WO2014163059A1 - Matériau de revêtement électriquement conducteur, et support l'utilisant - Google Patents

Matériau de revêtement électriquement conducteur, et support l'utilisant Download PDF

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Publication number
WO2014163059A1
WO2014163059A1 PCT/JP2014/059588 JP2014059588W WO2014163059A1 WO 2014163059 A1 WO2014163059 A1 WO 2014163059A1 JP 2014059588 W JP2014059588 W JP 2014059588W WO 2014163059 A1 WO2014163059 A1 WO 2014163059A1
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component
conductive
particles
adherend
coating
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PCT/JP2014/059588
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English (en)
Japanese (ja)
Inventor
俊之 長谷
小嶋　一宏
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スリーボンドファインケミカル株式会社
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Publication of WO2014163059A1 publication Critical patent/WO2014163059A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to a conductive paint containing a conductive polymer and an adherend using the same.
  • a display surface of a display device such as a liquid crystal display, a window material such as a clean room, a glass or plastic used as a packaging material such as an IC package, or an overhead display or a film used for a photograph.
  • a display surface of a display device such as a liquid crystal display, a window material such as a clean room, a glass or plastic used as a packaging material such as an IC package, or an overhead display or a film used for a photograph.
  • Such various transparent base materials are generally insulators and are easily charged with static electricity. For this reason, dust, dust, and the like are likely to adhere to the surface, and problems such as deterioration in visibility, generation of defective products due to mixing into products, malfunction of electronic devices, and the like may occur.
  • the influence of electromagnetic waves generated from these electronic devices on the human body is also a problem. Therefore, application examples of conductive paints containing conductive particles are increasing for preventing charging and shielding electromagnetic waves.
  • a conductive paint that can be used as a conductive adhesive is also useful when manufacturing electronic devices or when manufacturing parts used in electronic devices. For example, when stacking and connecting sheet-like electrodes and dielectrics, electrically connecting substrates such as printed wiring boards, or connecting parts such as semiconductor elements to the substrate Adhesives are widely used.
  • a composition using insulating particles coated with a conductive polymer is known.
  • the manufacturing method uses a ball mill and a large amount of solvent.
  • filtration is performed to collect the particles, it was not clear whether most of the initially charged conductive polymer was filtered together with the solvent and the conductive polymer remained on the surface of the insulating particles.
  • primary particles may be fused to form large secondary particles during drying, or the conductive polymer coated on the surface of insulating particles may be biased to a certain region due to surface tension during drying. Concerned. It is estimated that the process is complicated by a combination of drying, filtration, washing and the like, and is complicated.
  • a conductive paint containing a conductive polymer has poor wettability with respect to an adherend, particularly in the case of an aqueous system, and the conductive paint is evenly coated on the adherend of various materials. Was difficult. Further, when the adherend is particles, it has been particularly difficult to uniformly coat the conductive paint.
  • a further object of the present invention is to provide conductive particles uniformly coated with the conductive paint of the present invention and a method for producing the same. Furthermore, a further object of the present invention is to provide a conductive adhesive and an anisotropic conductive adhesive having improved conductivity by using the conductive particles of the present invention.
  • the present inventors have completed the present invention relating to a conductive paint containing a conductive polymer and an adherend using the same.
  • the first embodiment of the present invention is a conductive paint containing the components (A) to (D).
  • FIG. 1 shows the result of measuring the continuity of processed particles with a micro compression tester.
  • the present invention is a conductive paint containing a conductive polymer.
  • the paint exhibits conductivity.
  • the component (C) is water
  • the conductive paint of the present invention is water-based, has little influence on the environment, and is excellent in workability.
  • the silane coupling agent having an alicyclic epoxy group and / or a silane coupling agent having a (meth) acrylic group as the component (D)
  • the entire components (A) to (D) are integrated.
  • the conductive coating material can form a uniform film on various adherends.
  • the present invention has good wettability with respect to various adherends, and has an effect of obtaining an adherend by forming a uniform film.
