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WO2018139552A1 - Insulation covered conductive particles, anisotropic conductive film, method for producing anisotropic conductive film, connection structure and method for producing connection structure - Google Patents

Insulation covered conductive particles, anisotropic conductive film, method for producing anisotropic conductive film, connection structure and method for producing connection structure Download PDF

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Publication number
WO2018139552A1
WO2018139552A1 PCT/JP2018/002350 JP2018002350W WO2018139552A1 WO 2018139552 A1 WO2018139552 A1 WO 2018139552A1 JP 2018002350 W JP2018002350 W JP 2018002350W WO 2018139552 A1 WO2018139552 A1 WO 2018139552A1
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WO
WIPO (PCT)
Prior art keywords
particles
insulating
adhesive layer
particle
conductive
Prior art date
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PCT/JP2018/002350
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French (fr)
Japanese (ja)
Inventor
敏光 森谷
伊澤　弘行
邦彦 赤井
剛幸 市村
田中　勝
Original Assignee
日立化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to KR1020197024263A priority Critical patent/KR102422589B1/en
Priority to CN202110274170.9A priority patent/CN113053562B/en
Priority to CN201880008563.1A priority patent/CN110214353B/en
Priority to JP2018564633A priority patent/JP7077963B2/en
Publication of WO2018139552A1 publication Critical patent/WO2018139552A1/en

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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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • the present invention relates to an insulating coated conductive particle, an anisotropic conductive film, a method for manufacturing an anisotropic conductive film, a connection structure, and a method for manufacturing a connection structure.
  • conductive particles are dispersed in an adhesive film.
  • An anisotropic conductive film is used.
  • COG chip-on-glass
  • connection structure in which the interval between the connection electrodes is, for example, 15 ⁇ m or less is required, and the bump electrode of the connection member has also been reduced in area.
  • the bump electrode of the connection member In order to obtain a stable electrical connection in the bump connection with a reduced area, it is necessary that a sufficient number of conductive particles be interposed between the bump electrode and the circuit electrode on the substrate side.
  • Patent Documents 1 and 2 the conductive particles are unevenly distributed on the substrate side at a constant rate, and the conductive particles are aligned at equal intervals, thereby capturing the conductive particles of the bump electrode and the circuit electrode. And improving the insulation between the narrowed adjacent circuit electrodes.
  • the present invention provides insulating coated conductive particles and different conductive materials capable of ensuring both connection reliability between opposing electrodes and insulation between adjacent electrodes in the circuit member.
  • the present invention comprises a conductive base material particle and insulating fine particles covering the surface of the base material particle, a rough region having a small or zero number of insulating fine particles per unit area, and a rough region There are provided first insulating coated conductive particles having a dense region having a larger number of insulating fine particles per unit area.
  • the first insulating coated conductive particles of the present invention can ensure conductive properties by the rough region while ensuring insulation when the particles are in contact with each other by the dense region.
  • the first insulating coated conductive particles of the present invention can have two of the rough regions passing through the central axis passing through the center of the base material particles.
  • Such insulating coated conductive particles can ensure the connection reliability between the facing electrodes by bringing the two rough regions into contact with the facing electrodes in the connection between the circuit members having the facing electrodes, When other insulating coating conductive particles are in contact with each other, insulation can be ensured by the dense region.
  • the present invention also provides two spheres of a composite particle comprising conductive base particles and insulating fine particles covering the surface of the base particles when the base particles are cut in two parallel planes.
  • a second insulating coated conductive particle obtained by removing a part or all of the insulating fine particles in the crown region.
  • the second insulating coated conductive particles of the present invention are configured to bring the two spherical crown regions from which part or all of the insulating fine particles have been removed into contact with the opposing electrodes, respectively.
  • the connection reliability between the more opposing electrodes can be ensured, and the insulation can be ensured by the insulating fine particles in the spherical zone region when coming into contact with other insulating coating conductive particles.
  • the present invention also comprises conductive base particles and insulating fine particles covering the surface of the base particles, and is insulative in a spherical zone when the base particles are cut in two parallel planes.
  • a third insulating coated conductive particle in which fine particles are unevenly distributed is provided.
  • the third insulating coated conductive particle of the present invention ensures the connection reliability between the facing electrodes by bringing the two crown areas into contact with the facing electrodes in the connection between the circuit members having the facing electrodes. Insulating properties can be ensured by the insulating fine particles that are unevenly distributed in the spherical zone when contacting with other insulating coated conductive particles.
  • the present invention also provides an anisotropic conductive film comprising a conductive adhesive layer containing the first, second or third insulating coated conductive particles of the present invention and an adhesive component.
  • both the connection reliability between the facing electrodes and the insulation between adjacent electrodes in the circuit member are compatible. can do.
  • the anisotropic conductive film of the present invention includes the first insulating coated conductive particles of the present invention having two rough regions through which the central axis passing through the center of the substrate particles passes. And an axis parallel to the thickness direction of the conductive adhesive layer may pass through the two rough regions.
  • the two rough regions of the insulating coated conductive particles can be reliably brought into contact with the opposing electrodes, respectively.
  • insulating properties can be ensured by the dense regions of each other.
  • the anisotropic conductive film of the present invention includes the second insulating coating conductive particles of the present invention, and the insulating coating conductive particles pass through the center of the base particle and are parallel to the thickness direction of the conductive adhesive layer. May be arranged to pass through the two crown areas.
  • the two spherical crown regions of the insulating coated conductive particles can be reliably brought into contact with each other by the opposing electrodes.
  • the insulating properties can be ensured by the insulating fine particles in the respective spherical zone regions.
  • the anisotropic conductive film of the present invention includes the second or third insulating coated conductive particles of the present invention, and the insulating coated conductive particles pass through the center of the base particle and in the thickness direction of the conductive adhesive layer. You may arrange
  • the two spherical crown regions of the insulating coated conductive particles can be reliably brought into contact with each other by the opposing electrodes.
  • the insulating properties can be ensured by the insulating fine particles in the respective spherical zone regions.
  • the present invention also provides a step of preparing composite particles comprising conductive base particles and insulating fine particles covering the surface of the base particles, and a particle containing member provided with a hole having a closed end face Containing the composite particles in the pores, removing a part or all of the insulating fine particles in the crown region of the composite particles exposed from the pores, and forming the crown region on the first adhesive layer.
  • the composite particles from which the insulating fine particles have been removed are transferred from the particle containing member so that the spherical region is in contact with the first adhesive layer, and a part of the insulating fine particles of the composite particles are attached to the closed end surface of the particle containing member.
  • An anisotropic conductive film comprising a step of combining To provide a production method.
  • the insulating coated conductive particles having two spherical regions from which part or all of the insulating fine particles are removed are provided on the first adhesive layer.
  • the conductive adhesive layer containing the insulating coated conductive particles can be easily formed by attaching the second adhesive layer thereto.
  • the insulating coated conductive particles can be arranged so that an axis passing through the center of the base particle and parallel to the thickness direction of the conductive adhesive layer passes through the two crown regions.
  • the insulating coated conductive particles in the anisotropic conductive film can be regularly arranged by providing regularly arranged holes in the particle containing member.
  • a layer can be formed.
  • the present invention also provides a first circuit member having a bump electrode, a second circuit member having a circuit electrode corresponding to the bump electrode, and the bump electrode and the circuit electrode electrically interposed between the bump electrode and the circuit electrode.
  • a connection structure comprising the first, second, or third insulating coated conductive particles according to the present invention that are connected to each other.
  • connection structure of the present invention since the bump electrode and the circuit electrode are connected by the first, second, or third insulating coating conductive particles according to the present invention, the connection reliability between the opposing electrodes and the circuit member It is possible to achieve both insulating properties between adjacent electrodes.
  • the present invention also relates to the anisotropic conductive film according to the present invention or the above-described present invention between the first circuit member having a bump electrode and the second circuit member having a circuit electrode corresponding to the bump electrode.
  • a connection structure manufacturing method including a step of thermocompression bonding a first circuit member and a second circuit member with an anisotropic conductive film obtained by the method for manufacturing an anisotropic conductive film interposed therebetween.
  • connection structure of the present invention it is possible to obtain a connection structure that achieves both connection reliability between opposing electrodes and insulation between adjacent electrodes in a circuit member.
  • the insulating coated conductive particles capable of ensuring both the connection reliability between the opposing electrodes and the insulation between adjacent electrodes in the circuit member.
  • anisotropic conductive film, method for manufacturing anisotropic conductive film, and connection structure capable of achieving both connection reliability between opposing electrodes and insulation between adjacent electrodes in a circuit member, and method for manufacturing connection structure Can be provided.
  • FIG. 5 is a schematic cross-sectional view showing a step subsequent to FIG. 4.
  • FIG. 10 is a schematic cross-sectional view showing a step subsequent to FIG. 9.
  • FIG. 1A is a view showing the appearance of an embodiment of the insulating coated conductive particles according to the present invention
  • FIG. 1B is a schematic cross-sectional view along the central axis P shown in FIG. FIG.
  • the insulating coated conductive particle 10 includes a conductive base particle 1 and insulating fine particles 2 that cover the surface of the base particle 1.
  • the central axis P means an axis passing through the center of the base particle 1.
  • the base particle 1 may be a core-shell type particle composed of a core particle and a metal layer covering at least a part of the surface of the core particle. For example, what coated the core particle with the metal by plating is mentioned.
  • any of metal core particles, organic core particles, and inorganic core particles can be used. From the viewpoint of conductivity, it is preferable to use organic core particles.
  • the material of the organic core particles is not particularly limited, and examples thereof include acrylic resins such as polymethyl methacrylate and polymethyl acrylate, and polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polybutadiene.
  • the metals include gold, silver, copper, platinum, zinc, iron, palladium, nickel, tin, chromium, titanium, aluminum, cobalt, germanium, cadmium and other metals, ITO And metal compounds such as solder.
  • the structure of the metal layer covering the organic core particles is not particularly limited, but the outermost layer is preferably a nickel layer in terms of conductivity. Moreover, it is preferable that an outermost layer has a permite
  • the average primary particle diameter of the base particle 1 is preferably 1 ⁇ m or more and 10 ⁇ m or less, from the viewpoint of being able to absorb variations in the height of the electrode to be connected, and compatibility between conduction reliability and insulation reliability. It is more preferably 5 ⁇ m or less, and further preferably 2 ⁇ m or more and 3 ⁇ m or less.
  • the insulating fine particles 2 can be inorganic oxide fine particles, organic fine particles, and the like, and can be appropriately selected according to desired characteristics such as insulation and conductivity.
  • the insulating fine particles 2 are preferably core-shell type particles composed of core fine particles containing an organic polymer and a shell layer covering at least a part of the surface of the core fine particles. Examples of the material of the shell layer include cross-linked polysiloxane.
  • the average primary particle diameter of the insulating fine particles 2 is preferably 100 nm or more and 500 nm or less, more preferably 200 nm or more and 450 nm or less, and more preferably 250 nm or more and 350 nm or less, from the viewpoint of compatibility between conduction reliability and insulation reliability. More preferably. In particular, if the average primary particle diameter of the insulating fine particles 2 is 250 nm or more, even when the insulating coated conductive particles 10 are aggregated in the connection between the circuit members having the opposing electrodes, the adjacent circuit electrodes are adjacent to each other.
  • the insulating coated conductive particles 10 of the present embodiment may have a rough region where the number of insulating fine particles per unit area is small or zero and a dense region where the number of insulating fine particles per unit area is larger than that of the rough region. it can.
  • the insulating coated conductive particles 10 preferably have two rough regions through which the central axis P passing through the center of the base particle 1 passes.
  • the insulating coated conductive particles 10 preferably have a rough region in two spherical regions when the base particle 1 is cut by two parallel planes, and a dense region in the spherical region.
  • Such insulating coated conductive particles 10 are composed of composite particles comprising conductive base particles 1 and insulating fine particles 2 covering the surface of the base particles 1. It can be obtained by removing part or all of the insulating fine particles 2 in the two spherical crown regions when cut in a plane.
  • the boundary between the coarse region and the dense region is not necessarily clear, and the number of insulating fine particles per unit area is larger than that in the coarse region between the coarse region and the dense region. Fewer intermediate regions may be provided, and each region may be provided so that the number of insulating fine particles per unit area increases from the coarse region to the dense region.
  • Insulated coating conductive particles 10 from the viewpoint of low resistance when connecting between opposing circuits, have a coarse area particle density of the insulating fine particles 2 is at 0 / [mu] m 2 ⁇ 2.0 units / [mu] m 2 It is more preferable to have a rough region of 0 / ⁇ m 2 to 1.0 / ⁇ m 2 , and it is even more preferable to have a rough region of 0 / ⁇ m 2 to 0.5 / ⁇ m 2 .
  • the surface area of the base particle 1 is S 0 ⁇ m 2
  • the rough region is preferably 0.5 ⁇ S 0 ⁇ m 2 or more, and preferably 0.7 ⁇ S 0 ⁇ m 2 or more. More preferred.
  • Insulated coating conductive particles 10 preferably has a dense region in terms of insulation improvement, particle density of the insulating fine particles 2 is 2.0 pieces / [mu] m 2 ⁇ 5.0 units / [mu] m 2 between adjacent circuit It is more preferable to have a dense region of 2.5 / ⁇ m 2 to 4.5 / ⁇ m 2 , and to have a dense region of 3.0 / ⁇ m 2 to 3.5 / ⁇ m 2. Further preferred. Further, when the surface area of the base particle is S 0 ⁇ m 2 , the dense region is preferably 0.2 ⁇ S 0 ⁇ m 2 or more, and more preferably 0.3 ⁇ S 0 ⁇ m 2 or more. preferable.
  • the number of insulating fine particles per unit area in the rough region and the dense region is the center part of the base particle 1 in the SEM photograph of the insulating coated conductive particle (the length is half the diameter of the outer circumference of the base particle 1, It is measured by measuring the number of insulating particles existing in a circle concentric with the outer circumference circle).
  • the particle density of the insulating fine particles 2 can be calculated from the number of insulating fine particles per unit area.
  • the unit area can be set to a predetermined area of 0.04 ⁇ S 0 mm 2 to 0.20 ⁇ S 0 mm 2 when the surface area of the base particle 1 is S 0 mm 2 , 0.17 ⁇ may be set to S 0 mm 2.
  • the insulating coated conductive particles 10 have a region where the number of insulating fine particles is 0 in the spherical region of the base particle 1. 0.05 ⁇ S 0 ⁇ m 2 or more is preferable, and 0.10 ⁇ S 0 ⁇ m 2 or more is more preferable.
  • the coverage of the insulating fine particles 2 in the insulating coated conductive particles 10 is preferably 35 to 75%, more preferably 40 to 75%.
  • the coverage of the edge fine particles is the center part of the base particle 1 in the SEM photograph of the insulating coated conductive particles (the half length of the diameter of the outer peripheral circle of the base particle 1 is the diameter, and concentric with the outer peripheral circle. The value measured by analyzing the circle.
  • the total surface area of the center part of the base particle 1 in the SEM photograph is W (area calculated from the particle diameter of the conductive particles), and the insulating fine particles in the center part of the base particle 1 in the SEM picture
  • the coverage is expressed as P / W ⁇ 100 (%).
  • the surface area P of the portion analyzed to be covered in the present embodiment is an average value of the surface areas obtained from 200 SEM photographs of the insulating coated conductive particles.
  • the minimum diameter X ′ of the insulating coated conductive particle 10 is preferably not less than the diameter of the base particle 1 and not more than the total value of the diameter of the base particle 1 and the diameter of the insulating fine particles 2 from the viewpoint of conduction characteristics. Further, the maximum diameter Y ′ of the insulating coated conductive particles 10 is not less than the total value of the diameter of the base particle 1 and 2 ⁇ (the diameter of the insulating fine particles 2), from the viewpoint of insulation, It is preferable that it is below the total value of x (diameter of insulating fine particles 2).
  • the minimum diameter X ′ of the insulating coated conductive particle 10 shown in FIG. 1B is the diameter of the base particle 1
  • the maximum diameter Y ′ is the diameter of the base particle 1 and 2 ⁇ (2 ⁇ ( The case of the sum of the diameters of the insulating fine particles is shown.
  • the ratio X ′ / Y ′ between the minimum diameter X ′ and the maximum diameter Y ′ of the insulating coated conductive particles 10 is preferably 0.4 or more and 0.9 or less. .
  • X ′ / Y ′ By setting X ′ / Y ′ to 0.4 or more, even when the bump area of the circuit member is reduced, it becomes easy to ensure the trapping property of the insulating coated conductive particles 10, and X ′ / Y ′.
  • the connection resistance can be easily reduced.
  • Each method can be used to produce the insulating coated conductive particles 10 as described above.
  • base particles Examples include a method of preparing composite particles in which the entire surface of 1 is coated with insulating fine particles 2 and removing a part of the insulating fine particles 2 of the composite particles.
  • the base particles 1 and the insulating fine particles 2 are filled between parallel plates, and then insulative using an organic solvent or heat.
  • fine-particles 2 to the base particle 1 is mentioned.
  • a charging treatment material such as polyethyleneimine is applied to the base particle 1 and electrostatic force is applied.
  • a method of attaching the insulating fine particles 2 and a method of obtaining composite particles by chemical bonding by introducing functional groups capable of mutual bonding to the base particle 1 and the insulating fine particles 2.
  • a method of removing a part of the insulating fine particles 2 a method of removing the insulating fine particles 2 in the spherical crown region of the composite particles using an adhesive tape or the like can be mentioned as a simple method.
