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US20160149366A1 - Method for manufacturing electrically conductive adhesive film, electrically conductive adhesive film, and method for manufacturing connector - Google Patents

Method for manufacturing electrically conductive adhesive film, electrically conductive adhesive film, and method for manufacturing connector Download PDF

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Publication number
US20160149366A1
US20160149366A1 US14/904,443 US201414904443A US2016149366A1 US 20160149366 A1 US20160149366 A1 US 20160149366A1 US 201414904443 A US201414904443 A US 201414904443A US 2016149366 A1 US2016149366 A1 US 2016149366A1
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Prior art keywords
electrically conductive
conductive particles
film
manufacturing
adhesive layer
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Abandoned
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US14/904,443
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English (en)
Inventor
Yasushi Akutsu
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Dexerials Corp
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Dexerials Corp
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Publication of US20160149366A1 publication Critical patent/US20160149366A1/en
Abandoned legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/20Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for assembling or disassembling contact members with insulating base, case or sleeve
    • H01R43/205Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for assembling or disassembling contact members with insulating base, case or sleeve with a panel or printed circuit board
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • C09J7/02
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00Electrically-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
    • H01R4/04Electrically-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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/007Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for elastomeric connecting elements
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323Assembling 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres
    • C08K7/18Solid spheres inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients
    • C09J2201/122
    • C09J2201/602
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C09J2205/102
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/10Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R12/00Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
    • H01R12/50Fixed connections
    • H01R12/59Fixed connections for flexible printed circuits, flat or ribbon cables or like structures
    • H01R12/62Fixed connections for flexible printed circuits, flat or ribbon cables or like structures connecting to rigid printed circuits or like structures
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203Fillers and particles
    • H05K2201/0206Materials
    • H05K2201/0224Conductive particles having an insulating coating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/13Moulding and encapsulation; Deposition techniques; Protective layers
    • H05K2203/1333Deposition techniques, e.g. coating
    • H05K2203/1344Spraying small metal particles or droplets of molten metal
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/14Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
    • H05K3/143Masks therefor

Definitions

  • the present invention relates to an electrically conductive adhesive, particularly relates to a method for manufacturing an electrically conductive adhesive film that is suitably usable in anisotropic conductive connection, an electrically conductive adhesive film manufactured by using this manufacturing method, and a method for manufacturing a connector using this electrically conductive adhesive film.
  • an anisotropic conductive film obtained by molding a binder resin in which electrically conductive particles are dispersed into a film is used as an adhesive when connecting a rigid substrate such as a glass substrate or a glass epoxy substrate to a flexible substrate or an IC chip or when connecting flexible substrates to each other.
  • a rigid substrate such as a glass substrate or a glass epoxy substrate
  • IC chip when connecting flexible substrates to each other.
  • an anisotropic conductive film 53 is disposed between the regions in which both connecting terminals 52 and 55 of a flexible substrate 51 and a rigid substrate 54 are formed, a buffer material 50 is appropriately disposed on the flexible substrate 51 , and the substrates 51 and 54 are heat-pressurized from the top of the flexible substrate 51 by a heating and pressing head 56 .
  • the binder resin becomes fluid to flow out from between the connecting terminal 52 of the flexible substrate 51 and the connecting terminal 55 of the rigid substrate 54 and also the electrically conductive particles in the anisotropic conductive film 53 are pressed and deformed by being sandwiched between the two connecting terminals.
  • the connecting terminal 52 of the flexible substrate 51 and the connecting terminal 55 of the rigid substrate 54 are electrically connected to each other via the electrically conductive particles, and the binder resin is cured in this state.
  • the electrically conductive particles that are not present between the two connecting terminals 52 and 55 are dispersed in the binder resin and maintained in the electrically isolated state.
  • Patent Literature 1 JP 04-251337 A
  • Patent Literature 2 JP 2010-251337 A
  • Patent Literature 3 JP 4789738 B1
  • the microminiaturization of the connecting terminals due to an increase in terminals associated with high definition of the screen and miniaturization of the control IC and the narrowing of the interval between the adjacent connecting terminals have advanced in a so-called COG (Chip on Glass) connection to connect the control IC of a liquid crystal screen to the ITO wiring of a glass substrate.
  • COG Chip on Glass
  • an object of the invention is to provide a method for manufacturing an electrically conductive adhesive film which can capture electrically conductive particles in a microminiaturized connecting terminal as well as prevent a short circuit between terminals even though microminiaturization of the connecting terminal and the narrowing of the interval between connecting terminals advance and thus can meet the requirement of high density mounting, an electrically conductive adhesive film, and a method for manufacturing a connector.