  • the adherend is a particle
  • the conductive coating can be evenly coated on the particle surface by a preferable manufacturing method.
  • the component (A) that can be used in the conductive paint of the present invention is poly3,4-ethylenedioxythiophene as shown in the following formula 1. Moreover, the derivative
  • Poly3,4-ethylenedioxythiophene may be synthesized by itself, but a commercially available product can also be used. Specific examples of commercially available products include H.C. C. Examples thereof include Clevios MV2 manufactured by STARCK, but are not limited thereto.
  • R 1 and R 2 represent an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group.
  • R 1 and R 2 may be connected by a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms to form a ring.
  • the substituent is an organic group, and more preferably an alkyl group having 1 to 10 carbon atoms.
  • R 1 and R 2 are more preferably an ethylene group, a trimethylene group or a propylene group as a whole.
  • R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, or an organic group.
  • the organic group an alkyl group having 1 to 10 carbon atoms is preferable.
  • n is an integer.
  • iron (III) chloride In order to oxidatively polymerize thiophene, which is the main skeleton of component (A), iron (III) chloride, iron (III) chloride hydrate, iron (III) sulfide, copper perchlorate, iron perchlorate, para Other oxidizing agents including iron (III) toluenesulfonate are also used as catalysts.
  • iron (III) chloride and iron (III) paratoluenesulfonate are known to have good yields, but are not limited thereto.
  • the component (B) that can be used in the conductive paint of the present invention is polystyrene sulfonic acid.
  • guide_body is also contained in the (B) component of this invention, and the some (B) component may be mixed. Even if the site of the sulfonic acid is a metal salt such as sodium, potassium or iron, it can be used if there is no problem in the expression of conductivity.
  • the component (A) In order to develop conductivity, it is known to perform p-type doping on the component (A).
  • Various types of reagents are used as the dopant.
  • organic acids such as iodine, bromine, trifluoroacetic acid, propionic acid and sulfonic acid are used.
  • the component (B) is used as the dopant. It becomes a polymer which shows electroconductivity by combining (A) component and (B) component.
  • (A) component and (B) component can synthesize
  • a commercial item can also be used.
  • the mixing ratio of the component (A) and the component (B) is preferably 100 to 700 parts by weight of the component (B) with respect to 100 parts by weight of the component (A).
  • the component (B) is two or more, it means the total amount, and if the component (B) is 700 parts by mass or less, the conductivity can be reliably exhibited, and if the component (B) is 100 parts by mass or more, it is conductive. Can be demonstrated more reliably.
  • the component (C) that can be used in the conductive paint of the present invention is water.
  • water containing no ionic impurities such as purified water or distilled water is used.
  • the conductive paint of the present invention becomes a water-based paint, has little influence on the environment, and improves workability.
  • the component (A) and the component (B) are used by being dispersed in the water that is the component (C).
  • the components may be adjusted by themselves, or commercially available products in a state where these components are dispersed in water may be used.
  • component (A) and component (B) are dispersed (dispersion) in component (C).
  • C examples include, but are not limited to, Clevios P, PH and the like made by STARCK.
  • the mixing ratio it is preferable that 100 parts by mass of the mixture (solid content) of the component (A) and the component (B) is contained in an amount of 0.1 to 10% by mass of the component (C), more preferably 0.1 to 10%. 5% by mass. If 100 parts by mass of the mixture of the component (A) and the component (B) is 0.1% by mass or more, the conductivity of the coating film is surely expressed, and if it is 10% by mass or less, it is suitable for workability. It becomes a viscous paint.
  • the paint is water-based means that the main solvent is water.
  • the main solvent is water.
  • 100 parts by mass of the mixture of the component (A) and the component (B) is water.
  • the content is 0.1 to 10% by mass.
  • a form further including an organic solvent which is a component (E) described later as an additive is also preferable.
  • the component (E) is an additive, and the effect of improving the conductivity of the film can be obtained by adding this component.
  • the component (D) that can be used in the conductive paint of the present invention is at least one of a silane coupling agent having an alicyclic epoxy group and a silane coupling agent having a (meth) acryl group.