  • the method for producing an anisotropic conductive film according to the present invention which will be described later, is a particularly useful method because the insulating coated conductive particles 10 can be produced during the production of the anisotropic conductive film.
  • FIG. 3A is a schematic cross-sectional view showing an embodiment of the anisotropic conductive film according to the present invention
  • FIG. 3B is an enlarged schematic view of the main part of the anisotropic conductive film.
  • the anisotropic conductive film 11 with a peeling film shown by the figure is comprised from the peeling film 12, and the conductive adhesive layer (anisotropic conductive film) 13 in which the insulation coating electrically-conductive particle 10 and an adhesive agent component are contained.
  • the insulating coating conductive particles 10 are dispersed in the conductive adhesive layer 13.
  • a region where the insulating coating conductive particles 10 are not included in a cross section when the conductive adhesive layer 13 is cut along a plane perpendicular to the thickness direction is referred to as an adhesive region, and the insulating coating conductive particles 10 are The included region may be referred to as a conductive region.
  • the release film 12 is made of, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, or the like.
  • PET polyethylene terephthalate
  • the release film 12 may contain an arbitrary filler. Further, the surface of the release film 12 may be subjected to a mold release process or a plasma process.
  • Examples of the adhesive component contained in the conductive adhesive layer 13 include a monomer and a curing agent.
  • a monomer a cationic polymerizable compound, an anion polymerizable compound, or a radical polymerizable compound can be used.
  • examples of the cationic polymerizable compound and the anionic polymerizable compound include epoxy compounds.
  • epoxy compounds include epphenol hydrins and bisphenol type epoxy resins derived from bisphenol compounds such as bisphenol A, bisphenol F or bisphenol AD, and epoxy novolacs derived from epichlorohydrin and novolac resins such as phenol novolac or cresol novolac.
  • Resin and various epoxy compounds having two or more glycidyl groups in one molecule such as glycidylamine, glycidyl ether, biphenyl, and alicyclic can be used.
  • radical polymerizable compound a compound having a functional group that is polymerized by radicals can be used, and examples thereof include acrylic monomers such as (meth) acrylate, maleimide compounds, and styrene derivatives.
  • the radical polymerizable compound can be used in any state of a monomer or an oligomer, and a monomer and an oligomer may be mixed and used.
  • Monomers may be used alone or in combination of two or more.
  • examples of the curing agent include imidazole, hydrazide, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide and the like. It is preferable that these curing agents are coated with a polyurethane-based or polyester-based polymer substance and are microencapsulated from the viewpoint of extending the pot life.
  • the curing agent used in combination with the epoxy compound is appropriately selected depending on the intended connection temperature, connection time, storage stability, and the like. From the viewpoint of high reactivity, when the curing agent is a composition containing an epoxy compound and a curing agent, the gel time is preferably within 10 seconds at a predetermined temperature, from the viewpoint of storage stability, It is preferable that there is no difference in gel time with the composition after storage in a thermostatic bath at 40 ° C. for 10 days. From such points, the curing agent is preferably a sulfonium salt.
  • examples of the curing agent include those that decompose by heating, such as peroxide compounds and azo compounds, to generate free radicals.
  • the curing agent used in combination with the acrylic monomer is appropriately selected depending on the intended connection temperature, connection time, storage stability, and the like.
  • the curing agent is preferably an organic peroxide or an azo compound having a half-life of 10 hours at a temperature of 40 ° C. or more and a half-life of 1 minute at a temperature of 180 ° C. or less.
  • An organic peroxide or an azo compound having a 10-hour temperature of 60 ° C. or more and a half-life of 1 minute is 170 ° C. or less is more preferable.
  • the conductive adhesive layer 13 may further contain a decomposition accelerator, an inhibitor, and the like.
  • the blending amount of the curing agent is such that the monomer and the film-forming material described later can be obtained from the viewpoint of obtaining a sufficient reaction rate when the connection time is 10 seconds or less, regardless of whether the epoxy compound or the acrylic monomer is used.
  • the amount is preferably 0.1 to 40 parts by mass, more preferably 1 to 35 parts by mass with respect to 100 parts by mass in total.
  • the blending amount of the curing agent is 0.1 parts by mass or more, a sufficient reaction rate can be obtained, and good adhesive strength and small connection resistance can be easily obtained. It becomes easy to prevent the fluidity of the adhesive layer 13 from decreasing and the connection resistance from increasing, and to ensure the storage stability of the anisotropic conductive film.
  • the conductive adhesive layer 13 may contain a film forming material.
  • the film-forming material is a polymer that has an effect of facilitating the handling of a low-viscosity composition containing the monomer and the curing agent. By using the film forming material, it is possible to suppress the film from being easily split, cracked, or sticky, and the anisotropic conductive film 11 that is easy to handle can be obtained.
  • thermoplastic resin can be suitably used as the film forming material.
  • examples thereof include phenoxy resin, polyvinyl formal resin, polystyrene resin, polyvinyl butyral resin, polyester resin, polyamide resin, xylene resin, polyurethane resin, polyacrylic resin, and polyester urethane resin.
  • These polymers may contain siloxane bonds or fluorine substituents.
  • a phenoxy resin is preferably used from the viewpoints of adhesive strength, compatibility, heat resistance, and mechanical strength.
  • thermoplastic resins may be used alone or in combination of two or more.
  • the thermoplastic resin can be easily formed as the molecular weight increases, and the melt viscosity that affects the fluidity of the anisotropic conductive film 11 can be set in a wide range.
  • the weight average molecular weight of the thermoplastic resin is preferably 5000 to 150,000, and more preferably 10,000 to 80,000. When the weight average molecular weight of the thermoplastic resin is 5000 or more, good film formability is easily obtained, and when it is 150,000 or less, good compatibility with other components is easily obtained.
  • the weight average molecular weight is a value measured from a gel permeation chromatograph (GPC) using a standard polystyrene calibration curve according to the following conditions.
  • GPC gel permeation chromatograph
  • Equipment GPC-8020 manufactured by Tosoh Corporation Detector: RI-8020 manufactured by Tosoh Corporation Column: Hitachi Chemical Co., Ltd.
  • Solvent Tetrahydrofuran Injection volume: 60 ⁇ L Pressure: 2.94 ⁇ 106 Pa (30 kgf / cm 2 ) Flow rate: 1.00 mL / min
  • the blending amount of the film forming material is preferably 5% by mass to 80% by mass, and more preferably 15% by mass to 70% by mass based on the total amount of the monomer, the curing agent and the film forming material.
  • the blending amount of the film forming material is 5% by mass or more, good film formability is easily obtained, and when it is 80% by mass or less, the conductive adhesive layer 13 (particularly, the adhesive region) is favorable. It tends to show fluidity.
  • the conductive adhesive layer 13 is filled with a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, an isocyanate, and the like. Furthermore, you may contain.
  • the maximum diameter of the filler is preferably less than the minimum diameter of the insulating coated conductive particles 10.
  • the filler content in the conductive adhesive layer 13 is preferably 5 to 60 parts by volume with respect to 100 parts by volume of the conductive adhesive layer. If it is this range, it will become easy to acquire the effect of the reliability improvement according to the addition amount.
  • the insulating coated conductive particles 10 are preferably unevenly distributed on one side of both main surfaces of the conductive adhesive layer 13. As shown in FIG. 3B, when the insulating coated conductive particles 10 are unevenly distributed on the one surface side where the release film 12 of the conductive adhesive layer 13 is provided, the insulating coated conductive particles 10 and the insulating coated conductive particles 10 The shortest distance to the direction may be greater than 0 ⁇ m and 1 ⁇ m or less. By setting the shortest distance D within the above range, the flow of the insulating coated conductive particles 10 at the time of pressure bonding can be suppressed, and the capturing performance of the insulating coated conductive particles 10 can be improved.
  • the insulating coated conductive particles 10 have two rough regions in which the axis P ′ passing through the center of the base particle 1 and parallel to the thickness direction of the conductive adhesive layer 13 is two rough regions or
  • the insulating fine particles 2 are arranged so as to pass through the two spherical crown regions from which part or all of the insulating fine particles 2 have been removed, or the parallel axis P ′ and the two parallel planes (the two spherical crown regions and the spherical zone). It is preferable that they are arranged so as to be orthogonal to the plane dividing the region.
  • the particle diameter X in the direction of the axis P ′ and the particle diameter Y in the direction perpendicular to the axis P ′ of the insulating coated conductive particles 10 have a relationship of Y> X.
  • the direction orthogonal to the axis P ′ can also be referred to as the longitudinal direction when the anisotropic conductive film 11 has a strip shape.
  • the particle diameter X is preferably not less than the diameter of the base particle 1 and not more than the total value of the diameter of the base particle 1 and the diameter of the insulating fine particles 2.
  • the insulating coated conductive particles 10 are formed on at least one of the two spherical crown regions when they are cut by two parallel planes having the axis P ′ as a perpendicular line. It will be in the state which has the area
  • the insulating property is provided between the base particle 1 of the insulating coated conductive particles 10 and the electrodes. The fine particles 2 are prevented from being sandwiched, and a low resistance connection is facilitated.
  • the particle diameter Y is preferably not less than the total value of the diameter of the base particle 1 and 2 ⁇ (the diameter of the insulating fine particles 2) and not more than 2 ⁇ (the diameter of the base particle 1).
  • the insulating coated conductive particle 10 is a region covered with the insulating fine particles 2 in a spherical zone when cut by two parallel planes having the axis P ′ as a perpendicular line. Even if the insulation-coated conductive particles 10 are agglomerated in connection between circuit members having opposing electrodes, a short circuit due to the agglomerated particles can be suitably suppressed.
  • the particle diameter Y is equal to or smaller than 2 ⁇ (the diameter of the base particle 1), the insulating coated conductive particles 10 in the conductive adhesive layer 13 are used. It is preferable in terms of adjusting the particle density and controlling the fluidity of the conductive adhesive layer 13 during pressure bonding.
  • the ratio X / Y between the particle diameter X and the particle diameter Y is preferably 0.4 or more and 0.9 or less.
  • X / Y is 0.4 or more, even when the bump area of the circuit member is reduced, it becomes easy to ensure the trapping property of the insulating coated conductive particles 10, and X / Y is 0.9 or less. If it is, it becomes easy to make a connection resistance low.
  • the average of 80% or more of the insulating coated conductive particles satisfies the above conditions.
  • the particle diameter X, the particle diameter Y, and the shortest distance D pass through the anisotropic conductive film 11 through the center of the base particle 1 of the insulating coated conductive particle 10 and parallel to the thickness direction of the conductive adhesive layer 13. This can be confirmed by observing a cross section when cut along a smooth surface.
  • a processing / observation device such as a focused ion beam (FIB), a scanning electron microscope (SEM), or a transmission electron microscope (TEM).
  • FIB focused ion beam
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the cross-section of the conductive adhesive layer (anisotropic conductive film) 13 can be cut using FIB, and then observed and measured with an SEM.
  • the release film 12 side of the anisotropic conductive film 11 with a release film is fixed to a jig for sample processing / observation using a conductive carbon tape.
  • a platinum sputtering process is performed from the conductive adhesive layer (anisotropic conductive film) 13 side to form a 10 nm platinum film on the conductive adhesive layer (anisotropic conductive film) 13.
  • FIB focused ion beam
  • processing is performed from the side of the conductive adhesive layer 13 of the anisotropic conductive film 11 with a release film, and the processed cross section is observed with a
  • the thickness of the adhesive region in the conductive adhesive layer (anisotropic conductive film) 13 can be set as appropriate.
  • the thickness of the adhesive region opposite to the adhesive region satisfying the shortest distance D of the conductive region. can be appropriately set according to the height of the bump electrode.
  • the anisotropic conductive film may have a multilayer structure in which the conductive adhesive layer 13 is laminated with an insulating adhesive layer that does not contain conductive particles.
  • the insulating adhesive layer can contain the above-described monomers, curing agent, and film-forming material, and includes a filler, a softening agent, an accelerator, an anti-aging agent, a colorant, It may further contain a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, isocyanates and the like.
  • the insulating adhesive layer on the conductive adhesive layer 13 By laminating the insulating adhesive layer on the conductive adhesive layer 13, it becomes easy to make the insulating coated conductive particles 10 contained in the anisotropic conductive film unevenly distributed on one side of the film.
  • An anisotropic conductive film composed of the adhesive region can be formed. Further, by adjusting the difference in melt viscosity between the conductive adhesive layer 13 and the insulating adhesive layer, the fluidity of the insulating coated conductive particles 10 and the adhesive region at the time of circuit connection can be arbitrarily adjusted.
  • a film forming material having a predetermined glass transition temperature (Tg) is included in the conductive adhesive layer 13 and the insulating adhesive layer.
  • a thermoplastic resin (particularly phenoxy resin) having a Tg of 60 to 180 ° C. is used as the film forming material to be contained in the conductive adhesive layer 13, and the film forming material to be contained in the insulating adhesive layer.
  • the glass transition temperature is measured with a thermophysical property measuring device such as a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the film forming material is weighed into an aluminum sample pan and measured simultaneously with an empty aluminum sample pan to measure the difference in heat.
  • a measurement error may occur due to the influence of the melting of the film forming material and the like. Therefore, it is preferable to measure the glass transition temperature from the second and subsequent measurement data.
  • the insulating coating conductive particles 10 are preferably arranged in the conductive adhesive layer 13 in a regular arrangement.
  • the insulating coated conductive particles 10 are preferably arranged in the conductive adhesive layer 13 in a regular arrangement.
  • the arrangement pattern is an equilateral triangle type, an isosceles triangle type, a regular pentagon type, a tetragonal type, a rectangular type, or an arrangement in which these patterns are inclined as shapes included when the insulating coated conductive particles 10 are connected by a straight line.
  • a pattern etc. are mentioned.
  • the equilateral triangular arrangement is a pattern that allows the closest packing of the insulating coated conductive particles 10 and is a suitable arrangement pattern for increasing the number of insulating coated conductive particles captured between the opposing electrodes. .
  • the particle density of the insulating coated conductive particles 10 is preferably 5000 / mm 2 or more and 40000 / mm 2 or less. By satisfying this condition, it is possible to more suitably achieve both ensuring connection reliability between the opposing electrodes and ensuring insulation between adjacent electrodes in the circuit member.
  • Step 1 of preparing composite particles 20 comprising conductive base particles 1 and insulating fine particles 2 covering the surface of the base particles 1; Step 2 (see (a) of FIG. 4) in which the composite particles 20 are accommodated in the holes 32 of the particle accommodation member 30 provided with the holes 32 having the closed end surface S; Removing part or all of the insulating fine particles 2 in the spherical crown region 3 of the composite particles 20 exposed from the holes 32 (see FIG.
  • the composite particles 20 from which the insulating fine particles 2 in the spherical crown region 3 have been removed are transferred from the particle containing member 30 so that the spherical crown region 3 side is in contact with the first adhesive layer 13a.
  • the insulating coated conductive particles 10 are provided on the first adhesive layer 13a by removing a part of the insulating fine particles 2 of the composite particles 20 by attaching them to the closed end surface S of the particle containing member 30 (Step 4). (See (a) and (b) of FIG. 5), Step 5 (see (c) of FIG. 5) in which the second adhesive layer 13b is bonded to the side where the insulating coated conductive particles 10 of the first adhesive layer 13a are disposed; Is provided.
  • the composite particles 20 in Step 1 can be prepared as described in the above method (ii).
  • Examples of the material of the particle accommodating member 30 used in Step 2 include a cured product of a radical polymerizable compound such as acrylate and methacrylate.
  • the hole 32 may have any shape as long as the composite particle 20 can be accommodated and the spherical crown region 3 of the composite particle 20 can protrude from the particle accommodation member 30. Can be mentioned.
  • Examples of the shape of the closed end surface S include a circular shape (spherical shape) and a polygonal shape.
  • the holes 32 are preferably provided in a regular arrangement (for example, the arrangement shown in FIG. 7), whereby the conductive adhesive layer 13 in which the insulating coated conductive particles 10 are arranged in the arrangement pattern described above is formed. Can do.
  • Examples of the method of removing the insulating fine particles 2 in the spherical crown region 3 of the composite particle 20 include a method of scraping with a squeegee made of urethane rubber or metal, and a method of scraping with a brush or the like. .
  • the material constituting the first adhesive layer 13a examples include monomers, curing agents, and film forming materials contained in the conductive adhesive layer 13 described above.
  • the first adhesive layer 13a further contains a filler, softener, accelerator, anti-aging agent, colorant, flame retardant, thixotropic agent, coupling agent, phenol resin, melamine resin, isocyanates, and the like. You may do it.
  • a laminate in which the first adhesive layer 13a is formed on the release film 12 can be used.
  • the thickness of the first adhesive layer 13a can be appropriately set according to the height of the bump electrode.
  • the second adhesive layer 13b a laminate in which the second adhesive layer 13b is formed on the release film 12 can be used.
  • the thickness of the second adhesive layer 13b can be appropriately set according to the height of the bump electrode.
  • Examples of the material constituting the second adhesive layer 13b include monomers, curing agents, and film forming materials contained in the conductive adhesive layer 13 described above.
  • the second adhesive layer 13b further contains a filler, softener, accelerator, anti-aging agent, colorant, flame retardant, thixotropic agent, coupling agent, phenol resin, melamine resin, isocyanates, and the like. You may do it.
  • a bonding method for example, a laminating method in which an adhesive is bonded while heating can be mentioned. Further, if a vacuum heating laminator that performs lamination under reduced pressure as well as heating is used, it is possible to reduce entrainment of bubbles during bonding.