  • a method for manufacturing an electrically conductive adhesive film is a method which includes steps of providing an electrically conductive support plate to support a first base film having an adhesive layer formed on a surface, providing an array plate that is disposed to face the adhesive layer of the first base film supported by the support plate and has a plurality of through holes arranged in a pattern corresponding to an array pattern of electrically conductive particles formed thereon, providing a spray that is disposed on a side opposite to a side facing the support plate of the array plate and sprays electrically conductive particles together with a liquid while applying a voltage to the electrically conductive particles, spraying the electrically conductive particles charged with an electrical charge together with a liquid from the spray while applying a voltage between the spray and the support plate supporting a surface on the opposite side to a surface on which the adhesive layer is formed of the first base film, and arranging the electrically conductive particles which passed through the through holes of the array plate on the adhesive layer in an array pattern of the through holes.
  • an electrically conductive adhesive film according to the invention is one that is manufactured by the manufacturing method described above.
  • a method for manufacturing a connector according to the invention is a method for manufacturing a connector obtained by connecting a plurality of terminals arranged in parallel to one another by an anisotropic conductive film having electrically conductive particles arranged therein, in which the anisotropic conductive film is manufactured by steps of: providing an electrically conductive support plate to support a base film having an adhesive layer formed on a surface; providing an array plate that is disposed to face the adhesive layer of the base film supported by the support plate and has a plurality of through holes arranged in a pattern corresponding to an array pattern of electrically conductive particles formed thereon; providing a spray that is disposed above the array plate and sprays electrically conductive particles together with a liquid while applying a voltage to the electrically conductive particles; spraying the electrically conductive particles charged with an electrical charge together with a liquid from the spray while applying a voltage between the spray and the support plate to support the base film in a state in which the adhesive layer is turned upward; and arranging the electrically conductive particles which passed through
  • the invention it is possible to equally disperse and dispose the electrically conductive particles on the adhesive layer since the electrically conductive particles are arranged in a desired pattern in advance, and this makes it possible to provide an electrically conductive adhesive film which can capture the electrically conductive particles in the microminiaturized connecting terminal as well as prevent a short circuit between terminals even though microminiaturization of the connecting terminal and the narrowing of the interval between connecting terminals advance and thus can meet the requirement of high density mounting.
  • FIG. 1 is a cross-sectional view illustrating an anisotropic conductive film to which the invention is applied.
  • FIG. 2 is a cross-sectional view illustrating electrically conductive particles used in the invention.
  • FIG. 3 is cross-sectional view illustrating a step of arranging the electrically conductive particles in the manufacturing process of an anisotropic conductive film.
  • FIGS. 4(A) to 4(C) are cross-sectional views illustrating a step of laminating after the electrically conductive particles are arranged.
  • FIG. 5 is a perspective view illustrating a state in which an anisotropic conductive film is pasted to a rigid substrate having a plurality of connecting terminals arranged in parallel.
  • FIG. 6 is a cross-sectional view illustrating a manufacturing process using a roll-shaped support plate.
  • FIGS. 7(A) and 7(B) are cross-sectional views illustrating the manufacturing process of a connector using an anisotropic conductive film of prior art, in which FIG. 7(A) illustrates the state before pressure joining, and FIG. 7(B) illustrates the state after pressure joining.
  • FIGS. 8(A) and 8(B) are views illustrating a technique to separate the interval between the electrically conductive particles by biaxial stretching, in which FIG. 8(A) illustrates the state of the electrically conductive particles before being stretched, and FIG. 8(B) illustrates the state that the aggregate of particles remains after stretching.
  • the electrically conductive adhesive film to which the invention is applied is suitably used as an anisotropic conductive film 1 for achieving conduction between connecting terminals as electrically conductive particles are equally dispersed and disposed on a binder resin to be an adhesive in a predetermined pattern and the electrically conductive particles are sandwiched between the connecting terminals facing each other.
  • the connector using an electrically conductive adhesive film to which the invention is applied is, for example, a connector in which an IC or a flexible substrate is COG, FOB, or FOF connected using the anisotropic conductive film 1 and another connector, and the connector can be suitably used in any devices such as television, or PC, mobile phones, game machines, audio devices, and tablet terminators, or vehicle-mounted monitors.
  • the anisotropic conductive film 1 is a thermosetting adhesive or a photocurable adhesive such as an ultraviolet curable adhesive, is fluidized by being heated and pressurized by a pressure tool (not illustrated) so that the electrically conductive particles are pressed and deformed between the connecting terminals facing to each other, and is cured by being heated or irradiated with ultraviolet rays in a state in which the electrically conductive particles are pressed and deformed.
