount. A method for measuring the neutralized amount of KOH will be described later.
  • the substrate particles according to the present invention preferably have a carboxyl group on the surface. Due to the presence of the carboxyl group, the surface of the base particle is hydrophilized, and the adhesion between the base particle and the conductive metal layer is improved. The presence or absence of a carboxyl group on the surface of the substrate particle can be confirmed by an X-ray photoelectron analyzer (ESCA) or the like.
  • ESA X-ray photoelectron analyzer
  • the base particle according to the present invention may have —C (F) ⁇ O in addition to the carboxyl group on the surface thereof, and further, in addition to these groups on the surface or inside of the particle,
  • a fluorine component covalently bonded to hydrocarbon carbon also referred to as covalent bond fluorine
  • the covalently bonded fluorine has an effect of suppressing secondary aggregation between particles by coexisting with —C (F) ⁇ O and / or a carboxyl group, it is preferably present even in a trace amount.
  • hydrogen fluoride may be attached to the base particles of the present invention as a fluorine component. Since this HF may be harmful when handling the substrate fine particles of the present invention, the smaller the amount of adhesion, the better. More preferably, no HF is attached.
  • fluorine components can be distinguished by the eluting fluorine content and the non-eluting fluorine content. That is, in the dissolution test described later, fluorine ionized and eluted in the solvent is referred to as eluting fluorine, and the content thereof is defined as the eluting fluorine content.
  • the eluting fluorine includes fluorine derived from the attached (free) hydrogen fluoride and fluorine derived from —C (F) ⁇ O.
  • non-eluting fluorine is non-eluting fluorine, and its content is non-eluting fluorine content.
  • the non-eluting fluorine usually corresponds to the above-described covalently bonded fluorine, but may contain a free fluorine component that is incorporated into the particles and cannot be eluted.
  • the eluting fluorine content and the non-eluting fluorine content are expressed in terms of fluorine atom content (mg / g) contained per 1 g of particles.
  • non-eluting fluorine exists to some extent.
  • the range of 0.1 mg / g to 50 mg / g is preferable because the effect of suppressing the secondary aggregation described above is exhibited.
  • the amount is too large, the hydrophilicity may be insufficient or the mechanical properties of the particles may be deteriorated.
  • More preferable non-eluting fluorine content is 1 mg / g to 40 mg / g, and further preferably 2 mg / g to 20 mg / g.
  • the content of the eluting fluorine is preferably small or absent, and specifically, it is preferably less than 1 mg / g. It is more preferably 0.5 mg / g or less, further preferably 0.2 mg / g or less, still more preferably 0.1 mg / g or less, and particularly preferably 0.01 mg / g or less.
  • the amount F / C (atom number ratio) of fluorine atoms to carbon atoms present on the surface of the substrate particles measured by ESCA is preferably 0.5 ⁇ 10 ⁇ 2 to 30 ⁇ 10 ⁇ 2 . More preferably, it is 1 ⁇ 10 ⁇ 2 to 20 ⁇ 10 ⁇ 2 .
  • the substrate particles according to the present invention are preferably excellent in dispersibility in an alkaline solution.
  • the dispersion state of the base material particles in the alkaline solution is equivalent to the dispersion state of the base material particles in the ion-exchanged water containing the dispersant.
  • the dispersibility of the base particles in the alkaline solution is preferably such that the value of ⁇ (dispersibility in the alkaline solution) obtained by the following formula is 3% or less. More preferably, it is 2% or less.
  • ⁇ (%) (
  • Da represents the average dispersed particle size of the substrate particles in the alkaline solution
  • Db represents the average dispersed particle size of the substrate particles in the ion-exchanged water containing the dispersant.
  • the Da was added to 1 part of a base particle in 20 parts of a 0.1% by weight aqueous sodium hydroxide solution (mixed solution of water and methanol in a mass ratio of 1: 1) and stirred at 25 ° C. for 20 minutes.
  • the volume-based average particle diameter measured using a Multisizer III type (manufactured by Beckman Coulter, Inc., measurement range: 1 ⁇ m to 10 ⁇ m, with simultaneous passage correction).
  • Db is obtained by adding 1 part of base particles to 4000 parts of a 1% by weight Hytenol (registered trademark) N-08 (Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution and subjecting the base particles to ultrasonic treatment for 10 minutes. After being dispersed in an aqueous solution, it was magnified 500 times with a power high scope (manufactured by HiROX, KH-2700), and after confirming the absence of aggregated particles, Coulter Multisizer III (measurement range: 1 ⁇ m to 10 ⁇ m, simultaneous The volume-based average diameter measured using the “pass correction” was defined as Db (average primary particle diameter). That is, Db approximates the state in which the base particles are dispersed with primary particles.
  • the shape of the substrate particles used in the present invention is not particularly limited, and may be, for example, spherical, spheroid, confetti, thin plate, needle, or eyebrows, and the particle surface is smooth. Any of a bowl shape and a porous shape may be used. Among these, when used as conductive fine particles, a spherical shape is preferable in that a good surface contact state is formed when the particles are deformed between the electrodes.
  • the size of the base particles is 1 mm (1000 ⁇ m) or less in terms of mass average particle diameter. This is because base particles exceeding 1 mm have limited applications when processed into conductive particles, and there are few industrial applications.
  • the mass average particle diameter is preferably 0.1 ⁇ m to 1000 ⁇ m, more preferably 0.5 ⁇ m to 500 ⁇ m, and still more preferably 1 ⁇ m to 100 ⁇ m. When the mass average particle diameter of the substrate particles is too small, the particles are likely to aggregate when coating the conductive metal layer such as electroless plating, and it may be difficult to form a uniform conductive metal layer.
  • the mass average particle diameter means a value obtained as a volume average particle diameter in a conventionally known particle size distribution measurement method, and specifically, a precision particle size distribution measurement apparatus using the Coulter principle (for example, trade name “ It is a value measured by “Coulter Multisizer Type III”, manufactured by Beckman Coulter, Inc.).
  • the coefficient of variation (CV value) in the particle diameter of the base particles used in the present invention is preferably 15% or less, more preferably 10% or less, and further preferably 8% or less. This is because the smaller the CV value, the smaller the particle size distribution.
  • the CV value is a value obtained by applying the average particle diameter of the base material particle measured by a precision particle size distribution measuring apparatus using the Coulter principle and the standard deviation of the particle diameter of the base material particle to the following equation. .
  • Coefficient of variation (%) in particle diameter of substrate particles 100 ⁇ standard deviation of particle diameter / average particle diameter
  • the preferred range of the mass average particle diameter and coefficient of variation of the vinyl polymer fine particles before hydrophilization treatment described later is also the same as that of the base particles.
  • the base particles are preferably obtained by hydrophilizing vinyl polymer fine particles.
  • the dispersibility, mechanical characteristics, hue, and particle size distribution characteristics (CV value) of the base material particles and the vinyl polymer fine particles are preferably similar, and preferably not changed before and after the hydrophilization treatment.
  • the dispersibility is a property that the particles are not fixed or fused.
  • the mechanical characteristics can be evaluated by, for example, a compression elastic modulus, a compression fracture load, a recovery rate, and the like.
  • the compression elastic modulus of the present invention is the elastic modulus (N / mm 2 : MPa) when a particle is loaded and deformed by 10%, and the compressive fracture load is the load (mN) when compression is strengthened to cause fracture.
  • the recovery rate is the recovery rate after compression (%).
  • Substrate particles, in any of the vinyl polymer particles and the conductive fine particles, the compression modulus is preferably 1000 N / mm 2 or more, more preferably 2000N / mm 2 or more, 3000N / mm 2 or more is more preferable.
  • the compressive fracture load is preferably 1 mN or more, more preferably 3 mN or more, and further preferably 5 mN or more.
  • the recovery rate is preferably 0.5% or more, more preferably 1% or more, and further preferably 5% or more.
  • Examples of the method for measuring the mechanical characteristics include the following methods.
  • Compressive fracture load A load is applied to the particles in the same manner as the compression elastic modulus, and a load (mN) when the particles are broken by deformation is defined as a compression failure load.
  • the vinyl polymer fine particles used as the raw material for the base particles according to the present invention are not particularly limited as long as they are particles containing a vinyl polymer, and particles composed of only a vinyl polymer or a composite of organic and inorganic substances. Any of the organic-inorganic composite particles made of the prepared material can be used.
  • the term “vinyl” used in the present invention includes (meth) acryloyl.
  • the vinyl polymer fine particles include particles composed only of vinyl polymers such as (meth) acrylic (co) polymers, (meth) acrylic-styrene copolymers, and polymerizable ( Meaning of containing vinyl group; the same applies hereinafter) Organic radical composite particles and / or condensation polymers of alkoxysilane, and organic-inorganic composite particles such as a copolymer of polymerizable alkoxysilane and vinyl monomer.
  • the term “vinyl polymer” means an organic-only polymer obtained by polymerizing vinyl monomers.
  • the “vinyl polymer fine particles” as used in the present invention means particles containing a component or a skeleton made of “vinyl polymer”.
  • Vinyl polymer particles are obtained by polymerizing a monomer composition containing a monomer mixture containing a vinyl monomer.
  • the vinyl monomer contained in the monomer mixture is a non-crosslinkable monomer having one vinyl group in one molecule, and a crosslinkable monomer having two or more vinyl groups in one molecule. Any of these can be used.
  • non-crosslinkable monomer examples include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, glycidyl (meth) acrylate, cyclohex (Meth) acrylates such as xyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl
  • non-crosslinkable monomer when (meth) acrylic acid is used as the non-crosslinkable monomer, it may be partially neutralized with an alkali metal.
  • the above-mentioned non-crosslinkable monomers may be used alone or in combination of two or more.
  • a monomer having no ester bond in the molecule is preferably used as an essential component, and among them, a styrene monomer is preferable, and styrene, ⁇ -methylstyrene are particularly preferable. Ethyl vinyl benzene and the like are preferable.
  • crosslinkable monomer examples include trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, pentadecaethylene glycol dimethacrylate, pentacontact ethylene glycol dimethacrylate.