  • a release film 12 a conductive adhesive layer (an anisotropic conductive film) 13 containing insulating coating conductive particles 10 and an adhesive component, and a release film 12
  • An anisotropic conductive film with a release film having a laminated structure in which are laminated in this order is obtained.
  • the thickness Da of the first adhesive layer 13a and the thickness Db of the second adhesive layer 13b from the viewpoint of unevenly distributing the insulating coated conductive particles 10 on one side of the conductive adhesive layer 13.
  • the ratio Da / Db is preferably 20/1 to 15/5.
  • FIG. 8 is a schematic cross-sectional view showing an embodiment of a connection structure according to the present invention.
  • the connection structure 50 includes a first circuit member 52 and a second circuit member 53 that face each other, and a conductive adhesive (an anisotropic conductive film) that connects these circuit members 52 and 53. ) Cured product 54.
  • the first circuit member 52 is, for example, a tape carrier package (TCP), a printed wiring board, a semiconductor silicon chip, or the like.
  • the first circuit member 52 has a plurality of bump electrodes 6 on the mounting surface 5 a side of the main body 5.
  • the bump electrode 6 has, for example, a rectangular shape in plan view, and has a thickness of, for example, 3 ⁇ m or more and less than 18 ⁇ m.
  • Au or the like is used as a material for forming the bump electrode 6, and the bump electrode 6 is more easily deformed than the insulating coated conductive particles 10 included in the cured product 54 of the conductive adhesive (anisotropic conductive film).
  • an insulating layer may be formed on a portion of the mounting surface 5a where the bump electrode 6 is not formed.
  • the second circuit member 53 is, for example, a glass substrate or a plastic substrate, a flexible printed circuit board (FPC), a ceramic wiring board, or the like on which a circuit is formed of ITO, IZO, or metal used for a liquid crystal display.
  • the second circuit member 53 has a plurality of circuit electrodes 8 corresponding to the bump electrodes 6 on the mounting surface 7 a side of the main body 7.
  • the circuit electrode 8 has a rectangular shape, for example, in plan view, like the bump electrode 6, and has a thickness of, for example, about 100 nm.
  • the surface of the circuit electrode 8 is, for example, one selected from gold, silver, copper, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, indium tin oxide (ITO), and indium zinc oxide (IZO) or It is composed of two or more materials.
  • an insulating layer may be formed in a portion where the circuit electrode 8 is not formed.
  • the cured product 54 is formed using, for example, the anisotropic conductive film 11 with a release film shown in FIG. 3A, and can be a cured product of the conductive adhesive layer (anisotropic conductive film) 13. .
  • the layer in which the insulating coated conductive particles 10 are dispersed is referred to as a conductive adhesive layer 13, but the adhesive component itself constituting the layer is non-conductive.
  • the insulating coated conductive particles 10 may be unevenly distributed on the second circuit member 53 side, and are interposed between the bump electrode 6 and the circuit electrode 8 in a state of being slightly flattened by pressure bonding. . Thereby, electrical connection between the bump electrode 6 and the circuit electrode 8 is realized.
  • the insulating coating conductive particles 10 are spaced apart in a pattern pattern, and are adjacent to and adjacent to the bump electrodes 6 and 6. Electrical insulation between the circuit electrodes 8, 8 is realized.
  • connection structure 9 and 10 are schematic cross-sectional views showing the manufacturing process of the connection structure shown in FIG.
  • the release film 12 is peeled from the anisotropic conductive film 11 with a release film, and the conductive adhesive layer (anisotropic conductive film) 13 is formed so as to face the mounting surface 7 a.
  • Laminate on the second circuit member 53 Next, as shown in FIG. 10, the first is formed on the second circuit member 53 on which the conductive adhesive layer (anisotropic conductive film) 13 is laminated so that the bump electrode 6 and the circuit electrode 8 face each other.
  • the circuit member 52 is arranged. Then, the first circuit member 52 and the second circuit member 53 are pressed in the thickness direction while heating the conductive adhesive layer (anisotropic conductive film) 13.
  • the adhesive component of the conductive adhesive layer (anisotropic conductive film) 13 flows, the distance between the bump electrode 6 and the circuit electrode 8 is shortened, and the insulating coated conductive particles 10 are engaged with each other.
  • the agent layer 13 is cured.
  • the bump electrode 6 and the circuit electrode 8 are electrically connected, and the adjacent bump electrodes 6, 6 and the adjacent circuit electrodes 8, 8 are electrically insulated.
  • a cured product 54 of the conductive adhesive layer (anisotropic conductive film) 13 is formed, and the connection structure 50 shown in FIG. 8 is obtained.
  • the cured material 54 of the conductive adhesive layer (anisotropic conductive film) 13 sufficiently prevents the change with time in the distance between the bump electrode 6 and the circuit electrode 8, Long-term reliability of electrical characteristics can be secured.
  • the heating temperature at the time of connection is equal to or higher than a temperature at which polymerization active species are generated in the curing agent and polymerization of the polymerization monomer is started.
  • the heating temperature is, for example, 80 ° C. to 200 ° C., preferably 100 ° C. to 180 ° C.
  • the heating time is, for example, 0.1 second to 30 seconds, preferably 1 second to 20 seconds.
  • the heating temperature is less than 80 ° C., the curing rate is slow, and when it exceeds 200 ° C., unwanted side reactions tend to proceed.
  • the heating time is less than 0.1 seconds, the curing reaction does not proceed sufficiently, and when it exceeds 30 seconds, the productivity of the cured product 54 decreases, and undesired side reactions easily proceed.
  • connection structure of the present embodiment by using the conductive adhesive layer (anisotropic conductive film) 13 including the insulating coated conductive particles 10, the connection reliability between the opposing electrodes and the inside of the circuit member It is possible to obtain a connection structure that can achieve both insulating properties of adjacent electrodes.
  • Each adhesive layer was formed by the following method.
  • Adhesive layer 1 45 g of 4,4 ′-(9-fluorenylidene) -diphenol in a 3000 mL three-necked flask equipped with a Dimroth condenser, a calcium chloride tube, and a stirring bar made of polytetrafluoroethylene connected to a stirring motor ( Sigma Aldrich Japan Co., Ltd.) and 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether 50 g (Mitsubishi Chemical Co., Ltd .: YX-4000H) were dissolved in 1000 mL of N-methylpyrrolidone to obtain a reaction solution. It was.
  • the molecular weight and dispersity of the phenoxy resin a were measured by gel permeation chromatography (GPC) according to the following conditions.
  • GPC gel permeation chromatography
  • the glass transition temperature of the phenoxy resin a was 160 degreeC when it measured according to the following conditions about the glass transition temperature of the phenoxy resin a. (Measurement condition) Using a differential scanning calorimeter (manufactured by PerkinElmer Japan Co., Ltd., Pyeis), the temperature was increased twice in the range of 10 ° C./min and 30 to 250 ° C. in a nitrogen atmosphere, and the second measurement. The result was taken as the glass transition temperature.
  • the obtained adhesive paste was applied onto a PET resin film having a thickness of 50 ⁇ m using a coater and dried with hot air at 70 ° C. for 5 minutes to form an adhesive layer 1 having a thickness of 15 ⁇ m.
  • Adhesive layer 2 Similarly to the formation of the adhesive layer 1, an adhesive layer 2 having a thickness of 0.8 ⁇ m was formed.
  • Adhesive layer 3 45 parts by mass of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: jER807), 5 parts by mass of 4-hydroxyphenylmethylbenzylsulfonium hexafluoroantimonate as a curing agent, and phenoxy resin YP-70 (Nippon Steel & Sumitomo Metal) as a film forming material 55 parts by mass of Chemical Co.) was mixed to prepare an adhesive paste.
  • the obtained adhesive paste was applied onto a PET resin film having a thickness of 50 ⁇ m using a coater and dried with hot air at 70 ° C. for 5 minutes to form an adhesive layer 3 having a thickness of 15 ⁇ m.
  • Composite particles were prepared by the following methods.
  • Base particle 3 g of crosslinked polystyrene particles (resin fine particles) having an average particle size of 3.0 ⁇ m were neutralized with acid after alkaline degreasing. Next, the resin fine particles were added to 100 mL of a cationic polymer solution adjusted to pH 6.0, stirred at 60 ° C. for 1 hour, filtered through a membrane filter (Millipore) having a diameter of 3 ⁇ m, and washed with water.
  • a cationic polymer solution adjusted to pH 6.0
  • the resin fine particles after washing with water are added to 100 mL of palladium-catalyzed solution containing 8% by mass of Atotech Neogant 834 (trade name, manufactured by Atotech Japan Co., Ltd.), which is a palladium catalyst, and the mixture is stirred at 35 ° C. for 30 minutes and then filtered. , Washed with water.
  • resin fine particles after washing with water were added to a 3 g / L sodium hypophosphite solution to obtain resin fine particles (resin core particles) whose surface was activated.
  • the resin core particles, 1000 mL of water, and sodium malate (concentration 20 g / L) were put into a 2000 mL glass beaker and ultrasonically dispersed. Subsequently, the pH was adjusted to 5.5 or lower while stirring (600 rpm) with a fluorine stirring blade, and the dispersion was heated to 80 ° C.
  • the polymerization reaction was allowed to proceed for 6 hours while heating to 80 ° C. to obtain organic-inorganic hybrid particles having a primary particle size of 300 nm.
  • the dispersion containing the organic-inorganic hybrid particles is placed in a 20 mL container, and 3000 r. p. m.
  • the unreacted monomer was removed by centrifugation for 30 minutes (manufactured by Kokusan Co., Ltd .: H-103N). Further, 20 mL of methanol was added, and the mixture was ultrasonically dispersed and centrifuged again.
  • a ⁇ 3 ⁇ m membrane filter (manufactured by Millipore), which was stirred for 2 hours at room temperature (25 ° C.) using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., trade name: BL3000) equipped with a stirring blade having a diameter of 45 mm and washed with methanol The resultant was filtered through a coated type membrane filter) to obtain 10 g of base particles having a carboxyl group as a surface functional group.
  • a 30% by mass polyethyleneimine aqueous solution (trade name: 30% polyethyleneimine P-70 solution, manufactured by Wako Pure Chemical Industries, Ltd.) containing polyethyleneimine having a weight average molecular weight of 70,000 is diluted with ultrapure water to obtain 0.3% by mass polyethylene.
  • An aqueous imine solution was obtained.
  • 10 g of the above-mentioned base particles into which the carboxyl group was introduced were added.
  • the mixture was stirred at room temperature (25 ° C.) for 15 minutes and filtered through a membrane filter of ⁇ 3 ⁇ m to obtain particles in which polyethyleneimine as a polymer electrolyte was adsorbed on the surface.
  • the particles were mixed with 200 g of ultrapure water, stirred at room temperature (25 ° C.) for 5 minutes, and filtered.
  • the particles obtained by filtration were washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine not adsorbed on the particles.
  • the composite particles 1 taken out by filtration were put into a mixed solution of 50 g of silicone oligomer having a weight average molecular weight of 1000 (manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000) and 150 g of methanol, and stirred at room temperature (25 ° C.) for 1 hour. And filtered. Finally, the composite particles were placed in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 3 minutes, and filtered.
  • a 30% by mass polyethyleneimine aqueous solution (trade name: 30% polyethyleneimine P-70 solution, manufactured by Wako Pure Chemical Industries, Ltd.) containing polyethyleneimine having a weight average molecular weight of 70,000 is diluted with ultrapure water to obtain 0.3% by mass polyethylene.
  • An aqueous imine solution was obtained.
  • 10 g of the above-described substrate particles having the carboxyl group introduced were added. The mixture was stirred at room temperature (25 ° C.) for 15 minutes and filtered through a membrane filter having a diameter of 5 ⁇ m to obtain particles having polyethyleneimine as a polymer electrolyte adsorbed on the surface.
  • the particles were mixed with 200 g of ultrapure water, stirred at room temperature (25 ° C.) for 5 minutes, and filtered.
  • the particles obtained by filtration were washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine not adsorbed on the particles.
  • insulating fine particle dispersion obtained by diluting 10 g of base material particles adsorbed with polyethyleneimine with 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) with the insulating fine particles prepared above.
  • insulating fine particles prepared above.
  • the composite particles 2 taken out by filtration are put into a mixed solution of 50 g of a silicone oligomer having a weight average molecular weight of 1000 (manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000) and 150 g of methanol and stirred at room temperature (25 ° C.) for 1 hour. And filtered. Finally, the composite particles were placed in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 3 minutes, and filtered.
  • a silicone oligomer having a weight average molecular weight of 1000 manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000
  • toluene manufactured by Wako Pure Chemical Industries, Ltd.
  • the obtained composite particles 2 were vacuum dried at 150 ° C. for 1 hour. Thereafter, aggregates were removed with a swirling air flow classifier (Seishin Enterprise Co., Ltd.).
  • a 30% by mass polyethyleneimine aqueous solution (trade name: 30% polyethyleneimine P-70 solution, manufactured by Wako Pure Chemical Industries, Ltd.) containing polyethyleneimine having a weight average molecular weight of 70,000 is diluted with ultrapure water to obtain 0.3% by mass polyethylene.
  • An aqueous imine solution was obtained.
  • 10 g of the above-described substrate particles having the carboxyl group introduced were added. The mixture was stirred at room temperature (25 ° C.) for 15 minutes and filtered through a membrane filter having a diameter of 6 ⁇ m to obtain particles in which polyethyleneimine as a polymer electrolyte was adsorbed on the surface.
  • the particles were mixed with 200 g of ultrapure water, stirred at room temperature (25 ° C.) for 5 minutes, and filtered.
  • the particles obtained by filtration were washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine not adsorbed on the particles.
  • the composite particles 3 taken out by filtration were put into a mixed solution of 50 g of a silicone oligomer having a weight average molecular weight of 1000 (manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000) and 150 g of methanol and stirred at room temperature (25 ° C.) for 1 hour. And filtered. Finally, the composite particles were placed in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 3 minutes, and filtered.
  • a silicone oligomer having a weight average molecular weight of 1000 manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000
  • toluene manufactured by Wako Pure Chemical Industries, Ltd.
  • the obtained composite particles 3 were vacuum dried at 150 ° C. for 1 hour. Thereafter, aggregates were removed with a swirling air flow classifier (Seishin Enterprise Co., Ltd.).
  • a plate obtained by polymerization of methacrylate having a thickness of 5.0 ⁇ m has a cylindrical shape (4.0 ⁇ m in diameter and 3.8 ⁇ m in depth) having a closed end surface (bottom surface) and a density of 20000 / mm 2 in a square mold. It was provided so that it might be arranged in.
  • Cylindrical holes (diameter: 4.6 ⁇ m, depth: 3.8 ⁇ m) having a closed end surface (bottom surface) are formed in a plate obtained by polymerization of 5.0 ⁇ m-thick methacrylate in an equilateral triangle shape with 25000 holes / mm 2 . It arranged so that it might arrange with density.
  • Cylindrical holes (diameter: 5.2 ⁇ m, depth: 3.8 ⁇ m) having a closed end surface (bottom surface) on a plate obtained by polymerization of a 5.0 ⁇ m-thick methacrylate, are 20000 / mm 2 in an equilateral triangle shape. It arranged so that it might arrange with density.
  • Example 1 Similar to the method shown in FIGS. 4A and 4B, the composite particles 1 are accommodated in the holes of the particle accommodating member 1, and the end surfaces are exposed from the holes using a horizontal urethane rubber squeegee. The insulating fine particles in the spherical crown region of the composite particles were removed. By this operation, it was confirmed by observation with an SEM that a region where the number of insulating fine particles was 0 was provided in the spherical region of the composite particle by 54.7 ⁇ m 2 .
  • the adhesive layer 2 is bonded to the side of the adhesive layer 1 where the insulating coating conductive particles are arranged, and the conductive adhesive layer is sandwiched between the two PET resin films.
  • An anisotropic conductive film provided with was obtained.
  • Example 2 Using a particle containing member 2, except the provision of the square type disposed in particle density of 20000 / mm 2 an insulated coating conductive particles on the adhesive layer 1 in the same manner as in Example 1, different Hoshirubeden A film was obtained.
  • Example 3 An anisotropic conductive film was obtained in the same manner as in Example 1 except that the composite particle 2 was used instead of the composite particle 1 and the particle storage member 3 was used instead of the particle storage member 1. Also in this case, it can be confirmed that 50.2 ⁇ m 2 is provided in the spherical region of the composite particle in the region where the number of insulating fine particles is 0, and what is the portion in contact with the adhesive layer 1 of the insulating coated conductive particle? On the opposite side, it was confirmed that 48.7 ⁇ m 2 of a region having 0 insulating fine particles was provided.
  • Example 4 An anisotropic conductive film was obtained in the same manner as in Example 1 except that the composite particle 3 was used instead of the composite particle 1 and the particle storage member 4 was used instead of the particle storage member 1. Also in this case, it can be confirmed that the area where the number of insulating fine particles is 0 is provided in the spherical crown area of the composite particle, which is 53.3 ⁇ m 2, and the portion in contact with the adhesive layer 1 of the insulating coated conductive particles is On the opposite side, it was confirmed that 48.7 ⁇ m 2 of a region having 0 insulating fine particles was provided.
  • Example 5 An anisotropic conductive film was obtained in the same manner as in Example 1 except that the particle containing member 5 was used instead of the particle containing member 1. Also in this case, it can be confirmed that the area where the number of insulating fine particles is 0 is provided in the spherical crown area of the composite particle is 52.6 ⁇ m 2, and the portion of the insulating coated conductive particle that contacts the adhesive layer 1 is On the opposite side, it was confirmed that 47.9 ⁇ m 2 of regions having 0 insulating fine particles were provided.