  • a pressure tool not illustrated
  • the anisotropic conductive film 1 electrically and mechanically connects an IC or a flexible substrate to a connecting target such as a glass substrate.
  • the anisotropic conductive film 1 is one, for example, as illustrated in FIG. 1 , in which electrically conductive particles 3 are disposed on an ordinary binder resin 2 (adhesive) containing a film-forming resin, a thermosetting resin, a latent curing agent, a silane coupling agent, and the like in a predetermined pattern and this thermosetting adhesive composition is supported by first and second base films 4 and 5 of an upper and lower pair.
  • binder resin 2 adheresive
  • the first and second base films 4 and 5 are formed, for example, by coating a release agent such as silicone on PET (Poly Ethylene Terephthalate), OPP (Oriented Polypropylene), PMP (Poly-4-methylpentene-1), PTFE (Polytetrafluoroethylene), and the like.
  • a release agent such as silicone on PET (Poly Ethylene Terephthalate), OPP (Oriented Polypropylene), PMP (Poly-4-methylpentene-1), PTFE (Polytetrafluoroethylene), and the like.
  • the film forming resin contained in the binder resin 2 a resin having an average molecular weight of about from 10000 to 80000 is preferable.
  • the film forming resin may include various kinds of resins such as an epoxy resin, a modified epoxy resin, a urethane resin, and a phenoxy resin. Among them, a phenoxy resin is even more preferable from the viewpoint of the film formed state, connection reliability, and the like.
  • thermosetting resin is not particularly limited, and examples thereof may include an epoxy resin and an acrylic resin that are commercially available.
  • the epoxy resin is not particularly limited, and examples thereof may include a naphthalene type epoxy resin, a biphenyl type epoxy resin, a phenol novolak type epoxy resin, a bisphenol type epoxy resin, a stilbene type epoxy resin, a triphenol methane type epoxy resin, a phenol aralkyl type epoxy resin, a naphthol type epoxy resin, a dicyclopentadiene type epoxy resin, and a triphenylmethane type epoxy resin. These may be a single substance or a combination of two or more kinds thereof.
  • the acrylic resin is not particularly limited, and an acrylic compound, a liquid acrylate, and the like can be appropriately selected depending on the purpose. Examples thereof may include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, epoxy acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylol propane triacrylate, dimethylol tricyclodecane diacrylate, tetramethylene glycol tetraacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis[4-(acryloxymethoxy)phenyl]propane, 2,2-bis[4-(acryloxyethoxy)phenyl]propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tris(acryloxyethyl)isocyanurate, urethane acrylate, and epoxy acrylate. In addition, it is also possible to use those in which acrylate is converted to me
  • the latent curing agent is not particularly limited, and examples thereof may include various kinds of curing agents of a heat curing type, a UV curing type, and the like.
  • the latent curing agent does not react under a normal condition, but it is activated by various kinds of triggers which are selected depending on the application, such as heat, light, and pressurization and starts to react.
  • the method for activating a thermally activated latent curing agent there are a method in which active species (a cation or an anion, and a radical) are produced through the dissociation reaction caused by heating, and the like, a method in which the latent curing agent is stably dispersed in an epoxy resin at around room temperature, but at a higher temperature, it is compatible with and dissolves in the epoxy resin to start the curing reaction, a method in which a molecular sieve encapsulation type curing agent is eluted at a high temperature to start the curing reaction, a method of elution and curing by a microcapsule, and the like.
  • active species a cation or an anion, and a radical
  • thermally activated latent curing agent may include imidazole-based one, hydrazide-based one, a boron trifluoride-amine complex, a sulfonium salt, an amine imide, a polyamine salt, dicyandiamide, and any modified product thereof, and these may be a single substance or a mixture of two or more kinds thereof.
  • the microcapsule type imidazole-based latent curing agent is preferable.
  • the silane coupling agent is not particularly limited, and examples thereof may include epoxy-based one, amino-based one, mercapto and sulfide-based one, and ureido-based one.
  • the adhesive property at the interface between an organic material and an inorganic material is improved by adding a silane coupling agent.
  • Examples of the electrically conductive particles 3 may include particles of various kinds of metals such as nickel, iron, copper, aluminum, tin, lead, chromium, cobalt, silver, and gold, or particles of a metal alloy, a metal oxide, those obtained by coating a metal on the surface of particles of carbon, graphite, glass, a ceramic, a plastic, or the like.
  • examples of the resin particles may include particles of an epoxy resin, a phenolic resin, an acrylic resin, an acrylonitrile-styrene (AS) resin, a benzoguanamine resin, a divinylbenzene-based resin, and a styrene-based resin.