  • the silane coupling agent having an alicyclic epoxy group is not limited to this, but 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferably used.
  • Examples of commercially available silane coupling agents having an alicyclic epoxy group include KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd., A-186 manufactured by Nippon Unicar Co., Ltd., and the like.
  • silane coupling agent having a (meth) acryl group examples include, but are not limited to, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and the like. Of these, 3-methacryloxypropyltrimethoxysilane is more preferable for the desired effect of the present invention.
  • KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 and the like manufactured by Shin-Etsu Chemical Co., Ltd. are known. However, it is not limited to these.
  • component (D) may be mixed and used.
  • the component (D) is preferably contained in an amount of 10 to 1000 parts by mass, more preferably 10 to 500 parts by mass with respect to 100 parts by mass of the mixture of the component (A) and the component (B). .
  • (D) component is 2 or more types, it says the total amount of them.
  • the component (D) is preferably 0.01 to 10 parts by mass, more preferably 0 to 100 parts by mass of the total of the components (A), (B) and (C). 1 to 5 parts by mass.
  • the conductive paint of the present invention preferably further contains at least one solvent selected from glycol derivatives, pyrrolidone derivatives and sulfoxide derivatives as the component (E). That is, the second embodiment of the present invention is the conductive paint according to the first embodiment, further comprising at least one solvent selected from glycol derivatives, pyrrolidone derivatives, and sulfoxide derivatives as the component (E). is there. Further, two or more different types of (E) components may be mixed and used. Although the clear reason has not been elucidated, it has been found that the addition of the component (E) improves the conductivity of the conductive paint film.
  • glycol derivative examples include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-nbutyl ether and the like. More preferably, it is ethylene glycol from the viewpoint of availability and cost.
  • pyrrolidone derivatives include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, N -Phenyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone and the like. More preferred is N-methyl-2-pyrrolidone from the viewpoint of availability and cost.
  • sulfoxide derivatives examples include dialkyl sulfoxides such as dimethyl sulfoxide, tetramethylene sulfoxide, dioctyl sulfoxide, and dibenzyl sulfoxide; diaryl sulfoxides such as diphenyl sulfoxide, di-p-tolyl sulfoxide, and bis- (p-chlorophenyl) sulfoxide. . More preferred is dimethyl sulfoxide from the viewpoint of availability and cost.
  • the third embodiment of the present invention is the conductive paint according to the second embodiment, wherein the component (E) is at least one selected from ethylene glycol, N-methyl-2-pyrrolidone and dimethyl sulfoxide. It is.
  • the component (E) is preferably contained in an amount of 10 to 1000 parts by mass, more preferably 200 to 700 parts by mass with respect to 100 parts by mass of the mixture of the components (A) and (B).
  • the component (E) When there are two or more components, the total amount thereof is indicated. If it is 10 parts by mass or more, the conductivity can be improved, and if it is 1000 parts by mass or less, the component (E) is volatile, and the coating film is quickly dried, which is preferable.
  • the component (E) is preferably 0.1 to 20 parts by mass, more preferably 1 ⁇ 10 parts by mass.
  • the conductive paint of the present invention includes colorants such as pigments and dyes, metal powders, inorganic fillers such as calcium carbonate, talc, silica, alumina, aluminum hydroxide, and flame retardants, as long as the effects of the present invention are not impaired.
  • colorants such as pigments and dyes, metal powders, inorganic fillers such as calcium carbonate, talc, silica, alumina, aluminum hydroxide, and flame retardants, as long as the effects of the present invention are not impaired.
  • An appropriate amount of additives such as organic fillers, plasticizers, antioxidants, antifoaming agents, leveling agents, rheology control agents, and the like may be blended. By adding these, a coating film excellent in conductivity, flexibility, adhesive strength, workability and the like can be obtained.
  • the conductive paint can be applied to adherends of various materials to form a uniform coating film. That is, the fourth embodiment of the present invention is an adherend provided with a coating film, in which the conductive paint according to any one of the first to third embodiments is coated on the adherend.