  • Polyfunctional (meth) acrylates such as methacrylate, 1,3-butylene dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate Polyalkylene glycol di (meth) acrylates such as acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; N, Examples thereof include cross-linking agents such as N-divinylaniline, divinyl ether, divinyl sulfide, diviny
  • crosslinkable monomers may be used alone or in combination of two or more. Among these, it is preferable to use a monomer having no ester bond in the molecule as an essential component. Among them, an aromatic divinyl compound is preferable, and divinylbenzene is particularly preferable.
  • the amount of the styrene monomer and / or aromatic divinyl compound used is preferably 1% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the total vinyl monomer mixture. Further, it is preferably 30% by mass or more.
  • a styrene monomer is used as the non-crosslinkable monomer and an aromatic divinyl compound is used as the crosslinkable monomer, the plating property to the substrate particles is improved, which is preferable.
  • the content of the crosslinkable monomer in the monomer mixture is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the content of the crosslinkable monomer in the monomer mixture is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the solvent resistance and heat resistance of the vinyl polymer particles are increased, and the mechanical properties can be appropriately controlled.
  • the organic-inorganic composite particles described later for example, when a silicon compound (alkoxysilane) having a (meth) acryloyl group is used as a raw material, since this compound also functions as a crosslinking agent in the particles, Is also considered a crosslinkable monomer.
  • a polymerization initiator or a dispersion stabilizer may be used as necessary.
  • the polymerization initiator any of those usually used for polymerization can be used.
  • a peroxide initiator, an azo initiator, or the like can be used.
  • the peroxide initiator include hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide.
  • Oxide t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, diisopropyl
  • examples thereof include peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and the like.
  • azo initiator examples include dimethyl 2,2-azobisisobutyronitrile, azobiscyclohexacarbonitrile, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl). Valeronitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3-trimethyl) Butyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanopentanoic acid), Examples include 4,4′-azobis (4-cyanovaleric acid), di
  • These polymerization initiators may be used alone or in combination of two or more.
  • the addition amount of these polymerization initiators is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 5 parts by mass or less with respect to 100 parts by mass of the monomer mixture. It is preferable that it is 3 parts by mass or less.
  • the dispersion stabilizer is used to stabilize the droplet diameter of the monomer composition during the polymerization reaction when the monomer composition is polymerized using a suspension polymerization method or the like.
  • the dispersion stabilizer may be dissolved or dispersed in a solvent (for example, an aqueous solvent) as a dispersion medium without being contained in the monomer composition.
  • a solvent for example, an aqueous solvent
  • any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant may be used.
  • a dispersion stabilizer may be used independently and may use 2 or more types together.
  • fatty acid oils such as sodium oleate and castor oil potassium
  • alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate
  • polyoxyethylene distyryl phenyl ether sulfate ammonium salt polyoxyethylene distyryl phenyl ether sulfate
  • Polyoxyethylene distyryl phenyl ether sulfate such as sodium salt
  • alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate
  • alkyl naphthalene sulfonate, alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester, naphthalene Anion such as sulfonic acid formalin condensate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl sulfate Emissions surfactants
  • the amount of the dispersion stabilizer may be appropriately adjusted according to the desired size of the vinyl polymer particles.
  • the amount of dispersion stabilizer added may be 0.1 parts by mass or more with respect to 100 parts by mass of the monomer mixture.
  • it is 0.5 parts by mass or more, more preferably 1 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less.
  • pigments, plasticizers, polymerization stabilizers, fluorescent brighteners, magnetic powders, ultraviolet absorbers, antistatic agents, flame retardants, and the like may be added to the monomer composition.
  • the amount of these additives used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the monomer mixture. It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.
  • Method for producing vinyl polymer particles In the method for producing vinyl polymer particles, a monomer composition containing the monomer mixture as described above is polymerized.
  • a polymerization method well-known polymerization methods, such as suspension polymerization, seed polymerization, and emulsion polymerization, can be employ
  • the solvent used is not particularly limited as long as it does not completely dissolve the monomer composition, but an aqueous medium is preferably used. These solvents can be appropriately used within a range of usually 20 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the monomer composition.
  • a method for producing vinyl polymer particles a method in which a monomer composition containing a monomer mixture and a polymerization initiator is suspended and polymerized in an aqueous solvent in which a dispersion stabilizer is dissolved or dispersed is preferable. It is.
  • the polymerization temperature of the suspension polymerization is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, further preferably 60 ° C. or higher, preferably 95 ° C. or lower, more preferably 90 ° C. or lower, still more preferably. Is 85 ° C. or lower.
  • the polymerization reaction time is preferably 1 hour or longer, more preferably 2 hours or longer, further preferably 3 hours or longer, preferably 10 hours or shorter, more preferably 8 hours or shorter, still more preferably. 5 hours or less.
  • the polymerization reaction is preferably performed after regulating the droplet diameter of the monomer composition or while regulating the droplet diameter.
  • the regulation of the droplet diameter of the monomer composition is, for example, that a suspension in which the monomer composition is dispersed in an aqueous medium is changed to T.P. K. It can be carried out by stirring with a high-speed stirrer such as a homomixer or a line mixer.
  • the vinyl polymer fine particles generated by the polymerization reaction may be dried and further subjected to a classification process or the like if necessary.
  • the seed polymerization method it is preferable to use a styrene-based or (meth) acrylate-based polymer as the seed particle, and it is more preferable to use a non-crosslinked type or a fine particle having a low degree of crosslinking.
  • the average particle diameter of the seed particles is preferably 0.1 ⁇ m to 10 ⁇ m, and the value (CV value) represented by 100 ⁇ particle diameter standard deviation / average particle diameter is preferably 10 or less.
  • a conventionally used method can be employed, and examples thereof include soap-free emulsion polymerization and dispersion polymerization.
  • the charged amount of the monomer composition in the seed polymerization is preferably 0.5 to 50 parts by mass with respect to 1 part by mass of the seed particles. If the charged amount of the monomer composition is too small, the increase in the particle size due to polymerization is small, and if it is too large, the monomer composition is not completely absorbed by the seed particles and polymerizes independently in the medium. May produce abnormal particles. In addition, about the polymerization temperature and the drying conditions of the obtained particle
  • Organic-inorganic composite particles are particles comprising an organic part derived from a vinyl polymer and an inorganic part.
  • organic-inorganic composite particles an aspect in which inorganic fine particles such as metal oxides such as silica, alumina and titania, metal nitrides, metal sulfides and metal carbides are dispersed and contained in the vinyl polymer;
  • Organo A mode in which a metalloxane chain (molecular chain containing a “metal-oxygen-metal” bond) such as polysiloxane and polytitanoxane and an organic molecule are combined at the molecular level; a vinyl polymer such as vinyltrimethoxysilane is formed.
  • an embodiment composed of organic-inorganic composite particles including a vinyl polymer skeleton and a polysiloxane skeleton is particularly preferable.
  • composite particles organic-inorganic composite particles containing a vinyl polymer skeleton and a polysiloxane skeleton (hereinafter sometimes simply referred to as “composite particles”) will be described in detail.
  • the vinyl polymer skeleton is a vinyl polymer having a main chain composed of a repeating unit represented by the following formula (1), having a side chain, having a branched structure, and further having a crosslinked structure. It may be a thing.
  • the hardness of the composite particles can be controlled appropriately.
  • polysiloxane skeleton is defined as a portion in which a siloxane unit represented by the following formula (2) is continuously chemically bonded to form a network of a network structure.
  • the amount of SiO 2 constituting the polysiloxane skeleton is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 25% by mass or less with respect to the mass of the composite particles. More preferably, it is 10 mass% or less.
  • the amount of SiO 2 constituting the polysiloxane skeleton is a mass percentage obtained by measuring the mass before and after firing the particles at a temperature of 800 ° C. or higher in an oxidizing atmosphere such as air.
  • the composite particles can be arbitrarily adjusted by appropriately changing the ratio of the polysiloxane skeleton part and the vinyl polymer skeleton part with respect to each of the mechanical properties such as hardness and breaking strength.
  • the polysiloxane skeleton in the composite particles is preferably obtained by hydrolytic condensation reaction of a silane compound having a hydrolyzable group.
  • R ′ may have a substituent and represents at least one group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an unsaturated aliphatic group, and X represents a hydroxyl group, an alkoxy group. And represents at least one group selected from the group consisting of a group and an acyloxy group, and m is an integer from 0 to 3.
  • the derivative of the silane compound represented by the general formula (3) is not particularly limited.
  • a part of X is substituted with a group capable of forming a chelate compound such as a carboxyl group and a ⁇ -dicarbonyl group.
  • examples thereof include compounds and low condensates obtained by partially hydrolyzing the silane compound.
  • the hydrolyzable silane compound may be used alone or in combination of two or more.
  • the hydrolyzable silane compound It is necessary to use those having an organic group containing a vinyl bond.
  • Examples of the organic group containing a vinyl bond include organic groups represented by the following general formulas (4), (5), and (6).
  • CH 2 C (-R a ) -COOR b- (4)
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent.
  • CH 2 C (-R c )-(5)
  • R c represents a hydrogen atom or a methyl group.
  • CH 2 C (-R d ) -R e- (6)
  • R d represents a hydrogen atom or a methyl group
  • R e represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent.
  • Examples of the organic group of the general formula (4) include a (meth) acryloxy group, and the silane compound of the general formula (3) having a (meth) acryloxy group includes, for example, ⁇ -methacryloxypropyltrimethoxy.
  • Silane ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -methacryloxypropyltriacetoxysilane, ⁇ -methacryloxyethoxypropyltrimethoxysilane (or ⁇ -trimethoxysilylpropyl- ⁇ -methacryloxyethyl ether), ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane, ⁇ -acryloxypropylmethyldimethoxysilane, etc. You can. These may be used alone or in combination of two or more.
  • Examples of the organic group of the general formula (5) include a vinyl group and an isopropenyl group.
  • Examples of the silane compound of the general formula (3) having these organic groups include vinyl trimethoxysilane, Examples include vinyltriethoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldiacetoxysilane. These may be used alone or in combination of two or more.
  • Examples of the organic group of the general formula (6) include 1-alkenyl group or vinylphenyl group, isoalkenyl group or isopropenylphenyl group, and the silane of the general formula (3) having these organic groups.