  • an insulating film 3 a is formed as the surface of the electrically conductive particles 3 is covered with an insulating material. This makes it possible for the electrically conductive particles 3 to charge the insulating film 3 a with an electrical charge.
  • Examples of the insulating material constituting the insulating film 3 a may include various polymers such as an acrylic polymer, a urethane-based polymer, an epoxy-based polymer, an imide-based polymer, and an amide-based polymer.
  • examples of the method for forming the insulating film may include a “hybridization treatment”.
  • the hybridization treatment is to composite fine particles with fine particles and is one in which the fixation and film forming treatment of particles are conducted by applying mechanical heat energy mainly composed of an impact force to the particles while dispersing the mother particles and the child particles in the gas phase.
  • the insulating film 3 a is formed to have a film thickness of from 0.1 to 50% of the particle size of the electrically conductive particles 3 .
  • the electrically conductive particles 3 are required to be arranged on the binder resin 2 in a state of being charged, and thus it is concerned that the electrostatic property of the insulating film 3 a is lost before the electrically conductive particles 3 are attached to the binder resin 2 when the thickness of the insulating film 3 a that is charged with an electrical charge is thin and it is not possible to arrange the electrically conductive particles 3 in a predetermined pattern.
  • the conduction resistance between the connecting terminals increases when the insulating film 3 a of the electrically conductive particles 3 is too thick.
  • the film thickness of the insulating film 3 a can be decided based on the dielectric constant of the material constituting the insulating film 3 a .
  • the film thickness can be set to approximately from 0.004 to 2.0 ⁇ m.
  • the electrically conductive particles 3 are regularly arranged in a predetermined array pattern and thus the occurrence of coarseness and fineness due to aggregation of the electrically conductive particles is prevented.
  • the anisotropic conductive film 1 it is possible to prevent a short circuit between terminals by aggregates of the electrically conductive particles even though the narrowing of the interval between connecting terminals advances, it is also possible to capture the electrically conductive particles even in a microminiaturized connecting terminal and thus to meet the requirement of high density mounting.
  • the shape of the anisotropic conductive film 1 is not particularly limited, and for example, it may have a long tape shape capable of being wound around a take-up reel 6 as illustrated in FIG. 1 so that it may be cut by a predetermined length for use.
  • the anisotropic conductive film 1 has been described by taking an adhesive film obtained by molding a thermosetting resin composition containing the electrically conductive particles 3 in the binder resin 2 in a film shape as an example, but the adhesive according to the invention is not limited thereto, and for example, it may have a configuration in which an insulating adhesive layer composed of only the binder resin 2 and an electrically conductive particle-containing layer composed of the binder resin 2 containing the electrically conductive particles 3 are laminated.
  • the manufacturing process of the anisotropic conductive film 1 includes a step of arranging the electrically conductive particles 3 on the binder resin 2 formed on one surface of the first base film 4 in a predetermined pattern.
  • the electrically conductive particles 3 arranged on the binder resin 2 are pushed into the binder resin 2 as the second base film 5 is laminated on the surface on which the electrically conductive particles 3 are arranged of the binder resin 2 .
  • an electrically conductive support plate 10 to support the first base film 4 of which one surface is provided with the binder resin 2
  • an array plate 11 which is disposed to face the binder resin 2 of the first base film 4 supported by the support plate 10 and on which a plurality of through holes 12 arranged in a pattern corresponding to the array pattern of the electrically conductive particles 3 are formed
  • a spray 13 which is disposed above the array plate 11 and sprays the charged electrically conductive particles 3 together with a liquid while applying a voltage to the electrically conductive particles 3 are used.
  • the support plate 10 is one that allows the charged electrically conductive particles 3 to adsorb to the binder resin 2 that is provided to the first base film 4 as a voltage is applied between the support plate 10 and the spray 13 , and the support plate 10 is formed of a nickel plate, for example.
  • the material of the support plate 10 is not limited as long as it exhibits conductivity.
  • the array plate 11 is one that arranges the electrically conductive particles 3 which have passed through the through holes 12 on the surface of the binder resin 2 in the array pattern of the through holes 12 as the array plate 11 is disposed close onto the binder resin 2 .
  • a plurality of through holes 12 are formed in accordance with a predetermined array pattern of the electrically conductive particles 3 .
  • the array plate 11 has a plurality of through holes formed in a lattice shape at equal intervals.
  • the electrically conductive particles that have passed through the through holes 12 are equally disposed on the surface of the binder resin 2 in a lattice pattern.
  • the through holes 12 can be formed using a known processing technology such as laser processing.