  • the material of the adherend is not particularly limited, but (meth) acrylic resin, glass, polyphenylene sulfide, polybutylene terephthalate, polyethylene, nylon, polyacetal, liquid crystal polymer, hard vinyl chloride, polycarbonate, polyethylene terephthalate, cycloolefin resin , Polystyrene resin, phenol resin, acrylonitrile-butadiene-styrene resin, and the like.
  • the adherend is (meth) acrylic resin, glass, polyphenylene sulfide, polybutylene terephthalate, polyethylene, nylon, polyacetal, liquid crystal polymer, hard vinyl chloride, polycarbonate, polyethylene terephthalate, cycloolefin. It is a to-be-adhered body provided with the coating film as described in 4th Embodiment which is resin, a polystyrene resin, or a phenol resin.
  • a uniform coating film can be formed by the conductive paint of the present invention. In particular, it is possible to form a good coating film on acrylic resin or glass that is used for general purposes.
  • the shape of the adherend is not limited to a film shape, a sheet shape, a plate shape, and a flat plate shape.
  • a film can be formed.
  • the conductive coating film on the adherend there are no particular restrictions on the formation of the conductive coating film on the adherend, and methods such as bar coating, spray coating, curtain coating, spin coating, gravure coating, ink jet, and dip are used. be able to.
  • the coating thickness is preferably adjusted so that the film thickness after drying is 1 to 600 nm, more preferably 10 to 300 nm.
  • the coating film can be formed by drying at 40 to 150 ° C. in a hot air drying furnace or the like. If it is 150 degrees C or less, since it will not become high temperature even if it heats, it can maintain, without the electroconductivity of a conductive polymer falling. Further, bumping of the component (C) can be prevented.
  • the adherend provided with the coating film of the conductive paint of the present invention is obtained.
  • the sixth embodiment of the present invention is a conductive particle obtained by coating the particle with the conductive paint according to any one of the first to third embodiments.
  • the conductive paint of the present invention can be applied to various adherends to form a uniform coating film.
  • the particle-shaped adherend is coated to obtain conductive particles. It is suitable for.
  • the electroconductive particle of this invention is corresponded to the plating powder of a prior art, since a metal is not used, an inexpensive electroconductive particle can be manufactured without using a multistep process.
  • the adherend constituting the particle is not particularly limited, and the above-described adherend formed into particles can be used.
  • (meth) acrylic resin particles are preferred because there are particularly abundant particle variations and a more uniform coating can be formed by the conductive paint of the present invention.
  • 7th embodiment of this invention is the electroconductive particle as described in 6th embodiment in which the said particle
  • a conductive adhesive or an anisotropic conductive adhesive can be produced.
  • the above two types of adhesives can be made separately. That is, in the case of a conductive adhesive, the addition amount of conductive particles is 70 to 99% by mass, whereas in the anisotropic conductive adhesive, the addition amount is 1 to 10% by mass.
  • the curing method is also different. In the case of a conductive adhesive, conductivity is manifested by curing after application.
  • the ninth embodiment of the present invention is a conductive adhesive comprising the conductive particles described in the sixth or seventh embodiment or the conductive particles manufactured by the manufacturing method described in the eighth embodiment. It is. Further, the tenth embodiment of the present invention is an anisotropic conductive material including the conductive particles described in the sixth or seventh embodiment or the conductive particles manufactured by the manufacturing method described in the eighth embodiment. It is an adhesive.
  • the curing form of the curable resin various curing forms such as thermal curing, photocuring, anaerobic curing, and moisture curing can be used.
  • thermosetting a curable epoxy resin, a curable urethane resin, an addition-type silicone resin, or the like can be used, but is not limited thereto.
  • Photocuring includes, but is not limited to, curable acrylate resins, curable methacrylate resins, and curable vinyl ether resins.
  • Anaerobic curing is a form in which the resin is cured by contact with the adherend when the adherend is a metal.
  • a composition of a methacrylate compound and saccharin is representative, but is not limited thereto.