  • Example 6 An anisotropic conductive film was obtained in the same manner as in Example 1 except that the adhesive layer 3 was used in place of the adhesive layer 1.
  • connection structure As a first circuit member, an IC chip having a straight arrangement structure in which bump electrodes are arranged in a row (outer dimensions 2 mm ⁇ 20 mm, thickness 0.55 mm, bump electrode size 100 ⁇ m ⁇ 30 ⁇ m, distance between bump electrodes 8 ⁇ m, bump electrode thickness 15 ⁇ m) was prepared.
  • As the second circuit member an ITO wiring pattern (pattern width 21 ⁇ m, interelectrode space 17 ⁇ m) formed on the surface of a glass substrate (Corning Inc .: # 1737, 38 mm ⁇ 28 mm, thickness 0.3 mm) is used. Got ready.
  • One PET resin film of the anisotropic conductive films (2.5 mm ⁇ 25 mm) according to Examples 1 to 6 was peeled off, and a conductive adhesive layer was placed on a glass substrate with a stage (150 mm ⁇ 150 mm) composed of a ceramic heater, and Using a thermocompression bonding apparatus composed of a tool (3 mm ⁇ 20 mm), it was attached by heating and pressing for 2 seconds at 80 ° C. and 0.98 MPa (10 kgf / cm 2 ).
  • a stage (150 mm ⁇ 150 mm) comprising a ceramic heater and a tool ( 3 mm ⁇ 20 mm) using a thermocompression bonding apparatus, and heating and pressurizing for 5 seconds under the conditions of an actually measured maximum reached temperature of 170 ° C. of the conductive adhesive layer and an area conversion pressure of 70 MPa at the bump electrode.
  • a stage 150 mm ⁇ 150 mm
  • a tool 3 mm ⁇ 20 mm
  • connection resistance was evaluated by a four-terminal measurement method, and the average value of 14 measurements was used.
  • insulation resistance was evaluated by applying a voltage of 50 V to the connection structure and measuring the insulation resistance between a total of 1440 circuit electrodes in a lump. The results are shown in Table 2.
  • connection structures produced using the anisotropic conductive films of Examples 1 to 6 had a connection resistance value of 1.2 ⁇ or less and sufficient insulation resistance.
  • SYMBOLS 1 Base particle, 2 ... Insulating fine particle, 3 ... Spherical crown area

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Abstract

According to the present invention, each one of insulation covered conductive particles comprises a conductive base material particle and insulating fine particles that cover the surface of the base material particle, and has a sparse region where the number of the insulating fine particles per unit area is small or 0 and a dense region where the number of the insulating fine particles per unit area is larger than that of the sparse region.

Description

絶縁被覆導電粒子、異方導電フィルム、異方導電フィルムの製造方法、接続構造体及び接続構造体の製造方法Insulating coated conductive particles, anisotropic conductive film, method for manufacturing anisotropic conductive film, connection structure, and method for manufacturing connection structure
　本発明は、絶縁被覆導電粒子、異方導電フィルム、異方導電フィルムの製造方法、接続構造体及び接続構造体の製造方法に関する。 The present invention relates to an insulating coated conductive particle, an anisotropic conductive film, a method for manufacturing an anisotropic conductive film, a connection structure, and a method for manufacturing a connection structure.
　従来、例えば液晶ディスプレイとテープキャリアパッケージ（ＴＣＰ）との接続、フレキシブルプリント基板（ＦＰＣ）とＴＣＰとの接続、或いはＦＰＣとプリント配線板との接続には、接着剤フィルム中に導電粒子を分散させた異方導電フィルムが用いられている。また、半導体シリコンチップを基板に実装する場合にも、従来のワイヤーボンディングに代えて、半導体シリコンチップを基板に直接実装する、いわゆるチップオンガラス（ＣＯＧ）が行われており、ここでも異方導電フィルムが用いられている。 Conventionally, for example, for connection between a liquid crystal display and a tape carrier package (TCP), connection between a flexible printed circuit board (FPC) and TCP, or connection between an FPC and a printed wiring board, conductive particles are dispersed in an adhesive film. An anisotropic conductive film is used. In addition, when a semiconductor silicon chip is mounted on a substrate, so-called chip-on-glass (COG) in which the semiconductor silicon chip is directly mounted on the substrate is used instead of the conventional wire bonding. A film is used.
　近年では、電子機器の発達に伴い、配線の高密度化及び回路の高機能化が進んでいる。その結果、接続電極間の間隔が例えば１５μｍ以下となるような接続構造体が要求され、接続部材のバンプ電極も小面積化されてきている。小面積化されたバンプ接続において安定した電気的接続を得るためには、充分な数の導電粒子がバンプ電極と基板側の回路電極との間に介在している必要がある。 In recent years, with the development of electronic equipment, the density of wiring and the functionality of circuits have been advanced. As a result, a connection structure in which the interval between the connection electrodes is, for example, 15 μm or less is required, and the bump electrode of the connection member has also been reduced in area. In order to obtain a stable electrical connection in the bump connection with a reduced area, it is necessary that a sufficient number of conductive particles be interposed between the bump electrode and the circuit electrode on the substrate side.
　このような課題に対し、特許文献１及び２では、導電粒子を一定割合で基板側に偏在化させると共に、導電粒子を均等間隔に整列させることで、バンプ電極と回路電極の導電粒子の捕捉性を向上させるとともに、狭小化された隣り合う回路電極間の絶縁性の向上を提案している。 With respect to such problems, in Patent Documents 1 and 2, the conductive particles are unevenly distributed on the substrate side at a constant rate, and the conductive particles are aligned at equal intervals, thereby capturing the conductive particles of the bump electrode and the circuit electrode. And improving the insulation between the narrowed adjacent circuit electrodes.
特表２００９－５３５８４３号公報Special table 2009-535843 特開２０１５－２５１０４号公報Japanese Patent Laying-Open No. 2015-25104
　しかしながら、上述した従来の手法では、導電粒子が均等間隔に整列することで導電粒子の捕捉性を向上させ、接続信頼性を向上させることが可能であるが、回路接続時に異方導電フィルムが溶融し流動するため、均等間隔に整列させた導電粒子も流動する可能性があり、隣り合う回路電極間の絶縁性が低下する問題が生じるおそれがあった。 However, in the above-described conventional method, it is possible to improve the capturing property of the conductive particles and improve the connection reliability by arranging the conductive particles at equal intervals, but the anisotropic conductive film melts at the time of circuit connection. Therefore, there is a possibility that the conductive particles aligned at equal intervals may also flow, which may cause a problem that insulation between adjacent circuit electrodes is lowered.
　本発明は、対向する電極を有する回路部材同士の接続において、対向する電極間の接続信頼性の確保と回路部材内の隣り合う電極同士の絶縁性の確保とを両立できる絶縁被覆導電粒子及び異方導電フィルム、異方導電フィルムの製造方法、並びに、対向する電極間の接続信頼性と回路部材内の隣り合う電極同士の絶縁性とを両立できる接続構造体及び接続構造体の製造方法を提供することを目的する。 In connection between circuit members having opposing electrodes, the present invention provides insulating coated conductive particles and different conductive materials capable of ensuring both connection reliability between opposing electrodes and insulation between adjacent electrodes in the circuit member. A method for manufacturing an anisotropic conductive film, an anisotropic conductive film, a connection structure that can achieve both connection reliability between opposing electrodes and insulation between adjacent electrodes in a circuit member, and a method for manufacturing the connection structure Aim to do.
　本発明は、導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子と、を備え、単位面積当たりの絶縁性微粒子数が少ない若しくは０である粗領域と、粗領域よりも単位面積当たりの絶縁性微粒子数が多い密領域とを有する第１の絶縁被覆導電粒子を提供する。 The present invention comprises a conductive base material particle and insulating fine particles covering the surface of the base material particle, a rough region having a small or zero number of insulating fine particles per unit area, and a rough region There are provided first insulating coated conductive particles having a dense region having a larger number of insulating fine particles per unit area.
　本発明の第１の絶縁被覆導電粒子は、上記密領域によって粒子同士が接触したときの絶縁性を確保しつつ、上記粗領域によって導電特性を確保することができる。 The first insulating coated conductive particles of the present invention can ensure conductive properties by the rough region while ensuring insulation when the particles are in contact with each other by the dense region.
　本発明の第１の絶縁被覆導電粒子は、上記基材粒子の中心を通る中心軸が通る上記粗領域を２つ有することができる。 The first insulating coated conductive particles of the present invention can have two of the rough regions passing through the central axis passing through the center of the base material particles.
　このような絶縁被覆導電粒子は、対向する電極を有する回路部材同士の接続において、２つの粗領域を対向する電極にそれぞれ接触させることにより対向する電極間の接続信頼性を確保することができ、他の絶縁被覆導電粒子が接触する場合には上記密領域によって絶縁性を確保することができる。 Such insulating coated conductive particles can ensure the connection reliability between the facing electrodes by bringing the two rough regions into contact with the facing electrodes in the connection between the circuit members having the facing electrodes, When other insulating coating conductive particles are in contact with each other, insulation can be ensured by the dense region.
　本発明はまた、導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子とを備える複合粒子の、基材粒子を二つの平行な平面で切ったときの２つの球冠領域にある絶縁性微粒子の一部又は全部を除去してなる第２の絶縁被覆導電粒子を提供する。 The present invention also provides two spheres of a composite particle comprising conductive base particles and insulating fine particles covering the surface of the base particles when the base particles are cut in two parallel planes. Provided is a second insulating coated conductive particle obtained by removing a part or all of the insulating fine particles in the crown region.
　本発明の第２の絶縁被覆導電粒子は、対向する電極を有する回路部材同士の接続において、絶縁性微粒子の一部又は全部が除去された２つの球冠領域を対向する電極にそれぞれ接触させることより対向する電極間の接続信頼性を確保することができ、他の絶縁被覆導電粒子と接触するときには球帯領域にある絶縁性微粒子によって絶縁性を確保することができる。 In the connection between circuit members having opposing electrodes, the second insulating coated conductive particles of the present invention are configured to bring the two spherical crown regions from which part or all of the insulating fine particles have been removed into contact with the opposing electrodes, respectively. The connection reliability between the more opposing electrodes can be ensured, and the insulation can be ensured by the insulating fine particles in the spherical zone region when coming into contact with other insulating coating conductive particles.
　本発明はまた、導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子とを備え、基材粒子を二つの平行な平面で切ったときの球帯領域に絶縁性微粒子が偏在している第３の絶縁被覆導電粒子を提供する。 The present invention also comprises conductive base particles and insulating fine particles covering the surface of the base particles, and is insulative in a spherical zone when the base particles are cut in two parallel planes. A third insulating coated conductive particle in which fine particles are unevenly distributed is provided.
　本発明の第３の絶縁被覆導電粒子は、対向する電極を有する回路部材同士の接続において、２つの球冠領域を対向する電極にそれぞれ接触させることより対向する電極間の接続信頼性を確保することができ、他の絶縁被覆導電粒子と接触するときには球帯領域に偏在している絶縁性微粒子によって絶縁性を確保することができる。 The third insulating coated conductive particle of the present invention ensures the connection reliability between the facing electrodes by bringing the two crown areas into contact with the facing electrodes in the connection between the circuit members having the facing electrodes. Insulating properties can be ensured by the insulating fine particles that are unevenly distributed in the spherical zone when contacting with other insulating coated conductive particles.
　本発明はまた、上記本発明の第１、第２又は第３の絶縁被覆導電粒子と、接着剤成分とが含まれる導電性接着剤層を備える異方導電フィルムを提供する。 The present invention also provides an anisotropic conductive film comprising a conductive adhesive layer containing the first, second or third insulating coated conductive particles of the present invention and an adhesive component.
　本発明の異方導電フィルムによれば、対向する電極を有する回路部材同士の接続において、対向する電極間の接続信頼性の確保と回路部材内の隣り合う電極同士の絶縁性の確保とを両立することができる。 According to the anisotropic conductive film of the present invention, in connection between circuit members having opposing electrodes, both the connection reliability between the facing electrodes and the insulation between adjacent electrodes in the circuit member are compatible. can do.
　本発明の異方導電フィルムは、基材粒子の中心を通る中心軸が通る粗領域を２つ有する上記本発明の第１の絶縁被覆導電粒子を含み、該絶縁被覆導電粒子が、基材粒子の中心を通り且つ導電性接着剤層の厚み方向に平行な軸が２つの粗領域を通るように配されていてもよい。 The anisotropic conductive film of the present invention includes the first insulating coated conductive particles of the present invention having two rough regions through which the central axis passing through the center of the substrate particles passes. And an axis parallel to the thickness direction of the conductive adhesive layer may pass through the two rough regions.
　このような異方導電フィルムによれば、対向する電極を有する回路部材同士の接続において、絶縁被覆導電粒子が有する２つの粗領域をそれぞれ対向する電極により確実に接触させることができ、他の絶縁被覆導電粒子と接触する場合には互いの密領域によって絶縁性を確保することができる。これにより、対向する電極間の接続信頼性の確保と、回路部材内の隣り合う電極同士の絶縁性の確保とをより高水準で両立することができる。 According to such an anisotropic conductive film, in connection of circuit members having opposing electrodes, the two rough regions of the insulating coated conductive particles can be reliably brought into contact with the opposing electrodes, respectively, In the case of contact with the coated conductive particles, insulating properties can be ensured by the dense regions of each other. Thereby, securing of connection reliability between the electrodes facing each other and securing of insulation between adjacent electrodes in the circuit member can be achieved at a higher level.
　本発明の異方導電フィルムは、上記本発明の第２の絶縁被覆導電粒子を含み、該絶縁被覆導電粒子が、基材粒子の中心を通り且つ導電性接着剤層の厚み方向に平行な軸が２つの球冠領域を通るように配されていてもよい。 The anisotropic conductive film of the present invention includes the second insulating coating conductive particles of the present invention, and the insulating coating conductive particles pass through the center of the base particle and are parallel to the thickness direction of the conductive adhesive layer. May be arranged to pass through the two crown areas.
　このような異方導電フィルムによれば、対向する電極を有する回路部材同士の接続において、絶縁被覆導電粒子が有する２つの球冠領域をそれぞれ対向する電極により確実に接触させることができ、他の絶縁被覆導電粒子と接触する場合には互いの球帯領域にある絶縁性微粒子によって絶縁性を確保することができる。これにより、対向する電極間の接続信頼性の確保と、回路部材内の隣り合う電極同士の絶縁性の確保とをより高水準で両立することができる。 According to such an anisotropic conductive film, in connection of circuit members having opposing electrodes, the two spherical crown regions of the insulating coated conductive particles can be reliably brought into contact with each other by the opposing electrodes. In the case of contact with the insulating coated conductive particles, the insulating properties can be ensured by the insulating fine particles in the respective spherical zone regions. Thereby, securing of connection reliability between the electrodes facing each other and securing of insulation between adjacent electrodes in the circuit member can be achieved at a higher level.
　本発明の異方導電フィルムは、上記本発明の第２又は第３の絶縁被覆導電粒子を含み、該絶縁被覆導電粒子が、基材粒子の中心を通り且つ導電性接着剤層の厚み方向に平行な軸と上記二つの平行な平面とが直交するように、配されていてもよい。 The anisotropic conductive film of the present invention includes the second or third insulating coated conductive particles of the present invention, and the insulating coated conductive particles pass through the center of the base particle and in the thickness direction of the conductive adhesive layer. You may arrange | position so that a parallel axis | shaft and the said two parallel planes may orthogonally cross.
　このような異方導電フィルムによれば、対向する電極を有する回路部材同士の接続において、絶縁被覆導電粒子が有する２つの球冠領域をそれぞれ対向する電極により確実に接触させることができ、他の絶縁被覆導電粒子と接触する場合には互いの球帯領域にある絶縁性微粒子によって絶縁性を確保することができる。これにより、対向する電極間の接続信頼性の確保と、回路部材内の隣り合う電極同士の絶縁性の確保とをより高水準で両立することができる。 According to such an anisotropic conductive film, in connection of circuit members having opposing electrodes, the two spherical crown regions of the insulating coated conductive particles can be reliably brought into contact with each other by the opposing electrodes. In the case of contact with the insulating coated conductive particles, the insulating properties can be ensured by the insulating fine particles in the respective spherical zone regions. Thereby, securing of connection reliability between the electrodes facing each other and securing of insulation between adjacent electrodes in the circuit member can be achieved at a higher level.
　本発明はまた、導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子と、を備える複合粒子を用意するステップと、閉鎖端面を有する孔が設けられた粒子収容部材の孔に複合粒子を収容するステップと、孔から露出する複合粒子の球冠領域にある絶縁性微粒子の一部又は全部を除去するステップと、第１の接着剤層上に、球冠領域の絶縁性微粒子が除去された複合粒子を、球冠領域が第１の接着剤層に接するように粒子収容部材から移しつつ、複合粒子の絶縁性微粒子の一部を粒子収容部材の閉鎖端面に付着させて除去することにより、第１の接着剤層上に絶縁被覆導電粒子を設けるステップと、第１の接着剤層の絶縁被覆導電粒子が配されている側に第２の接着剤層を貼り合せるステップとを備える異方導電フィルムの製造方法を提供する。 The present invention also provides a step of preparing composite particles comprising conductive base particles and insulating fine particles covering the surface of the base particles, and a particle containing member provided with a hole having a closed end face Containing the composite particles in the pores, removing a part or all of the insulating fine particles in the crown region of the composite particles exposed from the pores, and forming the crown region on the first adhesive layer. The composite particles from which the insulating fine particles have been removed are transferred from the particle containing member so that the spherical region is in contact with the first adhesive layer, and a part of the insulating fine particles of the composite particles are attached to the closed end surface of the particle containing member. Removing the first adhesive layer by providing the insulating coating conductive particles on the first adhesive layer, and attaching the second adhesive layer to the side of the first adhesive layer on which the insulating coating conductive particles are disposed. An anisotropic conductive film comprising a step of combining To provide a production method.