  • Examples of the compound include 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, 1-decenyltrimethoxysilane, ⁇ -trimethoxysilylpropyl vinyl ether, ⁇ -trimethoxysilylundecane.
  • Examples include acid vinyl ester, p-trimethoxysilylstyrene, 1-hexenylmethyldimethoxysilane, 1-hexenylmethyldiethoxysilane, and the like. These may be used alone or in combination of two or more.
  • the vinyl polymer skeleton contained in the composite particles is obtained by allowing the particles having a polysiloxane skeleton obtained by the hydrolysis-condensation reaction of (I) silane compound to absorb the vinyl monomer component and then polymerizing the particles. be able to.
  • the silane compound has an organic group containing a vinyl bond together with a hydrolyzable group, it can also be obtained by polymerizing this after the hydrolysis condensation reaction of the (II) silane compound.
  • the composite particle has (i) a form in which the polysiloxane skeleton has an organosilicon atom in which a silicon atom is directly chemically bonded to at least one carbon atom in the vinyl polymer skeleton (chemical bond type).
  • the form (IPN type) does not have such an organosilicon atom in the molecule, and is not particularly limited, but the form (i) is preferred.
  • the vinyl polymer skeleton is obtained together with the polysiloxane skeleton by the method (I)
  • composite particles having the form (ii) are obtained.
  • the silane compound has a vinyl bond together with a hydrolyzable group.
  • composite particles having both the forms (i) and (ii) can be obtained. Further, when the vinyl polymer skeleton is obtained together with the polysiloxane skeleton as in (II), composite particles having the form (i) are obtained.
  • examples of the monomer that can be absorbed by the particles having a polysiloxane skeleton include the vinyl monomers described above, and depending on the desired physical properties of the composite particles. It can be selected appropriately. These may be used alone or in combination of two or more.
  • a hydrophobic vinyl-based monomer is preferable because a stable emulsion in which the monomer component is emulsified and dispersed can be generated when the monomer component is absorbed into particles having a polysiloxane skeleton.
  • the crosslinkable monomer described above if used, the mechanical properties of the resulting composite particles can be easily adjusted, and the solvent resistance of the composite particles can be improved.
  • the crosslinkable monomer those exemplified as those used for the vinyl polymer particles can be used.
  • an aromatic divinyl compound is preferable, and divinylbenzene is particularly preferable.
  • non-crosslinkable monomer illustrated regarding the said vinyl polymer particle as a monomer absorbed by the particle
  • styrene monomers are preferable, and styrene, ⁇ -methylstyrene, ethylvinylbenzene, and the like are particularly preferable.
  • the method for producing composite particles preferably includes a hydrolysis-condensation step and a polymerization step, and more preferably includes an absorption step for absorbing the polymerizable monomer after the hydrolysis and condensation step and before the polymerization step. .
  • the absorption step By including the absorption step, the content of the vinyl polymer skeleton component in the composite particles and the refractive index of the vinyl polymer skeleton contained can be adjusted.
  • the silane compound used in the hydrolysis-condensation step does not have an element that constitutes a vinyl polymer skeleton together with an element that can constitute a polysiloxane skeleton structure, the absorption step is essential, and this absorption step is followed.
  • a vinyl polymer skeleton is formed in the polymerization process.
  • the hydrolysis-condensation step is a step of performing a reaction in which a silane compound is hydrolyzed in a solvent containing water to undergo condensation polymerization.
  • a silane compound is hydrolyzed in a solvent containing water to undergo condensation polymerization.
  • particles having a polysiloxane skeleton can be obtained.
  • Hydrolysis and polycondensation can employ any method such as batch, split, and continuous.
  • basic catalysts such as ammonia, urea, ethanolamine, tetramethylammonium hydroxide, alkali metal hydroxide, and alkaline earth metal hydroxide can be preferably used as the catalyst.
  • an organic solvent can be contained in addition to water and the catalyst.
  • the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol; acetone, Examples thereof include ketones such as methyl ethyl ketone; esters such as ethyl acetate; (cyclo) paraffins such as isooctane and cyclohexane; aromatic hydrocarbons such as benzene and toluene. These may be used alone or in combination of two or more.
  • anionic, cationic and nonionic surfactants and polymer dispersants such as polyvinyl alcohol and polyvinylpyrrolidone can be used in combination. These may be used alone or in combination of two or more.
  • Hydrolytic condensation is performed by mixing the silane compound as a raw material with a solvent containing a catalyst, water, and an organic solvent, and then at a temperature of 0 ° C. to 100 ° C., preferably 0 ° C. to 70 ° C., for 30 minutes to 100 hours. It can carry out by stirring below. Thereby, polysiloxane particles are obtained. Moreover, after producing a particle by performing a hydrolysis-condensation reaction to a desired degree, this may be used as a seed particle, and a silane compound may be further added to the reaction system to grow the seed particle.
  • the absorption process is not particularly limited as long as it proceeds in the presence of the monomer component in the presence of the polysiloxane particles. Therefore, the monomer component may be added to the solvent in which the polysiloxane particles are dispersed, or the polysiloxane particles may be added to the solvent containing the monomer component. Especially, it is preferable to add a monomer component in the solvent which disperse
  • the method of adding the monomer component to the reaction liquid without taking out the polysiloxane particles obtained in the hydrolysis and condensation process from the reaction liquid (polysiloxane particle dispersion) does not complicate the process. It is preferable because of its excellent properties.
  • the monomer component is absorbed in the structure of the polysiloxane particle, but the concentration of each of the polysiloxane particle and the monomer component is increased so that the absorption of the monomer component proceeds quickly, It is preferable that the mixing ratio of the polysiloxane and the monomer component, the processing method and means for mixing, the temperature and time at the time of mixing, the processing method and means after mixing, etc. are appropriately set and performed under the conditions.
  • the amount of the monomer component added is preferably 0.01 to 100 times by mass with respect to the mass of the silane compound used as the raw material for the polysiloxane particles. More preferably, they are 0.1 times or more and 50 times or less, More preferably, they are 0.3 times or more and 30 times or less. If the amount added is less than the above range, the amount of monomer component absorption of the polysiloxane particles is reduced, the mechanical properties of the resulting composite particles may be insufficient, if exceeding the above range, There is a tendency that it is difficult to completely absorb the added monomer component in the polysiloxane particles, and the unabsorbed monomer component remains, and thus aggregation between particles is likely to occur in the subsequent polymerization stage. There is.
  • the timing of addition of the monomer component is not particularly limited, and may be added all at once, may be added in several times, or may be fed at an arbitrary rate.
  • either the monomer component alone or the solution of the monomer component may be added, but the monomer component is previously added to water or an aqueous medium with an emulsifier. It is preferable to mix the emulsified and emulsified liquid into the polysiloxane particles because the polysiloxane particles can be more efficiently absorbed.
  • the emulsifier is not particularly limited.
  • These emulsifiers may be used alone or in combination of two or more.
  • the amount of the emulsifier used is not particularly limited, and specifically, it is preferably 0.01 parts by mass or more, more preferably 0 with respect to 100 parts by mass of the total mass of the monomer components to be emulsified. 0.05 parts by mass or more, more preferably 1 part by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 5 parts by mass or less. When the amount is less than 0.01 parts by mass, a stable emulsion may not be obtained. When the amount exceeds 10 parts by mass, emulsion polymerization or the like may occur as a side reaction. In order to obtain an emulsified liquid, the monomer component may be made into an emulsion state in water using a homomixer or an ultrasonic homogenizer together with the emulsifier.
  • water or a water-soluble organic solvent that is 0.3 to 10 times the mass of the monomer component.
  • the water-soluble organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol; acetone And ketones such as methyl ethyl ketone; esters such as ethyl acetate;
  • the absorption step is preferably performed in the temperature range of 0 ° C. to 60 ° C. with stirring for 5 minutes to 720 minutes. These conditions may be set as appropriate depending on the type of polysiloxane particles and monomers to be used, and these conditions may be used alone or in combination of two or more.
  • the absorption process for determining whether the monomer component has been absorbed by the polysiloxane particles, for example, before adding the monomer component and after the absorption step, observe the particles with a microscope to absorb the monomer component. Thus, it can be easily determined by confirming that the particle size is increased.
  • the polymerization step is a step of obtaining particles having a vinyl polymer skeleton by polymerizing a monomer component.
  • a silane compound having an organic group having a vinyl bond it is a step of polymerizing the vinyl bond of the organic group to form a vinyl polymer skeleton.
  • the polymerization reaction may be performed in the middle of the hydrolysis-condensation step or the absorption step, and may be performed after one or both of the steps, and is not particularly limited, but usually after the hydrolysis-condensation step (the absorption step). If done, of course, start after the absorption step).
  • the polymerization method is not particularly limited, and for example, any of a method using a radical polymerization initiator, a method of irradiating ultraviolet rays or radiation, a method of applying heat, and the like can be adopted. Although it does not specifically limit as said radical polymerization initiator, For example, what is used for superposition
  • the amount of the radical polymerization initiator used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably 0.001 part by mass with respect to 100 parts by mass of the total mass of the monomer components. It is 1 part by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. When the usage-amount of a radical polymerization initiator is less than 0.001 mass part, the polymerization degree of a monomer component may not rise.
  • the method of charging the radical polymerization initiator into the solvent is not particularly limited, and is a method in which the entire amount is initially charged (before the reaction is started) (the mode in which the radical polymerization initiator is emulsified and dispersed together with the monomer component, the monomer component is A mode in which a radical polymerization initiator is charged after absorption), a method in which a part is first charged, a method in which the rest is continuously fed, a method in which pulses are intermittently added, or a method in which these are combined, etc. Any known method can be employed.
  • the reaction temperature for carrying out radical polymerization is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower. If the reaction temperature is too low, the degree of polymerization does not increase sufficiently and the mechanical properties of the composite particles tend to be insufficient. On the other hand, if the reaction temperature is too high, aggregation between particles occurs during the polymerization. It tends to happen easily.
  • the reaction time for performing radical polymerization may be appropriately changed according to the type of polymerization initiator used, but is usually preferably from 15 minutes to 600 minutes, more preferably from 60 minutes to 300 minutes. When the reaction time is too short, the degree of polymerization may not be sufficiently increased, and when the reaction time is too long, aggregation tends to occur between particles.