  • moisture curing include, but are not limited to, condensation-type silicone resins.
  • an anisotropic conductive adhesive when an anisotropic conductive adhesive is made by adding metal particles to a photocurable resin, the photocurable resin is colored and opaque due to the influence of the metal particles.
  • the conductive particles of the present invention when the conductive particles of the present invention are added to a photocurable resin, an anisotropic conductive adhesive having no color and good transparency can be produced.
  • the resin when trying to make an anisotropic conductive adhesive by adding metal particles to an anaerobic curable resin, the resin reacted with the metal particles and gelled.
  • the conductive particles of the present invention are not metals, they do not gel even when added to an anaerobic curable resin, and an anisotropic conductive adhesive having anaerobic curability can be made.
  • the conductive adhesive or anisotropic conductive adhesive of the present invention includes pigments, dyes and other colorants, metal powder, calcium carbonate, talc, silica, alumina, aluminum hydroxide as long as the effects of the present invention are not impaired.
  • An appropriate amount of additives such as inorganic fillers, flame retardants, organic fillers, plasticizers, antioxidants, antifoaming agents, leveling agents, rheology control agents and the like may be blended. By adding these, a composition excellent in conductivity, flexibility, adhesive strength, workability and the like can be obtained.
  • the conductive adhesive and the anisotropic conductive adhesive can be used as an electrical connection material in the electric / electronic field.
  • the conductive particles according to the sixth or seventh embodiment have a step of coating the particles with the conductive paint using a rolling fluidized bed granulation coating apparatus. It is a manufacturing method.
  • conductive particles are formed by adhering a conductive paint to the surface of the particles to be adhered and drying by heating.
  • the apparatus for forming conductive particles include a rolling fluid coating apparatus (for example, a rolling fluid coating apparatus-MP-01 (manufactured by POWREC Co., Ltd.)) and a centrifugal fluid coating granulator (for example, Granurex ( Freund Sangyo Co., Ltd.), composite granulation coating equipment (eg Spiraflow (Freund Sangyo Co., Ltd.), etc.), fluidized bed granulation drying equipment (eg GPCG / WSG-CT series (Powrec Co., Ltd.) ), Etc.), flow coater (Freund Sangyo Co., Ltd.), fine particle coating and granulating equipment-SFP series (manufactured by POWREC, Inc.), fine particle coating equipment GPCG-SCP series (manufactured by POWREC, Inc.),
  • secondary agglomerates may occur depending on the method of adhering the conductive coating to the particle surface, and when the secondary agglomerates occur, the particle size distribution of the original primary particles may change. There is.
  • the conductive paint may be biased on the particle surface, and a uniform coating film may not be obtained.
  • the specifications of the processing apparatus and the charging method such as dripping or spraying of the stock solution depend greatly. Therefore, as a specification for obtaining the conductive particles of the present invention, it is more preferable to use a rolling fluidized coating apparatus.
  • Rolling fluid coating equipment is characterized by a fluidized bed granulator that has a granular material flow and high-efficiency drying action by an air flow, and a stirring granulator that has a powder flow, rolling, and compaction action by a mechanical action. Is an apparatus for performing granulation and fine particle coating. Further, it is most preferable that the stock solution is charged by a spray method.
  • the coating material was applied to the substrate with a bar coater and left in a hot air drying oven at 100 ° C. for 5 minutes to evaporate the water and obtain a 100 nm coating film.
  • the substrate was confirmed to have “coating property (acrylic)” and “coating property (glass)” with respect to the acrylic resin plate and the glass plate, respectively.
  • confirmation was made visually by the following three stages.
  • ⁇ The coating film has a uniform thickness. ⁇ : Applied but the composition is partially biased. X: Completely repelled and not applied.
  • a coating film was prepared on the glass plate by the same method as the above coating film property confirmation, and the electrode width was 1 mm, the distance between the electrodes was 5 mm, and “surface resistance value (unit: ⁇ ) was measured with a tester (two-terminal method). ) ”Was measured.
  • M means 10 6 .