  • the opening size of the through holes 12 is 100% or more of the average particle size of the electrically conductive particles 3 and preferably from 120 to 200% of the average particle size of the electrically conductive particles 3 . It is difficult for the electrically conductive particles 3 to pass through the through holes 12 when the opening size of the through holes 12 is less than 100% of the average particle size of the electrically conductive particles 3 . In addition, when the opening size of the through holes 12 is 200% or more of the average particle size of the electrically conductive particles 3 , it is concerned that a plurality of electrically conductive particles 3 pass through one through hole 12 , it is not possible to equally disperse and dispose the electrically conductive particles, and also it is concerned that the aggregation of particles is caused.
  • the charging of the array plate 11 is prevented so that the passing of the charged electrically conductive particles 3 via the through holes 12 will not be impeded by attraction or repulsion.
  • the array plate 11 is prevented from being charged as it is grounded as well as formed using an electrically conductive material such as nickel.
  • the array plate 11 may be prevented from being charged as it is formed using a hardly charged material.
  • the spray 13 is provided above the array plate 11 and sprays the electrically conductive particles 3 dispersed in a liquid such as water together with the liquid via the array plate 11 toward the binder resin 2 of the first base film 4 that is supported by the support plate 10 . At this time, the spray 13 applies an electrical charge to have a polarity opposite to the voltage applied to the support plate 10 to the electrically conductive particles 3 .
  • the spray 13 can charge the electrically conductive particles 3 , for example, by conducting corona discharge at the nozzle tip.
  • the electrically conductive particles 3 which are charged with an electrical charge are sprayed together with the liquid from the spray 13 while applying a voltage between the spray 13 and the support plate 10 to support the first base film 4 in a state in which the binder resin 2 is turned upward.
  • the ejected electrically conductive particles 3 pass through the through holes 12 of the array plate 11 as well as are uniformly dispersed by the static electricity, and are attached onto the surface of the binder resin 2 on the first base film 4 supported by the support plate 10 to which the opposite polarity is applied in a pattern corresponding to the array pattern of the through holes 12 ( FIG. 4(A) ). Incidentally, the moisture attached to the electrically conductive particles 3 is thrown off from the surface of the electrically conductive particles 3 during a fall.
  • the electrically conductive particles 3 are attached onto the surface of the binder resin 2 by being attracted to the support plate 10 to which the opposite polarity is applied, and thus the electrically conductive particles 3 are required to be charged with an electrical charge at least until being attached onto the surface of the binder resin 2 .
  • the insulating film 3 a to be charged with an electrical charge is formed so as to have a film thickness of 0.1% or more of the particle size of the electrically conductive particles 3 , the electrically conductive particles 3 do not lose the electrostatic property before being attached to the binder resin 2 and are securely and equally dispersed and disposed in accordance with the pattern of the through holes 12 of the array plate 11 .
  • the conduction resistance between the connecting terminals increases when the insulating film 3 a of the electrically conductive particles 3 is too thick.
  • the respective electrically conductive particles 3 are charged with an electrical charge having the same polarity and thus repel one another. This makes it possible to prevent a plurality of electrically conductive particles 3 from passing through one through hole 12 , and the electrically conductive particles 3 are arranged on the surface of the binder resin 2 in a single layer in accordance with the pattern of the through holes 12 .
  • the second base film 5 is laminated on the binder resin 2 on which the electrically conductive particles 3 are arranged ( FIG. 4(B) ).
  • the second base film 5 pushes the electrically conductive particles 3 into the binder resin 2 so as to achieve the positioning of the electrically conductive particles 3 .
  • the electrically conductive particles 3 are held in the binder resin 2 that is coated on the first and second base films 4 and 5 as the release treated surface of the second base film 5 is bonded to the surface on which the electrically conductive particles 3 are transferred of the binder resin 2 .
  • the anisotropic conductive film 1 is formed in which the binder resin 2 containing the electrically conductive particles 3 is supported by the first base films 4 and 5 of an upper and lower pair.
  • the electrically conductive particles 3 are pushed into the binder resin 2 as the anisotropic conductive film 1 is appropriately pressed by a laminating roll 21 . Subsequently, the surface on which the electrically conductive particles 3 are pushed of the binder resin 2 is cured by being irradiated with ultraviolet rays from the first base film 4 side, and the like, and thus the anisotropic conductive film 1 is fixed in the pattern arranged with the electrically conductive particles 3 .
  • the anisotropic conductive film 1 can be suitably used in a connector in which an IC or a flexible substrate is COG, FOB, or FOF connected and any devices such as television, or PC, mobile phones, game machines, audio devices, and tablet terminators, or vehicle-mounted monitors.