　本発明の異方導電フィルムの製造方法によれば、第１の接着剤層上に、絶縁性微粒子の一部又は全部が除去された２つの球冠領域を有する絶縁被覆導電粒子を設けることができ、これに第２の接着剤層を貼り合せることにより、絶縁被覆導電粒子が含まれる導電性接着剤層を簡便に形成することができる。この導電性接着剤層においては、基材粒子の中心を通り且つ導電性接着剤層の厚み方向に平行な軸が２つの球冠領域を通るように絶縁被覆導電粒子を配することができる。 According to the method for producing the anisotropic conductive film of the present invention, the insulating coated conductive particles having two spherical regions from which part or all of the insulating fine particles are removed are provided on the first adhesive layer. The conductive adhesive layer containing the insulating coated conductive particles can be easily formed by attaching the second adhesive layer thereto. In this conductive adhesive layer, the insulating coated conductive particles can be arranged so that an axis passing through the center of the base particle and parallel to the thickness direction of the conductive adhesive layer passes through the two crown regions.
　また、本発明の異方導電フィルムの製造方法においては、粒子収容部材に規則的に配列された孔を設けることにより、異方導電フィルム内の絶縁被覆導電粒子を規則的に配列することができる。また、第１の接着剤層及び第２の接着剤層の厚みを調整することにより、絶縁被覆導電粒子が導電性接着剤層の両主面の一方側に偏在して含まれる導電性接着剤層を形成することができる。 In the method for producing an anisotropic conductive film of the present invention, the insulating coated conductive particles in the anisotropic conductive film can be regularly arranged by providing regularly arranged holes in the particle containing member. . Further, the conductive adhesive in which the insulating coated conductive particles are unevenly distributed on one side of both main surfaces of the conductive adhesive layer by adjusting the thicknesses of the first adhesive layer and the second adhesive layer. A layer can be formed.
　本発明はまた、バンプ電極を有する第１の回路部材と、バンプ電極に対応する回路電極を有する第２の回路部材と、バンプ電極及び回路電極の間に介在してバンプ電極及び回路電極を電気的に接続する上記本発明に係る第１、第２又は第３の絶縁被覆導電粒子とを備える接続構造体を提供する。 The present invention also provides a first circuit member having a bump electrode, a second circuit member having a circuit electrode corresponding to the bump electrode, and the bump electrode and the circuit electrode electrically interposed between the bump electrode and the circuit electrode. Provided is a connection structure comprising the first, second, or third insulating coated conductive particles according to the present invention that are connected to each other.
　本発明の接続構造体は、上記本発明に係る第１、第２又は第３の絶縁被覆導電粒子によってバンプ電極及び回路電極が接続されているため、対向する電極間の接続信頼性と回路部材内の隣り合う電極同士の絶縁性とを両立することができる。 In the connection structure of the present invention, since the bump electrode and the circuit electrode are connected by the first, second, or third insulating coating conductive particles according to the present invention, the connection reliability between the opposing electrodes and the circuit member It is possible to achieve both insulating properties between adjacent electrodes.
　本発明はまた、バンプ電極を有する第１の回路部材と、バンプ電極に対応する回路電極を有する第２の回路部材との間に、上記本発明に係る異方導電フィルム又は上記本発明に係る異方導電フィルムの製造方法によって得られる異方導電フィルムを介在させ、第１の回路部材と第２の回路部材とを熱圧着するステップを有する接続構造体の製造方法を提供する。 The present invention also relates to the anisotropic conductive film according to the present invention or the above-described present invention between the first circuit member having a bump electrode and the second circuit member having a circuit electrode corresponding to the bump electrode. Provided is a connection structure manufacturing method including a step of thermocompression bonding a first circuit member and a second circuit member with an anisotropic conductive film obtained by the method for manufacturing an anisotropic conductive film interposed therebetween.
　本発明の接続構造体の製造方法によれば、対向する電極間の接続信頼性と回路部材内の隣り合う電極同士の絶縁性とを両立する接続構造体を得ることができる。 According to the method for manufacturing a connection structure of the present invention, it is possible to obtain a connection structure that achieves both connection reliability between opposing electrodes and insulation between adjacent electrodes in a circuit member.
　本発明によれば、対向する電極を有する回路部材同士の接続において、対向する電極間の接続信頼性の確保と回路部材内の隣り合う電極同士の絶縁性の確保とを両立できる絶縁被覆導電粒子及び異方導電フィルム、異方導電フィルムの製造方法、並びに、対向する電極間の接続信頼性と回路部材内の隣り合う電極同士の絶縁性とを両立できる接続構造体及び接続構造体の製造方法を提供することができる。 According to the present invention, in the connection between circuit members having opposing electrodes, the insulating coated conductive particles capable of ensuring both the connection reliability between the opposing electrodes and the insulation between adjacent electrodes in the circuit member. And anisotropic conductive film, method for manufacturing anisotropic conductive film, and connection structure capable of achieving both connection reliability between opposing electrodes and insulation between adjacent electrodes in a circuit member, and method for manufacturing connection structure Can be provided.
（ａ）は本発明に係る絶縁被覆導電粒子の一実施形態を示す図であり、（ｂ）は（ａ）に示される中心軸Ｐに沿った断面を模式的に示す図である。(A) is a figure which shows one Embodiment of the insulation coating electrically-conductive particle which concerns on this invention, (b) is a figure which shows typically the cross section along the central axis P shown by (a). 本発明に係る絶縁被覆導電粒子における最大径及び最小径について説明する図である。It is a figure explaining the maximum diameter and the minimum diameter in the insulation coating electroconductive particle which concerns on this invention. （ａ）は本発明に係る異方導電フィルムの一実施形態を示す模式的断面図であり、（ｂ）は異方導電フィルムの要部拡大模式図である。(A) is typical sectional drawing which shows one Embodiment of the anisotropic conductive film which concerns on this invention, (b) is a principal part expansion schematic diagram of an anisotropic conductive film. 本発明に係る異方導電フィルムの製造工程を示す模式的断面図である。It is typical sectional drawing which shows the manufacturing process of the anisotropic conductive film which concerns on this invention. 図４の後続の工程を示す模式的断面図である。FIG. 5 is a schematic cross-sectional view showing a step subsequent to FIG. 4. 図５の工程を経て得られる異方導電フィルムを示す模式的断面図である。It is typical sectional drawing which shows the anisotropic conductive film obtained through the process of FIG. 絶縁被覆導電粒子の配列の例を示す図である。It is a figure which shows the example of the arrangement | sequence of insulation coating electrically-conductive particle. 本発明に係る接続構造体の一実施形態を示す模式的断面図である。It is a typical sectional view showing one embodiment of a connection structure concerning the present invention. 図８に示した接続構造体の製造工程を示す模式的断面図である。It is typical sectional drawing which shows the manufacturing process of the connection structure shown in FIG. 図９の後続の工程を示す模式的断面図である。FIG. 10 is a schematic cross-sectional view showing a step subsequent to FIG. 9.
　以下、図面を参照しながら、本発明に係る絶縁被覆導電粒子、異方導電フィルム、異方導電フィルムの製造方法、接続構造体及び接続構造体の製造方法の好適な実施形態について詳細を説明する。 Hereinafter, with reference to the drawings, preferred embodiments of the insulating coated conductive particles, the anisotropic conductive film, the anisotropic conductive film manufacturing method, the connection structure, and the connection structure manufacturing method according to the present invention will be described in detail. .
［絶縁被覆導電粒子の構成］
　図１の（ａ）は本発明に係る絶縁被覆導電粒子の一実施形態の外観を示す図であり、図１の（ｂ）は（ａ）に示される中心軸Ｐに沿った断面を模式的に示す図である。絶縁被覆導電粒子１０は、導電性を有する基材粒子１と、基材粒子１の表面を被覆する絶縁性微粒子２とを備えて構成される。中心軸Ｐは、基材粒子１の中心を通る軸を意味する。 [Configuration of insulating coated conductive particles]
FIG. 1A is a view showing the appearance of an embodiment of the insulating coated conductive particles according to the present invention, and FIG. 1B is a schematic cross-sectional view along the central axis P shown in FIG. FIG. The insulating coated conductive particle 10 includes a conductive base particle 1 and insulating fine particles 2 that cover the surface of the base particle 1. The central axis P means an axis passing through the center of the base particle 1.
　基材粒子１は、コア粒子と、コア粒子の表面の少なくとも一部を被覆する金属層とから構成されるコアシェル型の粒子であってよい。例えば、コア粒子をめっきにより金属で被覆したものが挙げられる。 The base particle 1 may be a core-shell type particle composed of a core particle and a metal layer covering at least a part of the surface of the core particle. For example, what coated the core particle with the metal by plating is mentioned.
　コア粒子は、金属コア粒子、有機コア粒子及び無機コア粒子のいずれかを用いることができる。導通性の点で、有機コア粒子を用いることが好ましい。 As the core particles, any of metal core particles, organic core particles, and inorganic core particles can be used. From the viewpoint of conductivity, it is preferable to use organic core particles.
　有機コア粒子の材質は、特に限定されないが、例えば、ポリメチルメタクリレート、ポリメチルアクリレート等のアクリル樹脂、ポリエチレン、ポリプロピレン、ポリイソブチレン、ポリブタジエン等のポリオレフィン樹脂などが挙げられる。 The material of the organic core particles is not particularly limited, and examples thereof include acrylic resins such as polymethyl methacrylate and polymethyl acrylate, and polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polybutadiene.
　有機コア粒子をめっき等で被覆する場合、その金属としては、金、銀、銅、白金、亜鉛、鉄、パラジウム、ニッケル、錫、クロム、チタン、アルミニウム、コバルト、ゲルマニウム、カドミウム等の金属、ＩＴＯ、及びはんだ等の金属化合物などが挙げられる。 When the organic core particles are coated by plating, the metals include gold, silver, copper, platinum, zinc, iron, palladium, nickel, tin, chromium, titanium, aluminum, cobalt, germanium, cadmium and other metals, ITO And metal compounds such as solder.
　有機コア粒子を被覆する金属層の構造は特に限定されないが、導通性の点で、最外層がニッケル層であることが好ましい。また、導通性の点で、最外層が突起（又は凸部）を有することが好ましい。ニッケル層の内側に銅等の金属層が更に設けられていてもよい。 The structure of the metal layer covering the organic core particles is not particularly limited, but the outermost layer is preferably a nickel layer in terms of conductivity. Moreover, it is preferable that an outermost layer has a processus | protrusion (or convex part) at the point of electroconductivity. A metal layer such as copper may be further provided inside the nickel layer.
　基材粒子１の平均一次粒子径は、接続する電極高さのばらつきを吸収できる点、及び導通信頼性と絶縁信頼性との両立の観点から、１μｍ以上１０μｍ以下であることが好ましく、２μｍ以上５μｍ以下であることがより好ましく、２μｍ以上３μｍ以下であることが更に好ましい。 The average primary particle diameter of the base particle 1 is preferably 1 μm or more and 10 μm or less, from the viewpoint of being able to absorb variations in the height of the electrode to be connected, and compatibility between conduction reliability and insulation reliability. It is more preferably 5 μm or less, and further preferably 2 μm or more and 3 μm or less.
　絶縁性微粒子２は、無機酸化物微粒子、有機微粒子などを用いることができ、絶縁性及び導通性等の所望の特性に応じて適宜選択することができる。絶縁性微粒子２は、有機ポリマーを含むコア微粒子と、コア微粒子の表面の少なくとも一部を被覆するシェル層とから構成されるコアシェル型の粒子を用いることが好ましい。シェル層の材質は、例えば架橋ポリシロキサンが挙げられる。 The insulating fine particles 2 can be inorganic oxide fine particles, organic fine particles, and the like, and can be appropriately selected according to desired characteristics such as insulation and conductivity. The insulating fine particles 2 are preferably core-shell type particles composed of core fine particles containing an organic polymer and a shell layer covering at least a part of the surface of the core fine particles. Examples of the material of the shell layer include cross-linked polysiloxane.
　絶縁性微粒子２の平均一次粒子径は、導通信頼性と絶縁信頼性との両立の観点から、１００ｎｍ以上５００ｎｍ以下であることが好ましく、２００ｎｍ以上４５０ｎｍ以下であることがより好ましく、２５０ｎｍ以上３５０ｎｍ以下であることが更に好ましい。特に、絶縁性微粒子２の平均一次粒子径が２５０ｎｍ以上であれば、対向する電極を有する回路部材間の接続において絶縁被覆導電粒子１０同士が凝集した場合であっても、隣り合う回路電極間の絶縁性を充分に確保することが容易となり、３５０ｎｍ以下であれば、後述する単位面積当たりの絶縁性微粒子数が少ない疎領域に絶縁性微粒子が存在していても、対向回路間の導通を充分に確保することが容易となる。 The average primary particle diameter of the insulating fine particles 2 is preferably 100 nm or more and 500 nm or less, more preferably 200 nm or more and 450 nm or less, and more preferably 250 nm or more and 350 nm or less, from the viewpoint of compatibility between conduction reliability and insulation reliability. More preferably. In particular, if the average primary particle diameter of the insulating fine particles 2 is 250 nm or more, even when the insulating coated conductive particles 10 are aggregated in the connection between the circuit members having the opposing electrodes, the adjacent circuit electrodes are adjacent to each other. It becomes easy to ensure sufficient insulation, and if it is 350 nm or less, even if insulating fine particles exist in a sparse region where the number of insulating fine particles per unit area described later is small, sufficient conduction between opposing circuits is achieved. It is easy to ensure.
　本実施形態の絶縁被覆導電粒子１０は、単位面積当たりの絶縁性微粒子数が少ない若しくは０である粗領域と、粗領域よりも単位面積当たりの絶縁性微粒子数が多い密領域とを有することができる。 The insulating coated conductive particles 10 of the present embodiment may have a rough region where the number of insulating fine particles per unit area is small or zero and a dense region where the number of insulating fine particles per unit area is larger than that of the rough region. it can.
　絶縁被覆導電粒子１０は、図１に示されるように、上記基材粒子１の中心を通る中心軸Ｐが通る上記粗領域を２つ有することが好ましい。言い換えると、絶縁被覆導電粒子１０は、基材粒子１を二つの平行な平面で切ったときの２つの球冠領域に粗領域を有し、球帯領域に密領域を有することが好ましい。さらに、言い換えると、絶縁被覆導電粒子１０は、基材粒子１を二つの平行な平面で切ったときの球帯領域に絶縁性微粒子２が偏在していることが好ましい。 As shown in FIG. 1, the insulating coated conductive particles 10 preferably have two rough regions through which the central axis P passing through the center of the base particle 1 passes. In other words, the insulating coated conductive particles 10 preferably have a rough region in two spherical regions when the base particle 1 is cut by two parallel planes, and a dense region in the spherical region. Furthermore, in other words, it is preferable that the insulating coated conductive particles 10 have the insulating fine particles 2 unevenly distributed in a spherical zone region when the base particle 1 is cut by two parallel planes.
　このような絶縁被覆導電粒子１０は、導電性を有する基材粒子１と、該基材粒子１の表面を被覆する絶縁性微粒子２とを備える複合粒子の、基材粒子１を二つの平行な平面で切ったときの２つの球冠領域にある絶縁性微粒子２の一部又は全部を除去することにより得ることができる。 Such insulating coated conductive particles 10 are composed of composite particles comprising conductive base particles 1 and insulating fine particles 2 covering the surface of the base particles 1. It can be obtained by removing part or all of the insulating fine particles 2 in the two spherical crown regions when cut in a plane.
　なお、本実施形態において、粗領域と密領域との境界は必ずしも明確である必要はなく、粗領域と密領域との間に単位面積当たりの絶縁性微粒子数が粗領域よりも多く且つ密領域よりも少ない中間領域が設けられていてもよく、粗領域から密領域にかけて単位面積当たりの絶縁性微粒子数が増加するようにそれぞれの領域が設けられていてもよい。 In this embodiment, the boundary between the coarse region and the dense region is not necessarily clear, and the number of insulating fine particles per unit area is larger than that in the coarse region between the coarse region and the dense region. Fewer intermediate regions may be provided, and each region may be provided so that the number of insulating fine particles per unit area increases from the coarse region to the dense region.
　絶縁被覆導電粒子１０は、対向回路間の接続時の低抵抗化の観点から、絶縁性微粒子２の粒子密度が０個／μｍ２～２．０個／μｍ２である粗領域を有することが好ましく、０個／μｍ２～１．０個／μｍ２である粗領域を有することがより好ましく、０個／μｍ２～０．５個／μｍ２である粗領域を有することが更に好ましい。また、基材粒子１の表面積をＳ０μｍ２としたときに、上記の粗領域が、０．５×Ｓ０μｍ２以上あることが好ましく、０．７×Ｓ０μｍ２以上あることがより好ましい。 Insulated coating conductive particles 10, from the viewpoint of low resistance when connecting between opposing circuits, have a coarse area particle density of the insulating fine particles 2 is at 0 / [mu] m 2 ~ 2.0 units / [mu] m 2 It is more preferable to have a rough region of 0 / μm 2 to 1.0 / μm 2 , and it is even more preferable to have a rough region of 0 / μm 2 to 0.5 / μm 2 . In addition, when the surface area of the base particle 1 is S 0 μm 2 , the rough region is preferably 0.5 × S 0 μm 2 or more, and preferably 0.7 × S 0 μm 2 or more. More preferred.