  • the composition may be biased even after application.
  • the viscosity of the paint may temporarily decrease and the paint may approach.
  • the paints of Examples 1 to 7 to which the component (D) was added formed an even coating film on both the acrylic resin and the glass.
  • Examples 2, 4 to 6 to which the component (E) was added a decrease in the surface resistance value could be confirmed as compared with Examples 1, 3, and 7 to which the component (E) was not added, and it was more conductive. It can be seen that a conductive paint having excellent properties was obtained.
  • Comparative Example 1 not including the component (D) and Comparative Examples 2 to 4 including the component (D ′) instead of the component (D), a coating film could not be formed on the acrylic resin. . Furthermore, in Comparative Example 5 which does not contain the components (A) to (C), a coating film could not be formed on both acrylic resin and glass.
  • Example 2 the coating properties of the conductive paint obtained in Example 2 were confirmed using materials other than glass and acrylic as adherends.
  • the test method and judgment criteria were the same as those for the above-described coating property confirmation.
  • Table 3 The results are summarized in Table 3 below. From Table 3, it was found that although some materials have “x”, good coating films can be formed on various materials other than acrylic and glass.
  • Example 8 Comparative Examples 5 to 6
  • the surface of polymethyl methacrylate particles having an average particle size of 15 ⁇ m was coated with the conductive paint obtained in Example 2 to produce conductive particles.
  • the following apparatuses 1 to 3 were used to attach the paint to the particle surfaces and dry them.
  • the particles processed by the apparatus are called processed particles.
  • the specifications of each apparatus are summarized in Table 4 below. Further, as described later, the conductivity of the treated particles was measured.
  • a particle and fine particle coating device that combines the characteristics of a fluidized bed granulator (powder flow by airflow, high-efficiency drying action) and agitation granulator (powder flow, rolling, compaction action by mechanical action). is there.
  • Apparatus 2 (UV type vibration stirrer): In the batch type vertical dryer, the vibration mechanism attaches two vibration motors to the side of the main body and generates a semi-elliptical vibration obliquely upward. The material to be dried inside the main body flows up and down in the radial direction while turning in the circumferential direction.
  • Device 3 high speed vacuum dryer: The inside of the can body is evacuated and the jacket is heated from the bottom and side surfaces of the can body. By stirring and rolling the material to be dried, heat can be uniformly applied and drying can be performed in a short time.
  • Example 8 The particles produced according to Table 4 were measured for conductivity with a micro compression tester manufactured by Shimadzu Corporation. The measured value when a particle having a particle size of 15 ⁇ m was compressed to 70% (10 ⁇ m) while compressing one particle at a load speed of 3.8 mN / sec was taken as a resistance value. The results of Example 8 are shown in FIG. The X axis is displacement (unit: ⁇ m), and the displacement of the probe in contact with the particles is 0 ⁇ m. The Y-axis is the resistance value at that time (unit: ⁇ 10 6 ⁇ ). Example 8 exhibited a conductivity of 0.06 ⁇ 10 6 ⁇ , but Comparative Examples 5 and 6 were insulating, and the resistance value could not be measured.
  • Example 8 Since only the conductivity of Example 8 was exhibited, it can be seen that the state of the coating film is greatly affected by the apparatus for forming the coating film.
  • the charging method of the composition it is considered that in the case of dropping, a nonuniform coating film is formed on the particle surface, and spraying forms a uniform coating film.
  • the rolling / flowing method is considered to be more suitable for stirring than for vibration.