  • a rigid substrate 22 that is connected to an IC or a flexible substrate via the anisotropic conductive film 1 is formed of a plurality of connecting terminals 23 arranged in parallel. These connecting terminals 23 are microminiaturized to meet the requirement of high density mounting and the interval between the connecting terminals is narrowed.
  • the anisotropic conductive film 1 is cut such that the size in the width direction corresponds to the size of the connecting terminal 23 , the first base film 4 is then peeled off therefrom, and the anisotropic conductive film 1 thus cut is pasted on the plurality of connecting terminals 23 by taking the parallel direction of the connecting terminals 23 as the longitudinal direction.
  • the connecting terminal of the IC or flexible substrate side is mounted on the connecting terminal 23 via the anisotropic conductive film 1 , and the resultant is heated and pressurized by a pressure tool (not illustrated) from the top of it.
  • the binder resin 2 is softened, the electrically conductive particles 3 are pressed and deformed between the connecting terminals facing each other, and the anisotropic conductive film 1 is cured in a state in which the electrically conductive particles 3 are pressed and deformed by being heated or irradiated with ultraviolet rays.
  • the anisotropic conductive film 1 electrically and mechanically connects an IC or a flexible substrate to a connecting target such as a glass substrate.
  • the electrically conductive particles 3 are equally arranged in a lattice shape throughout the longitudinal direction. Hence, it is possible to improve the conduction properties as the anisotropic conductive film 1 is securely captured on the microminiaturized connecting terminals 23 , and also it is possible to prevent a short circuit between adjacent terminals as the electrically conductive particles 3 are not linked to one another in the narrowed intervals between connecting terminals.
  • the electrically conductive particles 3 ejected from the spray 13 pass through the through holes 12 of the array plate 11 as well as are uniformly dispersed by the static electricity, and are attached onto the surface of the binder resin 2 on the first base film 4 in a pattern corresponding to the array pattern of the through holes 12 ( FIG. 4(A) ).
  • aggregates in which a plurality of electrically conductive particles 3 are linked to one another is within 15%, preferably within 8%, more preferably 5% of the total number of electrically conductive particles.
  • the size of the aggregate is set to be preferably 8 times or less and more preferably 5 times or less the average particle size of the electrically conductive particles at most.
  • the size of the aggregate mentioned here also includes the maximum length of the aggregate in which the electrically conductive particles 3 are linked to one another.
  • a fine abrasion which is believed to be generated by friction with the through holes 12 is generated on the electrically conductive particles 3 in some cases.
  • This abrasion is generated at approximately from 3 to 20% of the surface area of the electrically conductive particles 3 .
  • the conduction performance is not affected when the abraded electrically conductive particles 3 are within 30% of the total number of the electrically conductive particles, but it is preferable that the abraded electrically conductive particles 3 are within 15% of the total number of the electrically conductive particles.
  • the support plate to support the first base film may be formed in a roll shape as illustrated in FIG. 6 in addition to a plate shape.
  • the roll-shaped support plate 30 conveys the first base film 4 by being rotated.
  • the array plate 11 is disposed on the upper part of the first base film 4 supported by the roll-shaped support plate 30 .
  • a voltage is applied between the roll-shaped support plate 30 and the spray 13 facing the array plate 11 such that the roll-shaped support plate 30 is charged in a polarity opposite to the electrical charge of the electrically conductive particles that are ejected from the spray 13 .
  • the electrically conductive particles 3 ejected from the spray 13 pass through the through holes 12 of the array plate 11 and are attached onto the surface of the binder resin 2 provided on the base film 4 in a predetermined pattern when the first base film 4 moves on the upper part of the roll-shaped support plate 30 .
  • This makes it possible to continuously arrange the electrically conductive particles 3 on the binder resin 2 of the first base film 4 that is conveyed by the roll-shaped support plate 30 , and thus it is possible to improve the manufacturing efficiency.
  • the first base film 4 in which the electrically conductive particles 3 are arranged on the surface of the binder is continuously subjected to the roll lamination of the second base film 5 and the light curing of the adhesive layer on the downstream side in the conveying direction in the same manner, and thus it is possible to continuously form the anisotropic conductive film 1 by a series of steps.
  • a phenoxy resin (YP-50, manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.);
  • a cationic curing agent (SI-60L, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.)
  • a mixed solution was prepared by adjusting the solid content of these resin compositions to be 50% with toluene, the mixed solution was coated on a PET film having a thickness of 50 ⁇ m, and the coated PET film was dried in an oven at 80° C. for 5 minutes, thereby obtaining an anisotropic conductive film containing a binder resin having a thickness of 20 ⁇ m.