  • vinyl polymer fine particles having the above-mentioned preferable characteristics (mechanical characteristics, particle size distribution characteristics, etc.) can be obtained.
  • the base particles according to the present invention are obtained by hydrophilizing the vinyl polymer fine particles obtained as described above.
  • the hydrophilic treatment of the vinyl polymer fine particles will be described.
  • the hydrophilization treatment method is not particularly limited, but the vinyl polymer fine particles are brought into contact with a mixed gas containing a fluorine gas and a gas containing a compound containing an oxygen atom by contacting the vinyl polymer fine particles.
  • a treatment method for hydrophilizing the surface of is preferable.
  • this hydrophilic treatment method will be described.
  • the hydrophilization treatment is not particularly limited as long as the vinyl polymer fine particles and the mixed gas are in contact with each other, but the mixed gas is introduced into a container capable of holding the vinyl polymer fine particles and sealed for a predetermined time. Or a method of continuously supplying a mixed gas in a container capable of holding the vinyl polymer fine particles (a continuous supply method).
  • the treatment it is preferable to increase the contact efficiency between the mixed gas and the base material particles, and to make the mixture uniformly hydrophilic in a short time.
  • the mixed gas is diffused into the processing container.
  • the vinyl polymer fine particles may be agitated, and examples thereof include a method of rotating the processing vessel using a drum rotating device or the like, and a method of flowing the vinyl polymer fine particles with a stirrer. A plurality of these contact efficiency improving means may be used in combination.
  • the thickness of the vinyl polymer fine particle layer is 2 mm in the processing container in order to perform the hydrophilic treatment uniformly and without variation between the particles. It is preferred to load so that: A more preferable particle layer thickness is 0.5 mm or less.
  • the fluorine gas concentration in the mixed gas is 0.01% to 1.0% by volume.
  • the fluorine gas concentration is preferably 0.08% by volume or more.
  • the base material particles may be colored.
  • the fluorine gas concentration is 1.0% by volume or less, white or slightly colored. More preferably, it is 0.3 volume% or less.
  • the gas of the compound containing oxygen atoms is an essential component together with the fluorine gas.
  • Preferred examples of the compound gas containing oxygen atoms include oxygen, sulfur dioxide, carbon dioxide, carbon monoxide, and nitrogen dioxide.
  • oxygen gas is preferable because it has a high hydrophilization effect even under mild processing conditions.
  • an inert gas such as nitrogen, helium, or argon can be used in addition to the fluorine gas and the compound gas containing oxygen atoms.
  • nitrogen gas as an inert gas from the viewpoint of preventing dust explosion in the treatment in the gas phase and performing the hydrophilic treatment industrially and safely.
  • the mixed gas preferably has a composition comprising a fluorine gas, a compound gas containing oxygen atoms, and an inert gas, and more preferably a mixed gas containing fluorine gas, oxygen gas and nitrogen gas.
  • the base particles can be hydrophilized. If the concentration of the gas of the compound containing oxygen atoms in the mixed gas is 0.1 vol% to 99.99 vol%, the base particles can be hydrophilized. If the concentration of the gas of the compound containing oxygen atoms is less than 0.1% by volume, there is a possibility that particles with insufficient hydrophilization treatment exist. In order to obtain particles (powder) having a uniform degree of hydrophilization, and in order to obtain highly hydrophilic particles in a short time, the gas concentration of the compound containing oxygen atoms is 0.1% by volume. It is preferable that the amount be 0.5% by volume or more.
  • the high concentration of oxygen-containing compound gas does not adversely affect the hydrophilization of the particles, but the reason why dust explosion can be prevented in the hydrophilization treatment and the hydrophilization treatment can be performed safely.
  • the concentration of the inert gas is not particularly limited, and may be appropriately selected within a range that does not impair the effect of the hydrophilization treatment with a fluorine gas and a compound gas containing oxygen atoms. . Usually, 99 volume% or less is preferable. If it exceeds 99% by volume, there is a possibility that particles having insufficient hydrophilicity may exist.
  • the concentration of the inert gas is preferably 90% by volume or more, and more preferably 94% by mass or more from the reason that the occurrence of dust explosion in the hydrophilic treatment can be suppressed and the hydrophilic treatment can be performed safely.
  • the partial pressure of the fluorine gas in the mixed gas is 8 Pa (0.06 Torr) or more, the uniformity of the hydrophilic treatment is excellent, which is preferable. More preferably, it is 24 Pa (0.18 Torr) or more, and more preferably 64 Pa (0.48 Torr) or more. From the viewpoint of suppressing the decomposition and coloring of the vinyl polymer skeleton due to the hydrophilic treatment, the partial pressure of the fluorine gas is preferably 1000 Pa (7.5 Torr) or less, more preferably 700 Pa (5.25 Torr) or less. .
  • the partial pressure of oxygen gas is preferably 70 Pa (0.53 Torr) to 85000 Pa (637.6 Torr) from the viewpoint of performing the hydrophilic treatment uniformly. From the viewpoint of industrially and safely hydrophilizing treatment, it is preferably 70 Pa to 7998 Pa (60 Torr), and more preferably 70 Pa to 3999 Pa (30 Torr). The preferable range is the same with respect to the partial pressure of the gas of the compound containing an oxygen atom.
  • the partial pressure of the nitrogen gas is preferably 3199 Pa (24 Torr) to 79180 Pa (594 Torr), more preferably 71918 Pa from the viewpoint of industrially and safely hydrophilizing treatment. (540 Torr) to 79180 Pa (594 Torr).
  • the preferable range of the partial pressure of the other inert gas is the same.
  • the total pressure of the mixed gas is preferably 101.3 kPa (760 Torr) or less in order to safely perform the hydrophilic treatment. If it exceeds 101.3 kPa, the mixed gas may leak out of the container.
  • the ratio of the mixed gas to the vinyl polymer fine particles is preferably 30 L to 4000 L, preferably 1000 L to 3000 L, in terms of normal temperature and normal pressure with respect to 1 kg of the vinyl polymer fine particles. It is more preferable to supply as follows. In the case of the continuous supply type, it is preferable to supply the 1 kg of the base particles so that the total flow rate is 30 L to 15000 L, preferably 1000 L to 10000 L in terms of normal temperature and normal pressure.
  • the vinyl polymer fine particles contained in a container are put into a sealable chamber, the pressure is reduced, a mixed gas is introduced, and the treatment is performed for a predetermined time. If moisture remains, HF is generated and dangerous. Therefore, it is preferable to sufficiently evacuate when decompressing. In the case of the continuous supply type, the mixed gas may be introduced for a predetermined time.
  • reaction temperature is preferably about ⁇ 20 ° C. to 200 ° C., more preferably about 0 ° C. to 100 ° C., and further preferably 10 ° C. to 40 ° C. If the reaction temperature exceeds 200 ° C, the vinyl polymer particles may be decomposed. On the other hand, if the reaction temperature is lower than -20 ° C, the hydrophilization treatment may be insufficient. In addition, reaction temperature means the temperature of the gas in a chamber.
  • a compound gas containing oxygen atoms or other gas other than fluorine gas may be first introduced into the chamber, and then fluorine gas may be introduced, or a premixed gas may be introduced. Good.
  • the contact time (treatment time) between the vinyl polymer fine particles and the mixed gas is not particularly limited, and the treatment may be performed until the desired degree of hydrophilicity is achieved, but the treatment is completed in about 10 to 60 minutes. After the treatment, it is preferable to perform a step of reducing the pressure again to about 0.13 Pa (0.001 Torr) and then introducing nitrogen gas. When this step is completed, the pressure is released to atmospheric pressure.
  • the particles after contact with the mixed gas are further brought into contact with moisture after the contact treatment with the gas.
  • the —C (F) ⁇ O formed on the particle surface by contact with the mixed gas is more efficiently converted to a carboxyl group by contacting with moisture. Further, HF generated at this time and HF or F 2 adsorbed on the particle surface can be effectively removed.
  • the moisture is preferably an alkaline aqueous solution and / or water and / or water vapor.
  • the mode in which the particles after contact with the mixed gas are brought into contact with water is any of the mode in which an alkaline aqueous solution is used as the water; the mode in which water and / or water vapor is used; May be.
  • an embodiment using an alkaline aqueous solution and water and / or water vapor is preferable.
  • the order of contact is not particularly limited, but from the viewpoint of efficiently removing HF or F 2 adsorbed on the particle surface, the particle is brought into contact with an alkaline aqueous solution and then brought into contact with water and / or water vapor. Is desirable.
  • an alkali metal salt or amine salt of a carboxylic acid (hereinafter sometimes referred to as a carboxylate salt) is formed on the particle surface.
  • This carboxylate is preferable because it further increases the hydrophilicity of the particles, and then the excess alkaline aqueous solution can be washed by contacting the particles with water and / or water vapor.
  • alkali treatment the case of bringing particles into contact with an alkaline aqueous solution
  • water may be referred to as warm water cleaning.
  • a contact treatment method with water to efficiently promote conversion to a carboxyl group or a carboxylate salt effectively remove HF and F 2 adsorbed on the particle surface, and reduce eluting fluorine
  • the particles taken out from the chamber are dispersed in an alkaline aqueous solution and subjected to an alkali treatment, and then the particles are taken out and dispersed in water and washed with water or a solvent containing water. And the like.
  • the contact time with moisture is preferably about 1 to 600 minutes.
  • the temperature of (alkaline aqueous solution and / or water and / or water vapor) is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 60 ° C. or higher, and most preferably 80 ° C. or higher.
  • the particle concentration is preferably 0.5% by mass to 50% by mass in a total of 100% by mass of the solvent and the particles. If the particle concentration is less than 0.5% by mass, the amount of fluorine-containing wastewater generated when washing a predetermined amount of particles increases, which may increase the cost industrially. If the particle concentration exceeds 50% by mass, cleaning may be insufficient. In order to efficiently clean the particles, it is also preferable to perform ultrasonic dispersion with the particles in a solvent.
  • elution fluorine such as fluorine components adhering to the particle surface may cause problems such as corrosion due to the safety of the particles or contact with other materials, so reduce it as much as possible. It is preferable to remove, and when the alkaline treatment using an alkaline aqueous solution as the water is performed, the leachable fluorine adsorbed on the particle surface can be more efficiently removed.