　絶縁被覆導電粒子１０は、隣接回路間の絶縁性向上の観点から、絶縁性微粒子２の粒子密度が２．０個／μｍ２～５．０個／μｍ２である密領域を有することが好ましく、２．５個／μｍ２～４．５個／μｍ２である密領域を有することがより好ましく、３．０個／μｍ２～３．５個／μｍ２である密領域を有することが更に好ましい。また、基材粒子の表面積をＳ０μｍ２としたときに、上記の密領域が、０．２×Ｓ０μｍ２以上あることが好ましく、０．３×Ｓ０μｍ２以上あることがより好ましい。 Insulated coating conductive particles 10 preferably has a dense region in terms of insulation improvement, particle density of the insulating fine particles 2 is 2.0 pieces / [mu] m 2 ~ 5.0 units / [mu] m 2 between adjacent circuit It is more preferable to have a dense region of 2.5 / μm 2 to 4.5 / μm 2 , and to have a dense region of 3.0 / μm 2 to 3.5 / μm 2. Further preferred. Further, when the surface area of the base particle is S 0 μm 2 , the dense region is preferably 0.2 × S 0 μm 2 or more, and more preferably 0.3 × S 0 μm 2 or more. preferable.
　粗領域及び密領域における単位面積当たりの絶縁性微粒子数は、絶縁被覆導電粒子のＳＥＭ写真における基材粒子１の中心部（基材粒子１の外周円の直径の半分の長さを直径とし、当該外周円と同心円状の円）に存在する絶縁粒子数を計測することによって測定される。また、絶縁性微粒子２の粒子密度は、上記単位面積当たりの絶縁性微粒子数から算出することができる。単位面積は、基材粒子１の表面積をＳ０ｍｍ２としたときに、０．０４×Ｓ０ｍｍ２～０．２０×Ｓ０ｍｍ２のうちの所定の面積に設定することができ、０．１７×Ｓ０ｍｍ２に設定してもよい。 The number of insulating fine particles per unit area in the rough region and the dense region is the center part of the base particle 1 in the SEM photograph of the insulating coated conductive particle (the length is half the diameter of the outer circumference of the base particle 1, It is measured by measuring the number of insulating particles existing in a circle concentric with the outer circumference circle). The particle density of the insulating fine particles 2 can be calculated from the number of insulating fine particles per unit area. The unit area can be set to a predetermined area of 0.04 × S 0 mm 2 to 0.20 × S 0 mm 2 when the surface area of the base particle 1 is S 0 mm 2 , 0.17 × may be set to S 0 mm 2.
　対向回路間の接続時の電極同士と導電粒子が直接接触する面積を確保する観点から、絶縁被覆導電粒子１０は、基材粒子１の球冠領域に絶縁性微粒子数が０である領域が０．０５×Ｓ０μｍ２以上含まれることが好ましく、０．１０×Ｓ０μｍ２以上含まれることがより好ましい。 From the viewpoint of securing an area in which the conductive particles directly contact each other when the electrodes are connected to each other between the opposing circuits, the insulating coated conductive particles 10 have a region where the number of insulating fine particles is 0 in the spherical region of the base particle 1. 0.05 × S 0 μm 2 or more is preferable, and 0.10 × S 0 μm 2 or more is more preferable.
　絶縁被覆導電粒子１０における絶縁性微粒子２の被覆率は、３５～７５％が好ましく、４０～７５％がより好ましい。なお、縁性微粒子の被覆率は、絶縁被覆導電粒子のＳＥＭ写真における基材粒子１の中心部（基材粒子１の外周円の直径の半分の長さを直径とし、当該外周円と同心円状の円）を解析することによって測定される値を意味する。具体的には、上記ＳＥＭ写真における基材粒子１の中心部の総表面積をＷ（導電粒子の粒子径から算出した面積）、上記ＳＥＭ写真における基材粒子１の中心部のうち、絶縁性微粒子２で被覆されていると分析された部分の表面積をＰとしたときに、被覆率はＰ／Ｗ×１００（％）と表される。なお、本実施形態における上記被覆されていると分析された部分の表面積Ｐは、絶縁被覆導電粒子のＳＥＭ写真２００枚から求めた表面積の平均値である。 The coverage of the insulating fine particles 2 in the insulating coated conductive particles 10 is preferably 35 to 75%, more preferably 40 to 75%. The coverage of the edge fine particles is the center part of the base particle 1 in the SEM photograph of the insulating coated conductive particles (the half length of the diameter of the outer peripheral circle of the base particle 1 is the diameter, and concentric with the outer peripheral circle. The value measured by analyzing the circle. Specifically, the total surface area of the center part of the base particle 1 in the SEM photograph is W (area calculated from the particle diameter of the conductive particles), and the insulating fine particles in the center part of the base particle 1 in the SEM picture When the surface area of the portion analyzed to be covered with 2 is P, the coverage is expressed as P / W × 100 (%). In addition, the surface area P of the portion analyzed to be covered in the present embodiment is an average value of the surface areas obtained from 200 SEM photographs of the insulating coated conductive particles.
　絶縁被覆導電粒子１０の最小径Ｘ’は、導通特性の観点から、基材粒子１の直径以上、基材粒子１の直径及び絶縁性微粒子２の直径の合計値以下であることが好ましい。また、絶縁被覆導電粒子１０の最大径Ｙ’は、絶縁性の観点から、基材粒子１の直径及び２×（絶縁性微粒子２の直径）の合計値以上、基材粒子１の直径及び６×（絶縁性微粒子２の直径）の合計値以下であることが好ましい。なお、図２は、図１の（ｂ）に示される絶縁被覆導電粒子１０の最小径Ｘ’が基材粒子１の直径であり、最大径Ｙ’が基材粒子１の直径及び２×（絶縁性微粒子の直径）の合計である場合を示す。 The minimum diameter X ′ of the insulating coated conductive particle 10 is preferably not less than the diameter of the base particle 1 and not more than the total value of the diameter of the base particle 1 and the diameter of the insulating fine particles 2 from the viewpoint of conduction characteristics. Further, the maximum diameter Y ′ of the insulating coated conductive particles 10 is not less than the total value of the diameter of the base particle 1 and 2 × (the diameter of the insulating fine particles 2), from the viewpoint of insulation, It is preferable that it is below the total value of x (diameter of insulating fine particles 2). In FIG. 2, the minimum diameter X ′ of the insulating coated conductive particle 10 shown in FIG. 1B is the diameter of the base particle 1, and the maximum diameter Y ′ is the diameter of the base particle 1 and 2 × (2 × ( The case of the sum of the diameters of the insulating fine particles is shown.
　導通性と絶縁性とを両立する観点から、絶縁被覆導電粒子１０の最小径Ｘ’と最大径Ｙ’との比Ｘ’／Ｙ’は、０．４以上０．９以下であることが好ましい。Ｘ’／Ｙ’を０．４以上にすることで、回路部材のバンプ面積を小面積化した場合であっても、絶縁被覆導電粒子１０の捕捉性を確保しやすくなり、Ｘ’／Ｙ’を０．９以下にすることで、接続抵抗を低抵抗化しやすくなる。 From the viewpoint of achieving both conductivity and insulation, the ratio X ′ / Y ′ between the minimum diameter X ′ and the maximum diameter Y ′ of the insulating coated conductive particles 10 is preferably 0.4 or more and 0.9 or less. . By setting X ′ / Y ′ to 0.4 or more, even when the bump area of the circuit member is reduced, it becomes easy to ensure the trapping property of the insulating coated conductive particles 10, and X ′ / Y ′. By making the value 0.9 or less, the connection resistance can be easily reduced.
　上記のような絶縁被覆導電粒子１０を作製するには、各々の方法を用いることができる。例えば、（ｉ）基材粒子１をその粒子径と同じ隙間が設けられた平行板に充填し、充填された基材粒子１上に絶縁性微粒子２を付着させる方法、（ｉｉ）基材粒子１の表面全体を絶縁性微粒子２で被覆した複合粒子を用意し、この複合粒子の絶縁性微粒子２の一部を除去する方法などが挙げられる。 Each method can be used to produce the insulating coated conductive particles 10 as described above. For example, (i) a method in which base particles 1 are filled in parallel plates provided with the same gap as the particle diameter, and insulating fine particles 2 are adhered onto the filled base particles 1; (ii) base particles Examples include a method of preparing composite particles in which the entire surface of 1 is coated with insulating fine particles 2 and removing a part of the insulating fine particles 2 of the composite particles.
　（ｉ）で基材粒子１上に絶縁性微粒子２を付着させる方法としては、例えば、基材粒子１と絶縁性微粒子２を平行板間に充填した後、有機溶剤や熱を用いて絶縁性微粒子２を基材粒子１に溶着させる方法が挙げられる。 As a method of attaching the insulating fine particles 2 on the base particles 1 in (i), for example, the base particles 1 and the insulating fine particles 2 are filled between parallel plates, and then insulative using an organic solvent or heat. The method of welding the microparticles | fine-particles 2 to the base particle 1 is mentioned.
　（ｉｉ）で基材粒子１の表面全体を絶縁性微粒子２で被覆した複合粒子を得る方法としては、例えば、基材粒子１にポリエチレンイミンなどの帯電処理材を塗布し、静電気的な力で絶縁性微粒子２を付着させる手法、基材粒子１と絶縁性微粒子２に相互に結合可能な官能基を導入し、化学結合にて複合粒子を得る方法が挙げられる。また、絶縁性微粒子２の一部を除去する手段としては、粘着テープ等を用いて、複合粒子の球冠領域の絶縁性微粒子２を取り除く手法が簡便な手法として挙げられる。さらに、後述する本発明に係る異方導電フィルムの製造方法は、異方導電フィルムの作製中に絶縁被覆導電粒子１０を作製することができ、特に有用な方法である。 As a method for obtaining composite particles in which the entire surface of the base particle 1 is coated with the insulating fine particles 2 in (ii), for example, a charging treatment material such as polyethyleneimine is applied to the base particle 1 and electrostatic force is applied. Examples thereof include a method of attaching the insulating fine particles 2 and a method of obtaining composite particles by chemical bonding by introducing functional groups capable of mutual bonding to the base particle 1 and the insulating fine particles 2. Further, as a means for removing a part of the insulating fine particles 2, a method of removing the insulating fine particles 2 in the spherical crown region of the composite particles using an adhesive tape or the like can be mentioned as a simple method. Furthermore, the method for producing an anisotropic conductive film according to the present invention, which will be described later, is a particularly useful method because the insulating coated conductive particles 10 can be produced during the production of the anisotropic conductive film.
［異方導電フィルムの構成］
　図３の（ａ）は、本発明に係る異方導電フィルムの一実施形態を示す模式的断面図であり、図３の（ｂ）は異方導電フィルムの要部拡大模式図である。図に示される剥離フィルム付き異方導電フィルム１１は、剥離フィルム１２と、絶縁被覆導電粒子１０及び接着剤成分が含まれる導電性接着剤層（異方導電フィルム）１３とから構成されている。絶縁被覆導電粒子１０は導電性接着剤層１３中に分散している。本明細書においては、導電性接着剤層１３を厚み方向と垂直な面で切断したときの断面に絶縁被覆導電粒子１０が含まれていない領域を接着剤領域といい、絶縁被覆導電粒子１０が含まれている領域を導電領域という場合もある。 [Configuration of anisotropic conductive film]
FIG. 3A is a schematic cross-sectional view showing an embodiment of the anisotropic conductive film according to the present invention, and FIG. 3B is an enlarged schematic view of the main part of the anisotropic conductive film. The anisotropic conductive film 11 with a peeling film shown by the figure is comprised from the peeling film 12, and the conductive adhesive layer (anisotropic conductive film) 13 in which the insulation coating electrically-conductive particle 10 and an adhesive agent component are contained. The insulating coating conductive particles 10 are dispersed in the conductive adhesive layer 13. In the present specification, a region where the insulating coating conductive particles 10 are not included in a cross section when the conductive adhesive layer 13 is cut along a plane perpendicular to the thickness direction is referred to as an adhesive region, and the insulating coating conductive particles 10 are The included region may be referred to as a conductive region.
　剥離フィルム１２は、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン、ポリプロピレン等によって形成されている。剥離フィルム１２には、任意の充填剤を含有させてもよい。また、剥離フィルム１２の表面には、離型処理又はプラズマ処理等が施されていてもよい。 The release film 12 is made of, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, or the like. The release film 12 may contain an arbitrary filler. Further, the surface of the release film 12 may be subjected to a mold release process or a plasma process.
　導電性接着剤層１３に含まれる接着剤成分としては、モノマー及び硬化剤が挙げられる。モノマーは、カチオン重合性化合物、アニオン重合性化合物又はラジカル重合性化合物を用いることができる。カチオン重合性化合物及びアニオン重合性化合物としては、エポキシ系化合物が挙げられる。 Examples of the adhesive component contained in the conductive adhesive layer 13 include a monomer and a curing agent. As the monomer, a cationic polymerizable compound, an anion polymerizable compound, or a radical polymerizable compound can be used. Examples of the cationic polymerizable compound and the anionic polymerizable compound include epoxy compounds.
　エポキシ系化合物としては、エピクロルヒドリンと、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤ等のビスフェノール化合物とから誘導されるビスフェノール型エポキシ樹脂、エピクロルヒドリンと、フェノールノボラック又はクレゾールノボラック等のノボラック樹脂とから誘導されるエポキシノボラック樹脂、並びに、グリシジルアミン、グリシジルエーテル、ビフェニル、脂環式等の１分子内に２個以上のグリシジル基を有する各種のエポキシ化合物などを用いることができる。 Examples of epoxy compounds include epphenol hydrins and bisphenol type epoxy resins derived from bisphenol compounds such as bisphenol A, bisphenol F or bisphenol AD, and epoxy novolacs derived from epichlorohydrin and novolac resins such as phenol novolac or cresol novolac. Resin and various epoxy compounds having two or more glycidyl groups in one molecule such as glycidylamine, glycidyl ether, biphenyl, and alicyclic can be used.
　ラジカル重合性化合物としては、ラジカルにより重合する官能基を有する化合物を用いることができ、例えば、（メタ）アクリレート等のアクリルモノマー、マレイミド化合物、スチレン誘導体などが挙げられる。ラジカル重合性化合物は、モノマー又はオリゴマーのいずれの状態でも使用することができ、モノマーとオリゴマーとを混合して使用してもよい。 As the radical polymerizable compound, a compound having a functional group that is polymerized by radicals can be used, and examples thereof include acrylic monomers such as (meth) acrylate, maleimide compounds, and styrene derivatives. The radical polymerizable compound can be used in any state of a monomer or an oligomer, and a monomer and an oligomer may be mixed and used.
　モノマーは、１種を単独で用いてもよく、２種以上を併用してもよい。 Monomers may be used alone or in combination of two or more.
　エポキシ系化合物を用いる場合は、硬化剤として、イミダゾール系、ヒドラジド系、三フッ化ホウ素－アミン錯体、スルホニウム塩、アミンイミド、ポリアミンの塩、ジシアンジアミド等が挙げられる。これらの硬化剤は、ポリウレタン系、ポリエステル系の高分子物質等で被覆してマイクロカプセル化されていることが、可使時間が延長される点で好適である。 In the case of using an epoxy compound, examples of the curing agent include imidazole, hydrazide, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide and the like. It is preferable that these curing agents are coated with a polyurethane-based or polyester-based polymer substance and are microencapsulated from the viewpoint of extending the pot life.
　エポキシ系化合物と併用される硬化剤は、目的とする接続温度、接続時間、保存安定性等により適宜選定される。硬化剤は、高反応性の点から、エポキシ系化合物及び硬化剤が含まれる組成物としたときに、そのゲルタイムが所定の温度で１０秒以内となることが好ましく、保存安定性の点から、４０℃で１０日間恒温槽に保管後の組成物とのゲルタイムに差がないことが好ましい。このような点から、硬化剤はスルホニウム塩であることが好ましい。 The curing agent used in combination with the epoxy compound is appropriately selected depending on the intended connection temperature, connection time, storage stability, and the like. From the viewpoint of high reactivity, when the curing agent is a composition containing an epoxy compound and a curing agent, the gel time is preferably within 10 seconds at a predetermined temperature, from the viewpoint of storage stability, It is preferable that there is no difference in gel time with the composition after storage in a thermostatic bath at 40 ° C. for 10 days. From such points, the curing agent is preferably a sulfonium salt.
　アクリルモノマーを用いる場合は、硬化剤として、過酸化化合物、アゾ系化合物等の加熱により分解して遊離ラジカルを発生するものが挙げられる。 In the case of using an acrylic monomer, examples of the curing agent include those that decompose by heating, such as peroxide compounds and azo compounds, to generate free radicals.