  • Example 9 In order to prepare an anisotropic conductive adhesive using the conductive particles obtained in Example 8, the following components were prepared. All the following components were weighed and stirred for 30 minutes. Detailed preparation amounts are in accordance with Table 5, and all numerical values are expressed in parts by mass. ⁇ Polyethylene glycol # 400 diacrylate (A-400 Shin-Nakamura Chemical Co., Ltd.) 1-hydroxycyclohexyl phenyl ketone (IRGACURE (registered trademark) 184 manufactured by BASF) -Conductive particles of Example 8
  • Example 9 The conductivity of Example 9 above was measured. Two 10 mm ⁇ 25 mm ITO glass plates having a surface treated with ITO on one side were prepared. Among them, a strip-shaped PET film having a thickness of 12 ⁇ m was disposed on both sides of the ITO glass plate as a spacer on one conductive surface side. 0.5 mg of the anisotropic conductive adhesive of Example 9 was applied between PET films. On this coating film, the conductive surface of another ITO glass was shifted so that the bonded surface was 5 mm ⁇ 5 mm. After the bonded ITO glass was fixed with a clip, light irradiation was performed with an integrated light amount of 3000 mJ / cm 2 to cure the adhesive. The resistance value between the ITO glass of the test piece produced as described above was measured, and the total resistance value of the ITO glass and the conductive particles was measured and found to be 300 ⁇ .
  • the present invention is a conductive paint capable of forming an organic conductive layer on an adherend of various materials.
  • the conductive particles In the production of the conductive particles, it can be efficiently produced by using a specific type of apparatus.
  • the said electroconductive particle is corresponded to plating powder, since a metal is not used, an inexpensive electroconductive particle can be manufactured without using a multistep process.
  • the anisotropic conductive adhesive using the said electroconductive particle it can form the hardened

Abstract

Cette invention concerne un matériau de revêtement électriquement conducteur ayant une bonne mouillabilité sur divers supports et qui, quand les supports sont des particules, peut être appliqué uniformément aux surfaces des particules à l'aide d'un procédé de production spécifique. Le matériau de revêtement électriquement conducteur selon l'invention comprend les composants (A) à (D) suivants : (A) polyéthylène dioxythiophène; (B) sulfonate de polystyrène; (C) eau; et (D) agent de couplage silane contenant un groupe époxy alicyclique et/ou agent de couplage silane contenant un groupe (méth)acrylique.
PCT/JP2014/059588 2013-04-01 2014-03-31 Matériau de revêtement électriquement conducteur, et support l'utilisant WO2014163059A1 (fr)

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WO2018061374A1 (fr) * 2016-09-30 2018-04-05 積水化成品工業株式会社 Particules de résine conductrice et utilisation desdites particules

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JP6905744B2 (ja) * 2016-07-19 2021-07-21 丸尾カルシウム株式会社 導電性表面処理粉体填料及び該填料を含有してなる樹脂組成物
TWI651345B (zh) * 2017-09-29 2019-02-21 國立中山大學 可撓式透明導電膜之製造方法及使用此方法所製造之可撓式透明導電膜、透明電極及有機發光二極體

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JP2009199817A (ja) * 2008-02-20 2009-09-03 Teijin Dupont Films Japan Ltd 導電性フィルムおよびそれを用いたタッチパネル
JP2009230885A (ja) * 2008-03-19 2009-10-08 Teijin Dupont Films Japan Ltd 導電性フィルムおよびそれを用いたタッチパネル
WO2011093480A1 (fr) * 2010-01-26 2011-08-04 帝人デュポンフィルム株式会社 Film électriquement conducteur
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JP2006318876A (ja) * 2004-06-29 2006-11-24 Dainippon Printing Co Ltd エレクトロルミネッセント素子の製造方法及びエレクトロルミネッセント素子
JP2009170319A (ja) * 2008-01-17 2009-07-30 Toda Kogyo Corp 導電性粒子粉末
JP2009199817A (ja) * 2008-02-20 2009-09-03 Teijin Dupont Films Japan Ltd 導電性フィルムおよびそれを用いたタッチパネル
JP2009230885A (ja) * 2008-03-19 2009-10-08 Teijin Dupont Films Japan Ltd 導電性フィルムおよびそれを用いたタッチパネル
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WO2018061374A1 (fr) * 2016-09-30 2018-04-05 積水化成品工業株式会社 Particules de résine conductrice et utilisation desdites particules
JPWO2018061374A1 (ja) * 2016-09-30 2019-08-29 積水化成品工業株式会社 導電性樹脂粒子及びその用途

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