  • the carboxyl group on the surface of the base particle is converted to a carboxylate by the alkali treatment, the hydrophilicity of the particle is increased, and the plating property of the base particle is also improved.
  • alkaline aqueous solutions include aqueous solutions of water-soluble amines such as ammonia, monoethanolamine, and diethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, and lithium carbonate.
  • An aqueous solution containing an alkali metal element ion in which an alkali metal compound such as an alkali metal carbonate such as sodium carbonate, potassium carbonate, rubidium carbonate or cesium carbonate is dissolved in water is preferably used.
  • aqueous solutions containing alkali metal element ions are preferable, those having sodium ions are more preferable, and sodium hydroxide aqueous solutions are particularly preferable.
  • the concentration of the alkaline aqueous solution is preferably 0.01N to 5N. More preferably, it is 0.05N to 2N, and still more preferably 0.1N to 1N.
  • the specific method of the alkali treatment is not particularly limited. For example, after contact with the gas, the particles taken out from the chamber are dispersed in an alkaline aqueous solution having the above concentration, and then at a temperature of 80 ° C. or higher for 1 minute to 600 minutes. And a method of bringing the particles into contact with an alkaline aqueous solution.
  • the amount of fluorine atoms contained in the obtained base particles (total fluorine amount), the amount of fluorine atoms ionized and liberated (elutable fluorine content), and the non-eluting fluorine content are measured by the following methods. it can.
  • Total fluorine content oxygen combustion flask method 2 mg of particles are weighed on a 3 cm ⁇ 2 cm filter paper and wrapped so that the particles do not scatter.
  • the platinum basket attached to the oxygen flask is heated with a Bunsen burner and kept in a red hot state for about 5 seconds. When the basket cools, pack the filter paper wrapped in particles into the basket.
  • 15 ml of distilled water is put into a 500 ml oxygen flask and the inner wall of the flask is wetted, the inside of the flask is replaced with an oxygen atmosphere.
  • the filter paper in the basket is then ignited and quickly inserted into the flask.
  • the flask is shaken a few times and allowed to stand for 30 minutes, then the contents of the flask are transferred to a polypropylene beaker with a capacity of 100 ml, and further distilled water is added to adjust to a total of 50 ml.
  • the pH was adjusted to a constant level by adding 5 ml of a buffer solution, and the fluorine ion concentration was measured with an ion meter while stirring with a magnetic stirrer to determine the total fluorine amount (mg / g).
  • Non-eluting fluorine content (total fluorine content)-(eluting fluorine content)
  • the value measured by the following method was used as the acid value of the base particles obtained by the above-described hydrophilization treatment.
  • the method for producing conductive fine particles of the present invention is characterized in that a conductive metal layer is formed on the surface of the substrate particles.
  • the conductive metal layer is formed by an electroless plating method.
  • the adhesion between the base particle and the conductive metal layer is greatly influenced by the degree of hydrophilicity based on a hydrophilic group such as an acidic functional group on the surface of the base particle.
  • the substrate particles are preferably those having a high degree of hydrophilicity on the surface, and a mixed gas containing essentially a fluorine gas and a compound gas containing oxygen atoms in the above-mentioned vinyl polymer fine particles. It is preferably obtained by performing a treatment for contact (“hydrophilic treatment”).
  • the chelating effect of palladium ions which are the raw materials of the plating catalyst by the functional groups, is greatly enhanced, so that the plating catalyst has a high density and a strong base. Immobilized on the surface of the material particles. Further, the aggregation of the base material particles during the electroless plating treatment is prevented by the influence of the hydrophilic group remaining on the particle surface even after the catalyst treatment. For this reason, the bonding strength between the obtained conductive metal layer and the substrate surface is increased, and the conductive metal is uniformly formed without causing defects (unplated portions) such that the substrate particles are exposed. It is believed that a layer is formed.
  • the carboxyl group is present on the surface of the base particle, but the present invention It is not possible to obtain the same adhesion between the base particle / conductive metal layer. That is, in this method, since a carboxyl group is introduced during the polymerization reaction, the carboxyl group cannot be selectively introduced onto the surface of the polymer particles. In addition, even in a polymerization system having excellent dispersion stability, it is inevitable that slight aggregated particles are generated, and this causes a difference in carboxyl group introduction amount between individual polymer particles.
  • the preferable hydrophilization treatment described above is a gas phase reaction, the gas spreads over the entire surface of the fine particles by diffusion, so that a uniform and selective hydrophilization treatment is possible. It is considered that high adhesion between conductive metal layers can be obtained. Therefore, the conductive metal layer is not easily cracked or peeled off, and good electrical conductivity can be maintained even when the crimping process is performed.
  • the method of coating the surface of the substrate particles with the conductive metal layer is not particularly limited.
  • a plating method such as electroless plating or displacement plating; a paste obtained by mixing metal fine powder alone or mixed with a binder
  • Methods for coating particles physical vapor deposition methods such as vacuum vapor deposition, ion plating, ion sputtering and the like.
  • the electroless plating method is preferable because a conductive metal layer can be easily formed without requiring a large-scale apparatus.
  • a method for producing the conductive fine particles of the present invention by an electroless plating method will be described.
  • the recommended method for producing conductive fine particles of the present invention includes (i) a catalytic step and (ii) an electroless plating step.
  • a catalytic step includes (i) a catalytic step and (ii) an electroless plating step.
  • a catalyst layer serving as a base point of electroless plating performed in the next step is formed on the surface of the base particle made hydrophilic in the hydrophilizing treatment step.
  • the method for forming the catalyst layer is not particularly limited, and may be performed using a catalytic reagent commercially available for electroless plating. For example, after immersing the substrate particles in a solution containing palladium chloride and tin chloride as a catalyzing reagent to adsorb palladium ions on the surface of the substrate particles, an acid such as sulfuric acid and hydrochloric acid, sodium hydroxide, etc.
  • a method in which palladium ions are reduced with a solution containing a reducing agent to precipitate palladium on the surface of the substrate particles for example, a method in which palladium ions are reduced with a solution containing a reducing agent to precipitate palladium on the surface of the substrate particles.
  • Examples of the catalyst reagent include palladium chloride, palladium nitrate, tin chloride, and mixtures thereof.
  • the catalytic reagent is used after being dissolved in hydrochloric acid or the like.
  • Examples of the reducing agent include dimethylamine borane and hypophosphorous acid.
  • Electroless plating step Next, an electroless plating process for forming a conductive metal layer on the surface of the base material particle on which the catalyst layer is formed is performed.
  • the substrate particles on which the catalyst layer is formed are immersed in a plating solution in which a reducing agent and a desired metal salt are dissolved, and starting from the catalyst, the metal ions in the plating solution are reduced with a reducing agent to form a base.
  • a desired metal is deposited on the surface of the material particles to form a conductive metal layer.
  • the base particles subjected to the catalytic treatment are sufficiently dispersed in water to prepare an aqueous slurry of the base particles.
  • an untreated surface a surface on which no conductive metal layer is present
  • the hydrophilic functional groups are introduced into the surface of the particles with high density on the surface of the particles according to the present invention, the dispersibility of the substrate particles themselves in the plating solution is very high, and the electroless plating process is in progress. Aggregation of substrate particles is difficult to occur.
  • the base particles may be dispersed in water using a known dispersing means.
  • a conventionally known dispersing means normal stirring, high-speed stirring, or a shearing dispersion device such as a colloid mill or a homogenizer can be used.
  • ultrasonic waves may be used in the dispersion operation, and a dispersant such as a surfactant may be added as necessary.
  • an aqueous slurry of substrate particles is added to an electroless plating solution containing a desired conductive metal salt, a reducing agent, a complexing agent, and a main additive used as necessary, and electroless plating treatment is performed. Do.
  • the conductive metal salt examples include metal chlorides, sulfates, and acetates exemplified above as the conductive metal layer.
  • nickel salts such as nickel chloride, nickel sulfate, and nickel acetate can be used. What is necessary is just to determine suitably the density
  • sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, hydrazine and the like are used as the reducing agent.
  • a compound having a complexing action on the ions of the conductive metal to be used can be used.
  • compounds having a complexing action on nickel 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, and amino acids such as glycine.
  • Amine acids such as ethylenediamine and alkylamine, other ammonium, EDTA, pyrophosphate (salt), and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the preferable pH of the electroless plating solution in the electroless plating treatment step is 4 to 14.
  • the electroless plating reaction starts immediately when the base particle slurry is added. Further, this reaction is accompanied by generation of hydrogen gas. Therefore, the electroless plating treatment process ends when the generation of hydrogen gas is not completely recognized. After completion of the reaction, the conductive fine particles on which the conductive metal layer is formed are taken out from the reaction system, and washed and dried as necessary.
  • the conductive fine particles of the present invention can be obtained as described above, but the surface of the conductive fine particles can be coated with several layers of different metals by repeating the electroless plating process. For example, after nickel plating is applied to the substrate particles (nickel-coated particles), the gold-coated plating is performed by introducing the nickel-coated particles into the electroless gold plating solution, so that the outermost layer has a gold coating layer. Conductive fine particles are obtained.
  • the method for forming the insulating resin layer is not particularly limited, for example, in the presence of conductive fine particles after the electroless plating treatment, interfacial polymerization, suspension polymerization, emulsion polymerization of the raw material of the insulating resin layer is performed, A method of microencapsulating conductive fine particles with an insulating resin; a dipping method in which conductive fine particles are dispersed in an insulating resin solution in which an insulating resin is dissolved in an organic solvent and then dried; a spray drying method, by hybridization Any conventionally known method such as a method can be used.
  • the conductive fine particles of the present invention are also suitable as a constituent material of the anisotropic conductive material.
  • An anisotropic conductive material using the conductive fine particles of the present invention is also one of the preferred embodiments of the present invention. is there.
  • the form of the anisotropic conductive material is not particularly limited as long as the conductive fine particles of the present invention are used.
  • an anisotropic conductive film, an anisotropic conductive paste, an anisotropic conductive adhesive is used.
  • various forms such as anisotropic conductive ink. That is, electrical connection can be achieved by providing these anisotropic conductive materials between opposing substrates or between electrode terminals.