　アクリルモノマーと併用される硬化剤は、目的とする接続温度、接続時間、保存安定性等により適宜選定される。硬化剤は、高反応性と保存安定性の点から、半減期１０時間の温度が４０℃以上かつ半減期１分の温度が１８０℃以下の有機過酸化物又はアゾ系化合物が好ましく、半減期１０時間の温度が６０℃以上かつ半減期１分の温度が１７０℃以下の有機過酸化物又はアゾ系化合物がより好ましい。 The curing agent used in combination with the acrylic monomer is appropriately selected depending on the intended connection temperature, connection time, storage stability, and the like. From the viewpoint of high reactivity and storage stability, the curing agent is preferably an organic peroxide or an azo compound having a half-life of 10 hours at a temperature of 40 ° C. or more and a half-life of 1 minute at a temperature of 180 ° C. or less. An organic peroxide or an azo compound having a 10-hour temperature of 60 ° C. or more and a half-life of 1 minute is 170 ° C. or less is more preferable.
　硬化剤は、１種を単独で用いてもよく、２種以上を併用してもよい。導電性接着剤層１３には、分解促進剤、抑制剤等を更に含有させてもよい。 One curing agent may be used alone, or two or more curing agents may be used in combination. The conductive adhesive layer 13 may further contain a decomposition accelerator, an inhibitor, and the like.
　硬化剤の配合量は、エポキシ系化合物及びアクリルモノマーのいずれを用いた場合においても、接続時間を１０秒以下としたときに充分な反応率を得る観点から、モノマーと後述のフィルム形成材との合計１００質量部に対して、０．１質量部～４０質量部とすることが好ましく、１質量部～３５質量部とすることがより好ましい。硬化剤の配合量が０．１質量部以上であると、充分な反応率を得ることができ、良好な接着強度及び小さな接続抵抗が得られやすくなり、４０質量部以下であると、導電性接着剤層１３の流動性が低下して接続抵抗が上昇することを防止しやすくなり、また、異方導電フィルムの保存安定性を確保しやすくなる。 The blending amount of the curing agent is such that the monomer and the film-forming material described later can be obtained from the viewpoint of obtaining a sufficient reaction rate when the connection time is 10 seconds or less, regardless of whether the epoxy compound or the acrylic monomer is used. The amount is preferably 0.1 to 40 parts by mass, more preferably 1 to 35 parts by mass with respect to 100 parts by mass in total. When the blending amount of the curing agent is 0.1 parts by mass or more, a sufficient reaction rate can be obtained, and good adhesive strength and small connection resistance can be easily obtained. It becomes easy to prevent the fluidity of the adhesive layer 13 from decreasing and the connection resistance from increasing, and to ensure the storage stability of the anisotropic conductive film.
　導電性接着剤層１３はフィルム形成材を含んでいてもよい。フィルム形成材は、上記のモノマー及び硬化剤が含まれる粘度の低い組成物の取り扱いを容易にする作用を有するポリマーである。フィルム形成材を用いることによって、フィルムが容易に裂けたり、割れたり、べたついたりすることを抑制でき、取り扱いが容易な異方導電フィルム１１が得られる。 The conductive adhesive layer 13 may contain a film forming material. The film-forming material is a polymer that has an effect of facilitating the handling of a low-viscosity composition containing the monomer and the curing agent. By using the film forming material, it is possible to suppress the film from being easily split, cracked, or sticky, and the anisotropic conductive film 11 that is easy to handle can be obtained.
　フィルム形成材としては、熱可塑性樹脂を好適に用いることができる。例えば、フェノキシ樹脂、ポリビニルホルマール樹脂、ポリスチレン樹脂、ポリビニルブチラール樹脂、ポリエステル樹脂、ポリアミド樹脂、キシレン樹脂、ポリウレタン樹脂、ポリアクリル樹脂、ポリエステルウレタン樹脂等が挙げられる。これらのポリマー中には、シロキサン結合又はフッ素置換基が含まれていてもよい。上記の樹脂の中でも、接着強度、相溶性、耐熱性、及び機械強度の観点から、フェノキシ樹脂を用いることが好ましい。 A thermoplastic resin can be suitably used as the film forming material. Examples thereof include phenoxy resin, polyvinyl formal resin, polystyrene resin, polyvinyl butyral resin, polyester resin, polyamide resin, xylene resin, polyurethane resin, polyacrylic resin, and polyester urethane resin. These polymers may contain siloxane bonds or fluorine substituents. Among the above resins, a phenoxy resin is preferably used from the viewpoints of adhesive strength, compatibility, heat resistance, and mechanical strength.
　上記の熱可塑性樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。 The above thermoplastic resins may be used alone or in combination of two or more.
　熱可塑性樹脂は、分子量が大きいほどフィルム形成性が容易に得られ、また、異方導電フィルム１１の流動性に影響する溶融粘度を広範囲に設定できる。熱可塑性樹脂の重量平均分子量は、５０００～１５００００であることが好ましく、１００００～８００００であることがより好ましい。熱可塑性樹脂の重量平均分子量が５０００以上であると良好なフィルム形成性が得られやすく、１５００００以下であると他の成分との良好な相溶性が得られやすくなる。 The thermoplastic resin can be easily formed as the molecular weight increases, and the melt viscosity that affects the fluidity of the anisotropic conductive film 11 can be set in a wide range. The weight average molecular weight of the thermoplastic resin is preferably 5000 to 150,000, and more preferably 10,000 to 80,000. When the weight average molecular weight of the thermoplastic resin is 5000 or more, good film formability is easily obtained, and when it is 150,000 or less, good compatibility with other components is easily obtained.
　なお、本発明において、重量平均分子量は、下記の条件に従って、ゲル浸透クロマトグラフ（ＧＰＣ）より標準ポリスチレンによる検量線を用いて測定した値をいう。
（測定条件）
　装置：東ソー株式会社製　ＧＰＣ－８０２０
　検出器：東ソー株式会社製　ＲＩ－８０２０
　カラム：日立化成株式会社製　Ｇｅｌｐａｃｋ　ＧＬＡ１６０Ｓ＋ＧＬＡ１５０Ｓ
　試料濃度：１２０ｍｇ／３ｍＬ
　溶媒：テトラヒドロフラン
　注入量：６０μＬ
　圧力：２．９４×１０６Ｐａ（３０ｋｇｆ／ｃｍ２）
　流量：１．００ｍＬ／ｍｉｎ In the present invention, the weight average molecular weight is a value measured from a gel permeation chromatograph (GPC) using a standard polystyrene calibration curve according to the following conditions.
(Measurement condition)
Equipment: GPC-8020 manufactured by Tosoh Corporation
Detector: RI-8020 manufactured by Tosoh Corporation
Column: Hitachi Chemical Co., Ltd. Gelpack GLA160S + GLA150S
Sample concentration: 120 mg / 3 mL
Solvent: Tetrahydrofuran Injection volume: 60 μL
Pressure: 2.94 × 106 Pa (30 kgf / cm 2 )
Flow rate: 1.00 mL / min
　フィルム形成材の配合量は、モノマー、硬化剤及びフィルム形成材の総量を基準として５質量％～８０質量％であることが好ましく、１５質量％～７０質量％であることがより好ましい。フィルム形成材の配合量を５質量％以上とすることで良好なフィルム形成性が得られやすくなり、８０質量％以下とすることで導電性接着剤層１３（特には接着剤領域）が良好な流動性を示す傾向にある。 The blending amount of the film forming material is preferably 5% by mass to 80% by mass, and more preferably 15% by mass to 70% by mass based on the total amount of the monomer, the curing agent and the film forming material. When the blending amount of the film forming material is 5% by mass or more, good film formability is easily obtained, and when it is 80% by mass or less, the conductive adhesive layer 13 (particularly, the adhesive region) is favorable. It tends to show fluidity.
　また、導電性接着剤層１３には、充填剤、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤、カップリング剤、フェノール樹脂、メラミン樹脂、イソシアネート類等を更に含有していてもよい。 Further, the conductive adhesive layer 13 is filled with a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, an isocyanate, and the like. Furthermore, you may contain.
　導電性接着剤層１３が充填剤を含有する場合、接続信頼性の向上が更に期待できる。充填剤の最大径は、絶縁被覆導電粒子１０の最小径未満であることが好ましい。導電性接着剤層１３における充填剤の含有量は、導電性接着剤層１００体積部に対して５体積部～６０体積部であることが好ましい。この範囲であれば、添加量に見合った信頼性向上の効果が得られやすくなる。 When the conductive adhesive layer 13 contains a filler, further improvement in connection reliability can be expected. The maximum diameter of the filler is preferably less than the minimum diameter of the insulating coated conductive particles 10. The filler content in the conductive adhesive layer 13 is preferably 5 to 60 parts by volume with respect to 100 parts by volume of the conductive adhesive layer. If it is this range, it will become easy to acquire the effect of the reliability improvement according to the addition amount.
　本実施形態の導電性接着剤層（異方導電フィルム）１３において、絶縁被覆導電粒子１０は導電性接着剤層１３の両主面の一方面側に偏在していることが好ましい。図３の（ｂ）に示すように、絶縁被覆導電粒子１０が導電性接着剤層１３の離型フィルム１２が設けられている一方面側に偏在している場合、絶縁被覆導電粒子１０と一方面との最短距離は０μｍより大きく１μｍ以下であってもよい。最短距離Ｄを上記範囲内にすることで、圧着時の絶縁被覆導電粒子１０の流動を抑制することができ、絶縁被覆導電粒子１０の捕捉性能を向上させることができる。 In the conductive adhesive layer (anisotropic conductive film) 13 of the present embodiment, the insulating coated conductive particles 10 are preferably unevenly distributed on one side of both main surfaces of the conductive adhesive layer 13. As shown in FIG. 3B, when the insulating coated conductive particles 10 are unevenly distributed on the one surface side where the release film 12 of the conductive adhesive layer 13 is provided, the insulating coated conductive particles 10 and the insulating coated conductive particles 10 The shortest distance to the direction may be greater than 0 μm and 1 μm or less. By setting the shortest distance D within the above range, the flow of the insulating coated conductive particles 10 at the time of pressure bonding can be suppressed, and the capturing performance of the insulating coated conductive particles 10 can be improved.
　また、図３の（ｂ）に示すように、絶縁被覆導電粒子１０は、基材粒子１の中心を通り且つ導電性接着剤層１３の厚み方向に平行な軸Ｐ’が２つの粗領域若しくは絶縁性微粒子２の一部又は全部が除去された２つの球冠領域を通るように配されている、又は、平行な軸Ｐ’と上記二つの平行な平面（２つの球冠領域及び球帯領域を分ける平面）とが直交するように配されていることが好ましい。このような異方導電フィルム１１において、絶縁被覆導電粒子１０の、軸Ｐ’の方向における粒子径Ｘと、軸Ｐ’と直交する方向における粒子径Ｙとは、Ｙ＞Ｘの関係となる。なお、軸Ｐ’と直交する方向は、異方導電フィルム１１が帯状である場合にはその長手方向ということもできる。 Further, as shown in FIG. 3B, the insulating coated conductive particles 10 have two rough regions in which the axis P ′ passing through the center of the base particle 1 and parallel to the thickness direction of the conductive adhesive layer 13 is two rough regions or The insulating fine particles 2 are arranged so as to pass through the two spherical crown regions from which part or all of the insulating fine particles 2 have been removed, or the parallel axis P ′ and the two parallel planes (the two spherical crown regions and the spherical zone). It is preferable that they are arranged so as to be orthogonal to the plane dividing the region. In such an anisotropic conductive film 11, the particle diameter X in the direction of the axis P ′ and the particle diameter Y in the direction perpendicular to the axis P ′ of the insulating coated conductive particles 10 have a relationship of Y> X. The direction orthogonal to the axis P ′ can also be referred to as the longitudinal direction when the anisotropic conductive film 11 has a strip shape.
　また、上記粒子径Ｘは、基材粒子１の直径以上、基材粒子１の直径及び絶縁性微粒子２の直径の合計値以下であることが好ましい。粒子径Ｘがこのような条件を満たす場合、絶縁被覆導電粒子１０は、軸Ｐ’を垂線とする二つの平行な平面で切ったときの２つの球冠領域の少なくとも一方に、絶縁性微粒子２が存在しない領域を有する状態となる。この場合、対向する電極を有する回路部材同士の接続において、対向する電極間に絶縁被覆導電粒子１０が捕捉されるときに、絶縁被覆導電粒子１０の基材粒子１と電極との間に絶縁性微粒子２が挟まれることが抑制され、低抵抗接続が容易となる。 The particle diameter X is preferably not less than the diameter of the base particle 1 and not more than the total value of the diameter of the base particle 1 and the diameter of the insulating fine particles 2. In the case where the particle diameter X satisfies such a condition, the insulating coated conductive particles 10 are formed on at least one of the two spherical crown regions when they are cut by two parallel planes having the axis P ′ as a perpendicular line. It will be in the state which has the area | region which does not exist. In this case, in connection between circuit members having opposing electrodes, when the insulating coated conductive particles 10 are captured between the facing electrodes, the insulating property is provided between the base particle 1 of the insulating coated conductive particles 10 and the electrodes. The fine particles 2 are prevented from being sandwiched, and a low resistance connection is facilitated.
　また、上記粒子径Ｙは、基材粒子１の直径及び２×（絶縁性微粒子２の直径）の合計値以上、２×（基材粒子１の直径）の値以下であることが好ましい。粒子径Ｙがこのような条件を満たす場合、絶縁被覆導電粒子１０は、軸Ｐ’を垂線とする二つの平行な平面で切ったときの球帯領域に、絶縁性微粒子２で被覆された領域を有しており、対向する電極を有する回路部材同士の接続において絶縁被覆導電粒子１０の凝集が発生しても、凝集粒子による短絡を好適に抑制することができる。なお、粒子径Ｙが大きくなる程、短絡の抑制には効果的であるが、２×（基材粒子１の直径）の値以下であると、導電性接着剤層１３における絶縁被覆導電粒子１０の粒子密度の調整、及び圧着時の導電性接着剤層１３の流動性の制御の点で好ましい。 Further, the particle diameter Y is preferably not less than the total value of the diameter of the base particle 1 and 2 × (the diameter of the insulating fine particles 2) and not more than 2 × (the diameter of the base particle 1). In the case where the particle diameter Y satisfies such a condition, the insulating coated conductive particle 10 is a region covered with the insulating fine particles 2 in a spherical zone when cut by two parallel planes having the axis P ′ as a perpendicular line. Even if the insulation-coated conductive particles 10 are agglomerated in connection between circuit members having opposing electrodes, a short circuit due to the agglomerated particles can be suitably suppressed. The larger the particle diameter Y, the more effective the suppression of short-circuiting. However, when the particle diameter Y is equal to or smaller than 2 × (the diameter of the base particle 1), the insulating coated conductive particles 10 in the conductive adhesive layer 13 are used. It is preferable in terms of adjusting the particle density and controlling the fluidity of the conductive adhesive layer 13 during pressure bonding.
　また、導通性と絶縁性とを両立する観点から、上記粒子径Ｘと上記粒子径Ｙとの比Ｘ／Ｙが、０．４以上０．９以下であることが好ましい。Ｘ／Ｙが０．４以上であると、回路部材のバンプ面積を小面積化した場合であっても、絶縁被覆導電粒子１０の捕捉性を確保しやすくなり、Ｘ／Ｙが０．９以下であると、接続抵抗を低抵抗化しやすくなる。 Further, from the viewpoint of achieving both conductivity and insulation, the ratio X / Y between the particle diameter X and the particle diameter Y is preferably 0.4 or more and 0.9 or less. When X / Y is 0.4 or more, even when the bump area of the circuit member is reduced, it becomes easy to ensure the trapping property of the insulating coated conductive particles 10, and X / Y is 0.9 or less. If it is, it becomes easy to make a connection resistance low.
　本実施形態の導電性接着剤層（異方導電フィルム）１３においては、絶縁被覆導電粒子の８０％以上についての平均が上記の条件を満たしていることが好ましい。 In the conductive adhesive layer (anisotropic conductive film) 13 of the present embodiment, it is preferable that the average of 80% or more of the insulating coated conductive particles satisfies the above conditions.
　上記粒子径Ｘ、上記粒子径Ｙ、及び最短距離Ｄは、異方導電フィルム１１を、絶縁被覆導電粒子１０の基材粒子１の中心を通り、且つ導電性接着剤層１３の厚み方向に平行な面に沿って切断したときの断面を観察することにより確認することができる。 The particle diameter X, the particle diameter Y, and the shortest distance D pass through the anisotropic conductive film 11 through the center of the base particle 1 of the insulating coated conductive particle 10 and parallel to the thickness direction of the conductive adhesive layer 13. This can be confirmed by observing a cross section when cut along a smooth surface.
　断面観察は、収束イオンビーム（ＦＩＢ）、走査型電子顕微鏡（ＳＥＭ）、透過型電子顕微鏡（ＴＥＭ）などの加工・観察装置によって可能である。例えば、ＦＩＢを用いて、導電性接着剤層（異方導電フィルム）１３の断面を切削し、その後、ＳＥＭにて観察および測定することが可能である。具体的には、離型フィルム付き異方導電フィルム１１の離型フィルム１２側を導電性のカーボンテープを用いて、試料加工・観察用の冶具に固定する。その後、導電性接着剤層（異方導電フィルム）１３側から白金スパッタ処理を実施し、導電性接着剤層（異方導電フィルム）１３上に１０ｎｍの白金膜を形成する。収束イオンビーム（ＦＩＢ）を用いて、離型フィルム付き異方導電フィルム１１の導電性接着剤層１３側から加工を実施し、加工断面を走査型電子顕微鏡（ＳＥＭ）により観察する。 Cross-section observation is possible with a processing / observation device such as a focused ion beam (FIB), a scanning electron microscope (SEM), or a transmission electron microscope (TEM). For example, the cross-section of the conductive adhesive layer (anisotropic conductive film) 13 can be cut using FIB, and then observed and measured with an SEM. Specifically, the release film 12 side of the anisotropic conductive film 11 with a release film is fixed to a jig for sample processing / observation using a conductive carbon tape. Thereafter, a platinum sputtering process is performed from the conductive adhesive layer (anisotropic conductive film) 13 side to form a 10 nm platinum film on the conductive adhesive layer (anisotropic conductive film) 13. Using a focused ion beam (FIB), processing is performed from the side of the conductive adhesive layer 13 of the anisotropic conductive film 11 with a release film, and the processed cross section is observed with a scanning electron microscope (SEM).