  • AUL704 (resin core Au plating particles, average particle size: 4 ⁇ m, manufactured by SEKISUI CHEMICAL CO., LTD.) was used as the electrically conductive particles.
  • a glass substrate (trade name: 1737F, manufactured by Corning Incorporated, size: 50 mm ⁇ 30 mm, thickness: 0.5 mm) on which an aluminum wiring pattern corresponding to the pattern of the IC chip was formed was used as the glass substrate.
  • the connector sample to be used for the measurement of conduction resistance ( ⁇ ) was manufactured as follows.
  • the anisotropic conductive films according to Examples and Comparative Examples were disposed on this glass substrate, the IC chip (dimensions: 1.8 mm ⁇ 20.0 mm, thickness: 0.5 mm, gold bump size: 30 ⁇ m ⁇ 85 ⁇ m, bump height: 15 ⁇ m, pitch: 50 ⁇ m) was disposed on the anisotropic conductive film, and the resultant was heated and pressurized, thereby connecting the IC chip and the aluminum wiring patterned glass substrate to each other.
  • the condition for pressure joining was 180° C., 80 MPa, and 5 seconds.
  • the connector sample to be used for the measurement of proportion (ppm) of short circuit between terminals was manufactured as follows.
  • the anisotropic conductive films according to Examples and Comparative Examples were disposed on this glass substrate, the IC chip (size: 1.5 mm ⁇ 13.0 mm, thickness: 0.5 mm, gold bump size: 25 ⁇ m ⁇ 140 ⁇ m, bump height: 15 ⁇ m, pitch: 7.5 ⁇ m) was disposed on the anisotropic conductive film, and the resultant was heated and pressurized, thereby connecting the IC chip and the aluminum wiring patterned glass substrate to each other.
  • the condition for pressure joining was 180° C., 80 MPa, and 5 seconds.
  • the electrically conductive particles were arranged on the binder resin formed on one surface of a PET film in a predetermined pattern and then pushed into the binder resin by laminating a release-treated PET film on the surface on which the electrically conductive particles were arranged of the binder resin, thereby manufacturing the anisotropic conductive film.
  • an electrically conductive support plate to support a PET film provided with a binder resin
  • an array plate which was disposed to face the binder resin of the PET film supported by the support plate and on which a plurality of through holes arranged in a pattern corresponding to the array pattern of the electrically conductive particles were formed
  • a spray which was disposed above the array plate and sprayed the charged electrically conductive particles together with a liquid while applying a voltage to the electrically conductive particles were used (see FIG. 3 ).
  • the electrically conductive particles which were charged with an electrical charge were sprayed together with water from the spray while applying a voltage between the spray and the support plate.
  • the ejected electrically conductive particles passed through the through holes of the array plate as well as were uniformly dispersed by the static electricity, and were attached onto the surface of the binder resin on the PET film supported by the support plate to which the opposite polarity was applied in a pattern corresponding to the array pattern of the through holes.
  • the electrically conductive particles 3 were pushed into the binder resin by laminating a release-treated PET film on the surface of the binder resin using a laminating roll, thereby obtaining the anisotropic conductive film.
  • This anisotropic conductive film was pasted on a plurality of connecting terminals by taking the parallel direction of the connecting terminals of an aluminum wiring pattern formed on a glass substrate as the longitudinal direction.
  • Example 1 the insulating film (polymethyl methacrylate) was formed on the surface of the electrically conductive particles in a thickness of 0.1% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • Example 2 the conditions were the same as those in Example 1 except that the thickness of the insulating film formed on the surface of the electrically conductive particles was 10% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • Example 3 the conditions were the same as those in Example 1 except that the thickness of the insulating film formed on the surface of the electrically conductive particles was 50% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • an anisotropic conductive film was obtained by a manufacturing method of prior art.
  • an anisotropic conductive film molded in a film shape was obtained by coating a resin composition prepared by dispersing electrically conductive particles (AUL704) in the binder resin described above on a PET film and drying it.
  • the electrically conductive particles are randomly disposed in the binder resin.
  • the thickness of the insulating film formed on the surface of the electrically conductive particles was 10% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • This anisotropic conductive film was pasted on a plurality of connecting terminals by taking the parallel direction of the connecting terminals of an aluminum wiring pattern formed on a glass substrate as the longitudinal direction.
  • a pressure sensitive adhesive layer was formed by coating an acrylic polymer on a 100 ⁇ m of unstretched copolymerized polypropylene film and drying it.