  • the anisotropic conductive film for example, after adding a solvent to the film-forming composition containing the conductive fine particles of the present invention and a binder resin to form a solution, and applying this solution on a polyethylene terephthalate film, It can be obtained by evaporating the solvent.
  • the obtained anisotropic conductive film is disposed on, for example, electrodes, and is used for connection between the electrodes by superposing a counter electrode on the anisotropic conductive film and heating and compressing the counter electrode.
  • the anisotropic conductive paste is obtained, for example, by making a resin composition containing the conductive fine particles of the present invention and a binder resin into a paste.
  • the obtained anisotropic conductive paste is placed in, for example, a suitable dispenser, applied on the electrode to be connected with a desired thickness, and the counter electrode is superimposed on the coated anisotropic conductive paste. It is used for connection between electrodes by heating and pressurizing to cure the resin.
  • the anisotropic conductive adhesive is obtained, for example, by adjusting a resin composition containing the conductive fine particles of the present invention and a binder resin to a desired viscosity.
  • the obtained anisotropic conductive adhesive is used to connect between electrodes by coating the electrodes with a desired thickness, then overlaying the counter electrodes and bonding them together, as with the anisotropic conductive paste. Is done.
  • the anisotropic conductive ink can be obtained, for example, by adjusting a viscosity suitable for printing by adding a solvent to the resin composition containing the conductive fine particles of the present invention and a binder resin.
  • the obtained anisotropic conductive ink is obtained by, for example, screen-printing the electrode to be bonded, evaporating the solvent, overlaying the counter electrode on the printing surface with the anisotropic conductive ink, and heating and compressing the electrode. Used for connection between.
  • the anisotropic conductive material is manufactured by dispersing the conductive fine particles of the present invention in an insulating binder resin to obtain a desired form.
  • the insulating binder resin and the conductive fine particles May be used separately to connect between substrates or between electrode terminals.
  • the binder resin is not particularly limited, and examples thereof include thermoplastic resins such as acrylic resins, ethylene-vinyl acetate resins, and styrene-butadiene block copolymers; monomers and oligomers having a glycidyl group, and curing agents such as isocyanate. Examples thereof include a curable resin composition that is cured by reaction and a curable resin composition that is cured by light and heat.
  • the content ratio of the conductive fine particles in the anisotropic conductive material of the present invention may be appropriately determined according to the use.
  • the ratio of the conductive fine particles in the anisotropic conductive material is 2% by volume to 70% by volume is preferable, 5% by volume to 50% by volume is more preferable, and 10% by volume to 40% by volume is more preferable. If the content of the conductive fine particles is too small, it may be difficult to obtain sufficient electrical continuity. On the other hand, if the content of the conductive fine particles is too large, the conductive particles are in contact with each other and anisotropic The function as a conductive material may be difficult to be exhibited.
  • the film thickness of the anisotropic conductive material, the coating thickness of the paste and adhesive, and the printed thickness are calculated from the average particle diameter of the conductive fine particles used and the specifications of the electrode to be connected. It is preferable to set so that the conductive fine particles are held between the power electrodes and the gap between the bonding substrates on which the electrodes to be connected are formed is sufficiently filled with the binder resin layer.
  • the anisotropic conductive material of the present invention not only exhibits high conductivity, but also does not cause peeling or breakage of the conductive metal layer even when subjected to weight compression, and ensures electrical connection between opposing electrode substrates. can do.
  • the stability over time is excellent, the electrical connection between the electrode substrates can be maintained and the reliability can be improved without causing a decrease in conductivity due to plating cracking or the like even in long-term use.
  • Example 1 In a four-necked flask equipped with a condenser, a thermometer, and a dripping port, put 526 parts of ion-exchanged water, 1.6 parts of 25% aqueous ammonia and 118 parts of methanol, and with stirring, 3-methacryloxypropyl from the dripping port. 30 parts of trimethoxysilane was added, and hydrolysis and condensation reaction of 3-methacryloxypropyltrimethoxysilane was performed to prepare an emulsion of polysiloxane particles.
  • the obtained emulsion was added to an emulsion of polysiloxane particles and further stirred. Two hours after the addition of the emulsified liquid, the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles were enlarged by absorbing the monomer.
  • the reaction solution was heated to 65 ° C. in a nitrogen atmosphere and held at 65 ° C. for 2 hours to perform radical polymerization of the monomer component.
  • the emulsion after radical polymerization was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol, and then vacuum dried at 80 ° C. for 12 hours to obtain organic-inorganic composite particles.
  • the particle size of the organic-inorganic composite particles was measured by Coulter Multisizer III type (manufactured by Beckman Coulter, Inc.), the mass average particle size was 3.7 ⁇ m and the coefficient of variation (CV value) was 2.9%.
  • the measurement and calculation method of the CV value (variation coefficient) of the particle mass average particle diameter and particle diameter are values obtained according to the method described later.
  • fluorine (F 2 ) gas and oxygen (O 2 ) gas were introduced so that F 2 : 0.67 Pa (5 Torr) and O 2 : 80 kPa (600 Torr). F 2 was 0.83% by volume, and the balance was O 2 . Then, after processing at 30 degreeC for 60 minutes, the inside of a chamber was substituted with nitrogen, and it returned
  • ⁇ Catalytic treatment, electroless plating treatment> In a beaker, 50 parts of “Pink Summer (manufactured by Nippon Kanisen Co., Ltd.)” and 400 parts of ion-exchanged water were mixed. Separately, 50 parts of ion-exchanged water was prepared by ultrasonically dispersing 10 parts of the base particles (1), and this was put into the mixed solution and stirred at 30 ° C. for 10 minutes to form a suspension. The cake obtained by solid-liquid separation was washed in the order of ion-exchanged water and methanol, and vacuum dried at 100 ° C. for 2 hours in a nitrogen atmosphere.
  • Substrate particles activated with palladium were added to 500 parts of ion-exchanged water and subjected to ultrasonic treatment for 30 minutes to sufficiently disperse the particles to obtain a fine particle suspension. While stirring this fine particle suspension at 50 ° C., nickel sulfate hexahydrate 50 g / L, sodium hypophosphite monohydrate 20 g / L, dimethylamine borane 2.5 g / L, citric acid 50 g / L.
  • the electroless plating solution (pH 7.5) consisting of was gradually added to the fine particle suspension to perform electroless nickel plating of the substrate particles.
  • Particles during plating are sampled over time and observed with a scanning electron microscope (SEM, manufactured by HITACHI: “S-3500N”) while measuring the particle size of any 10 particles.
  • SEM scanning electron microscope
  • the plating thickness was calculated from the difference from the measurement results of the material particles, and the addition of the electroless plating solution was stopped when the plating thickness reached 0.1 ⁇ m.
  • the obtained conductive fine particles were separated by filtration, washed with ion-exchanged water, further washed with methanol, and vacuum dried at 60 ° C. for 12 hours to obtain conductive fine particles (1).
  • Example 2 In a four-necked flask equipped with a cooling tube, a thermometer, and a dropping port, 150 parts of an ion exchange aqueous solution in which 2 parts of the above-mentioned “Hytenol NF-08” was dissolved was charged. Next, 100 parts of divinylbenzene with the above-mentioned “V-65” dissolved therein as a polymerization initiator is added, and the suspension is emulsified and dispersed at 5000 rpm for 5 minutes with a TK homomixer (manufactured by Tokushu Kika Kogyo Co.). Adjusted.
  • a TK homomixer manufactured by Tokushu Kika Kogyo Co.
  • Example 2 120 parts of the obtained vinyl polymer fine particles were hydrophilized in the same manner as in Example 1 and subjected to precision classification to obtain substrate particles (2).
  • the mass average particle diameter of the substrate particles was 3.0 ⁇ m, and the coefficient of variation (CV value) was 4.0%.
  • CV value coefficient of variation
  • a carbon peak corresponding to a carboxyl group was observed at 288 eV by XPS (ESCA) analysis of the obtained base particle (2).
  • the alkali dispersibility of the substrate particles (2) was 0.6%.
  • Example 3 30 parts of the conductive fine particles (1) obtained in Example 1 and 3 parts of methyl methacrylate / styrene / divinylbenzene crosslinked resin fine particles having a mass average particle diameter of about 0.3 ⁇ m obtained by soap-free emulsion polymerization were mixed.
  • a hybridization system Nara Machinery Co., Ltd .: “Hybridization system NHS-0 type” by high-speed air current impact method (treatment condition: 13000 rpm, 10 minutes)
  • conductive fine particles (1) Insulation coating was performed to obtain conductive fine particles (3).
  • Comparative Example 1 A monomer mixture composed of 80 parts of divinylbenzene and 20 parts of 2-hydroxyethyl methacrylate was subjected to suspension polymerization. By classifying the obtained polymer, 10 parts of vinyl polymer particles having a hydroxyl group on the particle surface (mass average particle diameter 3.5 ⁇ m, coefficient of variation of particle diameter 4.9%) were obtained. Next, 10 parts of the obtained vinyl polymer fine particles were added to 100 parts of tetrahydrofuran (THF) and dispersed uniformly using an ultrasonic disperser.
  • THF tetrahydrofuran
  • Comparative Example 2 As seed particles, 5 parts of polystyrene particles having a mass average particle diameter of 0.8 ⁇ m are used, and this is mixed with 500 parts of ion-exchanged water and 100 parts of a 5% by weight polyvinyl alcohol aqueous solution, placed in a separable flask and stirred. Then, ultrasonic waves were added to uniformly disperse.
  • a dispersion stabilizer 250 parts of a 5% by weight aqueous polyvinyl alcohol solution and 250 parts by weight of a 30% by weight aqueous polyacrylic acid solution are added as a dispersion stabilizer, nitrogen gas is introduced, and the mixture is reacted at 90 ° C. for 9 hours.
  • the resulting emulsion was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol, and further classified.
  • the classified particles were dried at 80 ° C. for 12 hours to obtain substrate particles (4).
  • the obtained base particle (4) had a mass average particle diameter of 3.0 ⁇ m and a coefficient of variation (CV value) of the particle diameter of 4.3%.
  • Comparative Example 3 In a four-necked flask equipped with a condenser, thermometer and dropping port, methanol 200 parts, ultrapure water 15 parts, styrene 25 parts, 2,2′-azobis (2,4-dimethylvaleronitrile) 5 parts, polyvinyl 18.7 parts of pyrrolidone (molecular weight 40,000) (as a dispersion stabilizer) was added. Thereafter, the temperature of the mixed solution was raised to 60 ° C., and a polymerization reaction was performed for 24 hours in a nitrogen atmosphere.
  • the obtained polymer was subjected to solid-liquid separation, thoroughly washed with ultrapure water and methanol, and then vacuum dried at 50 ° C. for 12 hours to obtain polymer seed particles in powder form.
  • the obtained polymer seed particles had a mass average particle size of 1.13 ⁇ m and a coefficient of variation (CV value) of the particle size of 2.5%.
  • a monomer mixture of 60 parts of styrene and 40 parts of divinylbenzene was added to a solution obtained by dissolving 1.5 parts of benzoyl peroxide (initiator) in 300 parts of a 0.2% by weight aqueous sodium lauryl sulfate solution.
  • An emulsion of monomer components was prepared by emulsifying and dispersing at 6000 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The obtained emulsion of monomer components was added to a dispersion of polymer seed particles, and the monomer components were absorbed by the polymer seed particles at room temperature.
  • polyvinyl alcohol 500 parts of a 5% by weight aqueous solution is added, the temperature of the reactor is raised to 80 ° C., and the polymerization reaction is performed for 5 hours.
  • the obtained crosslinked polymer fine particles were washed several times with ultrapure water and ethanol and then vacuum-dried at room temperature.
  • the obtained crosslinked polymer fine particles had a mass average particle size of 3.5 ⁇ m and a variation in particle size.
  • the coefficient (CV value) was 2.6%.
  • the fluidized bed reactor (Fluidized bed type) was filled with 150 parts of crosslinked polymer fine particles, and the inside of the reactor was maintained in a vacuum state. Next, argon gas was injected into the reactor, and then the pressure in the reactor was fixed at 0.5 Torr. The fluidization speed of the crosslinked polymer fine particles at this time was 18.7 cm / s. After the plasma treatment was performed at an output of 100 W for 10 minutes, the fine particles were exposed to the air for 10 minutes to hydrophilize the surface of the crosslinked polymer fine particles to obtain substrate particles (5).
  • the mass average particle diameter of the substrate particles (5) was 3.5 ⁇ m, and the coefficient of variation (CV value) in particle diameter was 2.6%.
  • Comparative Example 4 Using 10 parts of the comparative conductive fine particles (3) obtained in Comparative Example 3, an insulating coating treatment was performed in the same manner as in Example 3 to obtain comparative conductive fine particles (4).
  • Comparative Example 5 0.5 parts of the base particle (1) obtained in Example 1 is added to 100 ml of an oxidation treatment mixed solution adjusted to 200 ml / l and chromic acid 400 g / l in advance, and heat-treated at 70 ° C. for 5 minutes. Went. After cooling to room temperature, the mixture was filtered, and the resulting fine particles were washed with water. Vacuum drying was performed at 80 ° C. for 12 hours to obtain substrate particles (6). When the obtained base particle (3) was analyzed by XPS (ESCA), a carbon peak corresponding to a carboxyl group was observed at 288 eV. The alkali dispersibility of the substrate particles (6) was 0.8%.
  • ESA XPS
  • Average particle size, coefficient of variation of particle size (CV value)
  • the average particle size of the particles was determined by measuring the particle size of 30000 particles using a Coulter Multisizer III type (manufactured by Beckman Coulter, Inc.) to determine the volume average particle size, and the value was taken as the mass average particle size.
  • the CV value (coefficient of variation) of the particle diameter was determined according to the following formula.
  • Total fluorine content, elution and non-elution fluorine content The total fluorine amount and the eluting fluorine content were determined by the above-described method, and the difference was defined as the non-eluting fluorine content.
  • Relative surface abundance of C atoms (%) 100 ⁇ [abundance of C atoms (mol%) / (abundance of C atoms (mol%) + abundance of N atoms (mol%) + abundance of O atoms (mol) %) + F atom abundance (mol%) + Na atom abundance (mol%) + Si atom abundance (mol%))]
  • Relative surface abundance of O atoms (%) 100 ⁇ [abundance of O atoms (mol%) / (abundance of C atoms (mol%) + abundance of N atoms (mol%) + abundance of O atoms (mol %) + F atom abundance (mol%) + Na atom abundance (mol%) + Si atom abundance (mol%))]
  • F-relative surface abundance (%) 100 ⁇ [F atom abundance (mol%) / (C atom abundance (mol%) + N atom abundance (mol%) + O atom abundance (mol %) + F atom abundance (mol%) + Na atom abundance (mol%) + Si atom abundance (
  • An anisotropic conductive material was produced using the conductive fine particles obtained in Examples 1 to 3 and Comparative Examples 1 to 5, and the resistance value between the electrodes was evaluated.
  • the resistance value increases before and after the PCT test. It can be seen that the rate is high and the adhesion between the substrate particles and the conductive metal layer in these conductive fine particles is poor.
  • the anisotropic conductive material using the conductive fine particles of the present invention which has excellent adhesion between the base particles and the conductive metal layer, peels off the conductive metal layer even during weight compression. No breakdown occurs and electrical connection between the opposing electrode substrates can be ensured.
  • it because it is excellent in stability over time, it does not cause deterioration in conductivity due to plating cracking even during long-term use, and it is highly reliable so that electrical connection between electrode substrates can be maintained. I understand that.
  • Example 4 In a four-necked flask equipped with a condenser, thermometer, and dripping port, 135 parts of ion-exchanged water, 0.2 part of 25% aqueous ammonia and 67 parts of methanol are placed, and 3-methacryloxypropyl is added from the dripping port with stirring.
  • An emulsion of polysiloxane particles was prepared by adding 12 parts of trimethoxysilane and hydrolyzing and condensing 3-methacryloxypropyltrimethoxysilane.
  • the solution was added and emulsified and dispersed at 6000 rpm for 5 minutes with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an emulsion of monomer components.
  • TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.
  • the obtained emulsion was added to an emulsion of polysiloxane particles and further stirred. Two hours after the addition of the emulsified liquid, the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles were enlarged by absorbing the monomer.
  • the reaction solution was heated to 65 ° C. in a nitrogen atmosphere and held at 65 ° C. for 2 hours to perform radical polymerization of the monomer component.
  • the emulsion after radical polymerization was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol, and then vacuum dried at 80 ° C. for 12 hours to obtain organic-inorganic composite particles.
  • the particle diameter of the organic-inorganic composite particles was measured by Coulter Multisizer III type (manufactured by Beckman Coulter, Inc.), the mass average particle diameter was 3.0 ⁇ m and the coefficient of variation (CV value) was 3.3%.
  • the composition of the mixed gas and the gas temperature in the chamber were changed to the conditions shown in Table 4, and a hydrophilic treatment was performed in the same manner as in Example 1 to obtain substrate particles (7).
  • XPS XPS
  • a carbon peak corresponding to a carboxyl group was observed at 288 eV.
  • characteristic evaluation was performed by the said method and the evaluation result was shown in Table 4.
  • Example 5 Hydrophilic treatment was performed with the composition of the mixed gas and the gas temperature in the chamber as the conditions shown in Table 4. Next, 7 g of the particles after the hydrophilization treatment were immersed in a 0.25N sodium hydroxide aqueous solution (particle concentration: 2 mass%), and subjected to alkali treatment at 85 ° C. for 3 hours with stirring. After filtering the particles, they were immersed in ion-exchanged water at 85 ° C. (particle concentration: 6.3% by mass) and washed at the same temperature for 3 hours. After cooling to room temperature, the particles were filtered, washed with ion-exchanged water and methanol in that order, and further vacuum-dried at 80 ° C. for 12 hours to obtain substrate particles (8). By XPS (ESCA) analysis of the obtained base particle (8), a carbon peak corresponding to a carboxylate was observed at 288 eV, and the presence of Na was also confirmed.
  • ESA XPS
  • Example 6 A base particle (9) was obtained by carrying out a hydrophilization treatment and an alkali treatment in the same manner as in Example 5 except that the composition of the mixed gas and the gas temperature in the chamber were changed to the conditions shown in Table 4.
  • XPS XPS
  • Example 7 In a four-necked flask equipped with a condenser, thermometer, and dripping port, 135 parts of ion-exchanged water, 0.2 part of 25% aqueous ammonia and 67 parts of methanol are placed, and 3-methacryloxypropyl is added from the dripping port with stirring.
  • An emulsion of polysiloxane particles was prepared by adding 10 parts of trimethoxysilane and subjecting 3-methacryloxypropyltrimethoxysilane to hydrolysis and condensation.
  • the obtained emulsion was added to an emulsion of polysiloxane particles and further stirred. Two hours after the addition of the emulsified liquid, the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles were enlarged by absorbing the monomer.
  • the reaction solution was heated to 65 ° C. in a nitrogen atmosphere and held at 65 ° C. for 2 hours to perform radical polymerization of the monomer component.
  • the emulsion after radical polymerization was subjected to solid-liquid separation, and the resulting cake was washed with ion-exchanged water and methanol, and then vacuum dried at 80 ° C. for 12 hours to obtain organic-inorganic composite particles.
  • the particle size of the organic-inorganic composite particles was measured by Coulter Multisizer III type (manufactured by Beckman Coulter, Inc.), the mass average particle size was 2.9 ⁇ m and the coefficient of variation (CV value) was 3.6%.
  • a base particle (10) was obtained by performing a hydrophilization treatment and an alkali treatment in the same manner as in Example 5 except that the composition of the mixed gas and the gas temperature in the chamber were changed to the conditions shown in Table 4.
  • XPS XPS
  • Example 8 Except that the composition of the mixed gas and the gas temperature in the chamber were the conditions shown in Table 4, hydrophilic treatment and hot water washing were performed in the same manner as in Example 5 to obtain base particles (11). According to XPS (ESCA) analysis of the obtained base particle (11), a carbon peak corresponding to a carboxyl group was observed at 288 eV.