  • the electrically conductive particles (AUL704) were filled all over this pressure sensitive adhesive material layer, and the electrically conductive particles that did not reach the pressure sensitive adhesive were removed by air blowing, thereby forming a single-layer electrically conductive particle layer having a filling rate of 60%.
  • this polypropylene film on which the electrically conductive particles were fixed was stretched to 2.0 times at 135° C. and at a ratio of 10%/sec in both vertical and horizontal directions using a biaxial stretching apparatus for test and was gradually cooled up to room temperature, thereby obtaining an array sheet.
  • a PET film coated with a binder resin was superimposed on the electrically conductive particle side of this array sheet and laminated under the condition of 60° C. and 0.3 MPa to embed the electrically conductive particles into the binder resin, and the polypropylene film and the pressure sensitive adhesive were peeled off therefrom. Thereafter, a second PET film was bonded on the PET film in the same manner as in Example 1, thereby obtaining an anisotropic conductive film.
  • This anisotropic conductive film was pasted on a plurality of connecting terminals by taking the parallel direction of the connecting terminals of an aluminum wiring pattern formed on a glass substrate as the longitudinal direction.
  • the thickness of the insulating film formed on the surface of the electrically conductive particles was 10% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • Comparative Example 3 the conditions were the same as those in Example 1 except that the thickness of the insulating film formed on the surface of the electrically conductive particles was 0.05% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • Comparative Example 4 the conditions were the same as those in Example 1 except that the thickness of the insulating film formed on the surface of the electrically conductive particles was 80% of the average particle size (4 ⁇ m) of the electrically conductive particles.
  • the conduction resistance between the IC chip and the connecting terminal formed on the glass substrate was as low as 0.5 ⁇ or less and the proportion of short circuit between the terminals was also 1 ppm or less.
  • Comparative Example 1 although the conduction resistance was as low as 0.2 ⁇ , the proportion of short circuit between the terminals was as frequent as 3000 ppm. In the same manner, in Comparative Example 2, although the conduction resistance was as low as 0.2 ⁇ , the proportion of short circuit between the terminals was as frequent as 3000 ppm, and in Comparative Example 3 as well, although the conduction resistance was as low as 0.2 ⁇ , the proportion of short circuit between the terminals was as frequent as 130 ppm. In addition, in Comparative Example 4, although the proportion of short circuit between the terminals was as rare as 1 ppm or less, the conduction resistance was as high as 2.0 ⁇ .
  • Comparative Example 1 the electrically conductive particles were randomly dispersed in the binder resin, and thus the locations at which the electrically conductive particles were concentrated and the locations at which the electrically conductive particles were dispersed were generated in the binder resin, the electrically conductive particles were linked to one another between the adjacent terminals having a narrowed interval, and thus a short circuit between terminals occurred as frequently as 3000 ppm.
  • Comparative Example 2 not all of the electrically conductive particles were separated from one another by the method to separate the electrically conductive particles from one another by biaxial stretching, the aggregate of particles in which a plurality of electrically conductive particles were linked to one another remained, and the short circuit between the adjacent terminals having a narrowed interval occurred as frequently as 300 ppm, and thus it was not possible to completely prevent the short circuit.
  • the film thickness of the insulating film formed on the surface of the electrically conductive particles was less than 0.1% of the average particle size of the electrically conductive particles, thus the electrically conductive particles lost the electrostatic property after being ejected from the spray but before being attached onto the surface of the binder resin, and because of this, the electrically conductive particles were randomly scattered, and also the electrically conductive particles were not equally dispersed and disposed as a plurality of electrically conductive particles passed through one through hole.
  • the film thickness of the insulating film formed on the surface of the electrically conductive particles was thick to be 80% of the average particle size of the electrically conductive particles, and the thick insulating film inhibited the conduction properties when the anisotropic conductive film was sandwiched between the connecting terminals.
  • the electrostatic property was favorable and the proportion of short circuit between the adjacent terminals was 1 ppm to be favorable, but the conduction resistance was as high as 2.0 ⁇ .
  • the thickness of the insulating film formed on the surface of the electrically conductive particles is 0.1% or more and 50% or less of the particle size of the electrically conductive particles.

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KR20160039181A (ko) 2016-04-08
US20190214781A1 (en) 2019-07-11
CN105358641A (zh) 2016-02-24
KR20180054935A (ko) 2018-05-24
CN109722174B (zh) 2022-04-29
KR101861451B1 (ko) 2018-05-29
KR101986470B1 (ko) 2019-06-05
US11139629B2 (en) 2021-10-05
HK1219969A1 (zh) 2017-04-21
WO2015016168A1 (ja) 2015-02-05
CN109722174A (zh) 2019-05-07
JP2015025103A (ja) 2015-02-05

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