  • ESA XPS
  • Example 9 A base particle (12) was obtained by carrying out a hydrophilization treatment and an alkali treatment in the same manner as in Example 5 except that the composition of the mixed gas and the gas temperature in the chamber were changed to the conditions shown in Table 4. According to XPS (ESCA) analysis of the obtained substrate particles (12), a carbon peak corresponding to a carboxylate was observed at 288 eV.
  • XPS XPS
  • Example 10 In the emulsion of the monomer component of Example 7, 10 parts of 1,6-hexanediol dimethacrylate was changed to 3 parts of styrene and 7 parts of divinylbenzene 960 (manufactured by Nippon Steel Chemical Co., Ltd.). Similarly, organic-inorganic composite particles were obtained. The organic inorganic composite particles had an average particle size of 3.1 ⁇ m and a coefficient of variation (CV value) of 3.5%.
  • CV value coefficient of variation
  • Example 11 In the emulsion of the monomer component of Example 7, the same procedure as in Example 7 except that 10 parts of 1,6-hexanediol dimethacrylate was changed to 7 parts of methyl methacrylate and 3 parts of ethylene glycol dimethacrylate. Thus, organic-inorganic composite particles were obtained.
  • the organic inorganic composite particles had an average particle size of 3.1 ⁇ m and a coefficient of variation (CV value) of 3.5%.
  • Comparative Example 6 In a four-necked flask equipped with a condenser, thermometer, and dripping port, 900 parts of ion-exchanged water, 1.2 parts of 25% aqueous ammonia, and 225 parts of methanol were added and pre-adjusted from the dripping port with stirring. A mixed solution of 50 parts of methacryloxypropyltrimethoxysilane and 75 parts of methanol was added, and hydrolysis and condensation reaction of 3-methacryloxypropyltrimethoxysilane was performed to prepare an emulsion of polysiloxane particles.
  • the obtained emulsion was added to an emulsion of polysiloxane particles and further stirred. Two hours after the addition of the emulsified liquid, the mixed liquid was sampled and observed with a microscope. As a result, it was confirmed that the polysiloxane particles were enlarged by absorbing the monomer.
  • Comparative Example 7 Substrate particles in the same manner as in Comparative Example 6 except that the composition of the emulsion of the monomer component was changed to 112.5 parts of styrene, 112.5 parts of divinylbenzene 960 (manufactured by Nippon Steel Chemical Co., Ltd.) and 25 parts of methacrylic acid. (16) was obtained. When the XPS (ESCA) analysis of the obtained base particle (16) was performed, a carbon peak corresponding to a carboxyl group was confirmed at 288 eV, but the presence of Na was not confirmed.
  • ESA XPS
  • Comparative Example 8 Base material particles (17) were obtained in the same manner as in Example 1 except that the hydrophilic treatment was not performed. XPS (ESCA) analysis of the obtained substrate particles (17) was performed, but no carbon peak corresponding to the carboxyl group was confirmed.
  • the substrate particles obtained in Examples 1 to 11 had a hydrophobization degree of 0 due to the hydrophilization treatment. Further, from the results of Examples 5 to 10, it can be seen that the hydrophilic treatment proceeds in the same manner even when the mixed gas contains an inert gas, and hydrophilic fine particles are obtained.
  • the suspension was solid-liquid separated, and the base particles were washed with 100 parts by mass of ion-exchanged water, and then further washed with 33 parts by mass of methanol to wash the base particles, and then at 120 ° C. Vacuum dried for hours.
  • ⁇ Palladium adsorption treatment> 10 parts of “Pink Summer (manufactured by Nippon Kanigen Co., Ltd.)” and 70 parts of ion-exchanged water were mixed. Separately, 10 parts of ion-exchanged water was prepared by ultrasonically dispersing 2 parts of base particles, and this was added to the mixed solution, and 10 parts of ion-exchanged water that was washed inside the beaker was also added to the mixed solution. did. The mixed solution was stirred at 30 ° C. for 10 minutes to form a suspension, and the cake obtained by solid-liquid separation was washed with 30 parts of ion-exchanged water.
  • the obtained cake was transferred to a beaker and ultrasonically dispersed in 80 parts of ion-exchanged water.
  • 20 parts of “Red Schumer (manufactured by Nippon Kanisen Co., Ltd.)” was added and stirred at 30 ° C. for 10 minutes to obtain a suspension It was.
  • This suspension was subjected to solid-liquid separation, and the resulting cake was washed with 20 parts of ion-exchanged water and vacuum-dried at 100 ° C. for 2 hours under a nitrogen atmosphere to obtain base particles having palladium adsorbed on the surface. .
  • ⁇ Catalytic treatment> 10 parts of “Pink Summer (manufactured by Nippon Kanigen Co., Ltd.)” and 70 parts of ion-exchanged water were mixed. Separately, in a beaker, 10 parts of ion-exchanged water in which 2 parts of base particles are ultrasonically dispersed is prepared, and this is put into the mixed solution. To the mixed solution. The mixed solution was stirred at 30 ° C. for 10 minutes to form a suspension, and the cake obtained by solid-liquid separation was washed with 30 parts of ion-exchanged water.
  • Table 6 shows the results of observation and evaluation of the degree of hydrophobicity and alkali dispersibility of the base particles, and plating cracks and plating defects of the conductive fine particles after the plating treatment.
  • SEM images of the conductive fine particles (6) and (9) obtained from the base particles of Examples 6 and 9 are shown in FIGS. 1 and 2, and an FE-SEM image of the conductive fine particles (9) is shown in FIG.
  • FIG. 4 shows an element distribution diagram
  • FIG. 5 shows a cross-sectional FE-SEM image of the conductive fine particles (9).
  • the conductive fine particles of the present invention using base particles having an M / C of 0.5 ⁇ 10 ⁇ 2 or more and a degree of hydrophobicity of less than 2% have no plating cracks or plating defects. Thus, it can be seen that it has excellent plating properties.
  • conductive fine particles (Example 6) having base particles using a styrene monomer and an aromatic divinyl compound as monomer components have base material particles having an acrylic monomer. It turns out that it is excellent in plating property compared with the electroconductive fine particles (Example 9) which consist of a body.
  • 3 is an FE-SEM image of the conductive fine particles (9) obtained in Example 9
  • FIG. 4 is a result of elemental analysis by EDS of a portion surrounded by a white frame on the particle surface of FIG.
  • FIG. 5 is an FE-SEM image showing a cross section of the conductive fine particles (9) obtained in Example 9. From these drawings, the conductive fine particles (9) It can be confirmed that the surfaces of the particles (12) are coated with nickel.
  • P is a component derived from a reducing agent in the plating solution.
  • the conductive fine particles (7) and (8) obtained in Examples 7 and 8 were observed with an SEM, the conductive fine particles (7) obtained by subjecting the base particles to an alkali treatment showed good surface properties. However, in the conductive fine particles (8) in which the substrate particles were washed with warm water and not subjected to the alkali treatment, abnormal precipitation of nickel was confirmed.
  • the conductive fine particles of the present invention are excellent in adhesion between the base particles and the conductive metal layer, and do not cause a decrease in conductivity due to plating cracks or the like even during long-term use. It can be used as a conductive material that connects electrodes, such as anisotropic conductive films, anisotropic conductive pastes, conductive adhesives, and conductive adhesives. It is done.

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Abstract

L'invention concerne des particules électroconductrices dans lesquelles ne se produit qu'un faible nombre de défauts, tels que des fissures dans la couche métallique électroconductrice; l'adhérence entre les particules de base et la couche métallique électroconductrice est supérieure, et une couche électroconductrice peut uniformément recouvrir les surfaces des particules de base alors que, dans un même temps, il est possible de simplifier considérablement le procédé classique pour appliquer une couche métallique électroconductrice et un matériau électroconducteur anisotrope qui utilise les particules électroconductrices. Les particules électroconductrices comprennent: des particules de base composées de polymères vinyliques qui présentent un rapport atomique M/C (M indiquant le nombre total d'atomes de l'élément métallique alcalin et C le nombre d'atomes de l'élément azote) pour les particules de base d'au moins 0,5 x 10-2 après traitement par absorption du sodium mesuré par spectroscopie de photoélectrons X (ESCA), un degré d'hydrophobisation inférieur à 2%, et un diamètre des particules moyen en masse égal ou inférieur à 1000 μm; et des couches métalliques électroconductrices recouvrant les surfaces des particules de base. Les particules électroconductrices sont obtenues par formation des couches métalliques électroconductrices sur les surfaces des particules de base par dépôt anélectrolytique.
PCT/JP2009/066455 2008-09-19 2009-09-18 Particules électroconductrices et matériau électroconducteur anisotrope utilisant ces particules WO2010032854A1 (fr)

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JP2012243582A (ja) * 2011-05-19 2012-12-10 Nippon Shokubai Co Ltd 導電性微粒子及びその製造方法
JP2013120293A (ja) * 2011-12-07 2013-06-17 Nippon Shokubai Co Ltd スペーサー粒子、導電性スペーサー粒子及び異方性導電材料
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EP3378914A4 (fr) * 2015-11-20 2019-07-03 Sekisui Chemical Co., Ltd. Particules, matériau de liaison et structure de liaison
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JP2012079635A (ja) * 2010-10-05 2012-04-19 Nippon Shokubai Co Ltd 導電性微粒子、絶縁性樹脂被覆導電性微粒子及び異方性導電材料
JP2012185918A (ja) * 2011-03-03 2012-09-27 Nippon Shokubai Co Ltd 導電性微粒子及びそれを用いた異方性導電材料
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JP2013120293A (ja) * 2011-12-07 2013-06-17 Nippon Shokubai Co Ltd スペーサー粒子、導電性スペーサー粒子及び異方性導電材料
JPWO2016006567A1 (ja) * 2014-07-08 2017-04-27 ユーエムジー・エービーエス株式会社 熱可塑性樹脂組成物およびその成形品
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US11017916B2 (en) 2015-11-20 2021-05-25 Sekisui Chemical Co., Ltd. Particles, connecting material and connection structure
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US11027374B2 (en) 2015-11-20 2021-06-08 Sekisui Chemical Co., Ltd. Particles, connecting material and connection structure
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JP2020095941A (ja) * 2018-10-03 2020-06-18 デクセリアルズ株式会社 異方性導電フィルム、接続構造体、接続構造体の製造方法
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