　導電性接着剤層（異方導電フィルム）１３における接着剤領域の厚みは適宜設定することができ、例えば、導電領域の上記最短距離Ｄを満たす接着剤領域とは反対側の接着剤領域の厚みは、バンプ電極の高さに応じて適宜設定することができる。 The thickness of the adhesive region in the conductive adhesive layer (anisotropic conductive film) 13 can be set as appropriate. For example, the thickness of the adhesive region opposite to the adhesive region satisfying the shortest distance D of the conductive region. Can be appropriately set according to the height of the bump electrode.
　異方導電フィルムは、導電性接着剤層１３に、導電粒子を含有しない絶縁性接着剤層を積層した多層構成にすることも可能である。 The anisotropic conductive film may have a multilayer structure in which the conductive adhesive layer 13 is laminated with an insulating adhesive layer that does not contain conductive particles.
　絶縁性接着剤層は、導電性接着剤層１３と同様に、上述したモノマー、硬化剤及びフィルム形成材を含有することができ、充填剤、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤、カップリング剤、フェノール樹脂、メラミン樹脂、イソシアネート類等を更に含有していてもよい。 As with the conductive adhesive layer 13, the insulating adhesive layer can contain the above-described monomers, curing agent, and film-forming material, and includes a filler, a softening agent, an accelerator, an anti-aging agent, a colorant, It may further contain a flame retardant, a thixotropic agent, a coupling agent, a phenol resin, a melamine resin, isocyanates and the like.
　導電性接着剤層１３に絶縁性接着剤層を積層することで、異方導電フィルムに含まれる絶縁被覆導電粒子１０をフィルムの一方面側に偏在させることが容易になる。この場合、導電性接着剤層１３に由来する第１の接着剤領域／導電領域／第２の接着剤領域と、第２の接着剤領域に隣接し、絶縁性接着剤層に由来する第３の接着剤領域とから構成される異方導電フィルムを形成することができる。また、導電性接着剤層１３と絶縁性接着剤層の溶融粘度の差を調節することによって、回路接続時の絶縁被覆導電粒子１０及び接着剤領域の流動性を任意に調整することができる。 By laminating the insulating adhesive layer on the conductive adhesive layer 13, it becomes easy to make the insulating coated conductive particles 10 contained in the anisotropic conductive film unevenly distributed on one side of the film. In this case, the first adhesive region / conductive region / second adhesive region derived from the conductive adhesive layer 13 and the third adhesive layer adjacent to the second adhesive region and derived from the insulating adhesive layer. An anisotropic conductive film composed of the adhesive region can be formed. Further, by adjusting the difference in melt viscosity between the conductive adhesive layer 13 and the insulating adhesive layer, the fluidity of the insulating coated conductive particles 10 and the adhesive region at the time of circuit connection can be arbitrarily adjusted.
　調整方法としては、例えば、所定のガラス転移温度（Ｔｇ）を有するフィルム形成材を導電性接着剤層１３及び絶縁性接着剤層に含有させることが挙げられる。本実施形態においては、導電性接着剤層１３に含有させるフィルム形成材として、Ｔｇが６０～１８０℃の熱可塑性樹脂（特にはフェノキシ樹脂）を用い、絶縁性接着剤層に含有させるフィルム形成材として、Ｔｇが４０～１００℃の熱可塑性樹脂（特にはフェノキシ樹脂）を用いることが好ましい。なお、ガラス転移温度は、示差走査熱量計（ＤＳＣ）等の熱物性測定装置で測定される。例えば、フィルム成形材をアルミニウム製のサンプルパンに秤量し、空のアルミニウム製サンプルパンと同時に測定することで、熱量の差を計測する。この際、１度目の測定では、フィルム形成材の溶融等の影響により測定誤差が生じる場合があるため、２度目以降の測定データからガラス転移温度を測定することが好ましい。 As an adjustment method, for example, a film forming material having a predetermined glass transition temperature (Tg) is included in the conductive adhesive layer 13 and the insulating adhesive layer. In the present embodiment, a thermoplastic resin (particularly phenoxy resin) having a Tg of 60 to 180 ° C. is used as the film forming material to be contained in the conductive adhesive layer 13, and the film forming material to be contained in the insulating adhesive layer. It is preferable to use a thermoplastic resin (particularly a phenoxy resin) having a Tg of 40 to 100 ° C. The glass transition temperature is measured with a thermophysical property measuring device such as a differential scanning calorimeter (DSC). For example, the film forming material is weighed into an aluminum sample pan and measured simultaneously with an empty aluminum sample pan to measure the difference in heat. At this time, in the first measurement, a measurement error may occur due to the influence of the melting of the film forming material and the like. Therefore, it is preferable to measure the glass transition temperature from the second and subsequent measurement data.
　絶縁被覆導電粒子１０は、規則的な配列で導電性接着剤層１３中に配されていることが好ましい。例えば、導電性接着剤層１３の厚み方向から見たときに、図７に示されるような配列模様を形成するように絶縁被覆導電粒子１０を配列させるとことが好ましい。配列模様は、絶縁被覆導電粒子１０同士を直線で結んだときに含まれる形状として、正三角形型、二等辺三角形型、正五角形型、正方系型、長方形型、これらの模様を傾斜させた配列模様等が挙げられる。この中でも、正三角形型の配列は、絶縁被覆導電粒子１０の最密充填が可能な模様であり、対向する電極間に捕捉される絶縁被覆導電粒子数を増加させるために好適な配列模様である。 The insulating coating conductive particles 10 are preferably arranged in the conductive adhesive layer 13 in a regular arrangement. For example, it is preferable to arrange the insulating coated conductive particles 10 so as to form an arrangement pattern as shown in FIG. 7 when viewed from the thickness direction of the conductive adhesive layer 13. The arrangement pattern is an equilateral triangle type, an isosceles triangle type, a regular pentagon type, a tetragonal type, a rectangular type, or an arrangement in which these patterns are inclined as shapes included when the insulating coated conductive particles 10 are connected by a straight line. A pattern etc. are mentioned. Among them, the equilateral triangular arrangement is a pattern that allows the closest packing of the insulating coated conductive particles 10 and is a suitable arrangement pattern for increasing the number of insulating coated conductive particles captured between the opposing electrodes. .
　絶縁被覆導電粒子１０の粒子密度は、５０００個／ｍｍ２以上４００００個／ｍｍ２以下であることが好ましい。この条件を満たすことにより、対向する電極間の接続信頼性の確保と、回路部材内の隣り合う電極同士の絶縁性の確保とをより好適に両立できる。 The particle density of the insulating coated conductive particles 10 is preferably 5000 / mm 2 or more and 40000 / mm 2 or less. By satisfying this condition, it is possible to more suitably achieve both ensuring connection reliability between the opposing electrodes and ensuring insulation between adjacent electrodes in the circuit member.
［異方導電フィルムの製造方法］
　次に、本発明に係る異方導電フィルムの製造方法の一実施形態について、図４～図６を参照しながら説明する。 [Method for producing anisotropic conductive film]
Next, an embodiment of a method for producing an anisotropic conductive film according to the present invention will be described with reference to FIGS.
　図４～図６に示される本実施形態の異方導電フィルムの製造方法は、
　導電性を有する基材粒子１と、該基材粒子１の表面を被覆する絶縁性微粒子２と、を備える複合粒子２０を用意するステップ１と、
　閉鎖端面Ｓを有する孔３２が設けられた粒子収容部材３０の孔３２に複合粒子２０を収容するステップ２（図４の（ａ）を参照）と、
　孔３２から露出する複合粒子２０の球冠領域３にある絶縁性微粒子２の一部又は全部を除去するステップ３（図４の（ｂ）を参照）と、
　第１の接着剤層１３ａ上に、球冠領域３の絶縁性微粒子２が除去された複合粒子２０を、球冠領域３側が第１の接着剤層１３ａに接するように粒子収容部材３０から移しつつ、複合粒子２０の絶縁性微粒子２の一部を粒子収容部材３０の閉鎖端面Ｓに付着させて除去することにより、第１の接着剤層１３ａ上に絶縁被覆導電粒子１０を設けるステップ４（図５の（ａ）及び（ｂ）を参照）と、
　第１の接着剤層１３ａの絶縁被覆導電粒子１０が配されている側に第２の接着剤層１３ｂを貼り合せるステップ５（図５の（ｃ）を参照）と、
を備える。 The method for producing the anisotropic conductive film of the present embodiment shown in FIGS.
Step 1 of preparing composite particles 20 comprising conductive base particles 1 and insulating fine particles 2 covering the surface of the base particles 1;
Step 2 (see (a) of FIG. 4) in which the composite particles 20 are accommodated in the holes 32 of the particle accommodation member 30 provided with the holes 32 having the closed end surface S;
Removing part or all of the insulating fine particles 2 in the spherical crown region 3 of the composite particles 20 exposed from the holes 32 (see FIG. 4B);
On the first adhesive layer 13a, the composite particles 20 from which the insulating fine particles 2 in the spherical crown region 3 have been removed are transferred from the particle containing member 30 so that the spherical crown region 3 side is in contact with the first adhesive layer 13a. On the other hand, the insulating coated conductive particles 10 are provided on the first adhesive layer 13a by removing a part of the insulating fine particles 2 of the composite particles 20 by attaching them to the closed end surface S of the particle containing member 30 (Step 4). (See (a) and (b) of FIG. 5),
Step 5 (see (c) of FIG. 5) in which the second adhesive layer 13b is bonded to the side where the insulating coated conductive particles 10 of the first adhesive layer 13a are disposed;
Is provided.
　ステップ１における複合粒子２０は、上述した（ｉｉ）の方法で説明したようにして用意することができる。 The composite particles 20 in Step 1 can be prepared as described in the above method (ii).
　ステップ２で用いられる粒子収容部材３０の材質としては、例えば、アクリレート、メタクリレート等のラジカル重合性化合物の硬化物が挙げられる。孔３２の形状としては、複合粒子２０を収容でき、複合粒子２０の球冠領域３が粒子収容部材３０から突出することができるものであればよく、例えば、円柱、円錐、角柱、角推が挙げられる。閉鎖端面Ｓの形状としては、例えば、円形状（球面状）、多角形状が挙げられる。 Examples of the material of the particle accommodating member 30 used in Step 2 include a cured product of a radical polymerizable compound such as acrylate and methacrylate. The hole 32 may have any shape as long as the composite particle 20 can be accommodated and the spherical crown region 3 of the composite particle 20 can protrude from the particle accommodation member 30. Can be mentioned. Examples of the shape of the closed end surface S include a circular shape (spherical shape) and a polygonal shape.
　孔３２は、規則的な配列（例えば、図７に示される配列）で設けることが好ましく、これにより、上述した配列模様で絶縁被覆導電粒子１０を配した導電性接着剤層１３を形成することができる。 The holes 32 are preferably provided in a regular arrangement (for example, the arrangement shown in FIG. 7), whereby the conductive adhesive layer 13 in which the insulating coated conductive particles 10 are arranged in the arrangement pattern described above is formed. Can do.
　複合粒子２０の球冠領域３にある絶縁性微粒子２を除去する方法としては、例えば、ウレタンゴム製、金属製等のスキージを用いて掻きとる手法、刷毛等を用いて掻きとる手法が挙げられる。 Examples of the method of removing the insulating fine particles 2 in the spherical crown region 3 of the composite particle 20 include a method of scraping with a squeegee made of urethane rubber or metal, and a method of scraping with a brush or the like. .
　第１の接着剤層１３ａを構成する材料としては、上述した導電性接着剤層１３に含まれる、モノマー、硬化剤及びフィルム形成材が挙げられる。第１の接着剤層１３ａは、充填剤、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤、カップリング剤、フェノール樹脂、メラミン樹脂、イソシアネート類等を更に含有していてもよい。 Examples of the material constituting the first adhesive layer 13a include monomers, curing agents, and film forming materials contained in the conductive adhesive layer 13 described above. The first adhesive layer 13a further contains a filler, softener, accelerator, anti-aging agent, colorant, flame retardant, thixotropic agent, coupling agent, phenol resin, melamine resin, isocyanates, and the like. You may do it.
　本実施形態においては、図５の（ａ）に示されるように、剥離フィルム１２上に第１の接着剤層１３ａを形成した積層体を用いることができる。第１の接着剤層１３ａの厚みは、バンプ電極の高さに応じて適宜設定することができる。 In the present embodiment, as shown in FIG. 5A, a laminate in which the first adhesive layer 13a is formed on the release film 12 can be used. The thickness of the first adhesive layer 13a can be appropriately set according to the height of the bump electrode.
　また、第２の接着剤層１３ｂの貼り合せにおいても、剥離フィルム１２上に第２の接着剤層１３ｂを形成した積層体を用いることができる。第２の接着剤層１３ｂの厚みは、バンプ電極の高さに応じて適宜設定することができる。第２の接着剤層１３ｂを構成する材料としては、上述した導電性接着剤層１３に含まれる、モノマー、硬化剤及びフィルム形成材が挙げられる。第２の接着剤層１３ｂは、充填剤、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤、カップリング剤、フェノール樹脂、メラミン樹脂、イソシアネート類等を更に含有していてもよい。 Further, also in the bonding of the second adhesive layer 13b, a laminate in which the second adhesive layer 13b is formed on the release film 12 can be used. The thickness of the second adhesive layer 13b can be appropriately set according to the height of the bump electrode. Examples of the material constituting the second adhesive layer 13b include monomers, curing agents, and film forming materials contained in the conductive adhesive layer 13 described above. The second adhesive layer 13b further contains a filler, softener, accelerator, anti-aging agent, colorant, flame retardant, thixotropic agent, coupling agent, phenol resin, melamine resin, isocyanates, and the like. You may do it.
　貼り合せの方法としては、例えば、接着剤を加熱しながら貼り合せるラミネート手法が挙げられる。また、加熱だけでなく、減圧下にてラミネートを行う真空加熱ラミネータを用いれば、貼り合せ時に気泡の巻き込みを低減することが可能である。 As a bonding method, for example, a laminating method in which an adhesive is bonded while heating can be mentioned. Further, if a vacuum heating laminator that performs lamination under reduced pressure as well as heating is used, it is possible to reduce entrainment of bubbles during bonding.
　上記ステップ１～５を経て、図６に示されるような、剥離フィルム１２と、絶縁被覆導電粒子１０及び接着剤成分が含まれる導電性接着剤層（異方導電フィルム）１３と、剥離フィルム１２とがこの順に積層された積層構造を有する剥離フィルム付き異方導電フィルムが得られる。 Through the above steps 1 to 5, as shown in FIG. 6, a release film 12, a conductive adhesive layer (an anisotropic conductive film) 13 containing insulating coating conductive particles 10 and an adhesive component, and a release film 12 An anisotropic conductive film with a release film having a laminated structure in which are laminated in this order is obtained.
　本実施形態においては、絶縁被覆導電粒子１０を導電性接着剤層１３の一方面側に偏在させる観点から、第１の接着剤層１３ａの厚みＤａと、第２の接着剤層１３ｂの厚みＤｂとの比Ｄａ／Ｄｂを、２０／１～１５／５とすることが好ましい。 In the present embodiment, the thickness Da of the first adhesive layer 13a and the thickness Db of the second adhesive layer 13b from the viewpoint of unevenly distributing the insulating coated conductive particles 10 on one side of the conductive adhesive layer 13. The ratio Da / Db is preferably 20/1 to 15/5.
［接続構造体の構成］
　図８は、本発明に係る接続構造体の一実施形態を示す模式的断面図である。同図に示すように、接続構造体５０は、互いに対向する第１の回路部材５２及び第２の回路部材５３と、これらの回路部材５２，５３を接続する導電性接着剤（異方導電フィルム）の硬化物５４とを備えて構成されている。 [Configuration of connection structure]
FIG. 8 is a schematic cross-sectional view showing an embodiment of a connection structure according to the present invention. As shown in the figure, the connection structure 50 includes a first circuit member 52 and a second circuit member 53 that face each other, and a conductive adhesive (an anisotropic conductive film) that connects these circuit members 52 and 53. ) Cured product 54.
　第１の回路部材５２は、例えばテープキャリアパッケージ（ＴＣＰ）、プリント配線板、半導体シリコンチップ等である。第１の回路部材５２は、本体部５の実装面５ａ側に複数のバンプ電極６を有している。バンプ電極６は、例えば平面視で矩形状をなしており、厚みは例えば３μｍ以上１８μｍ未満となっている。バンプ電極６の形成材料には、例えばＡｕ等が用いられ、導電性接着剤（異方導電フィルム）の硬化物５４に含まれる絶縁被覆導電粒子１０よりも変形し易くなっている。なお、実装面５ａにおいて、バンプ電極６が形成されていない部分には、絶縁層が形成されていてもよい。 The first circuit member 52 is, for example, a tape carrier package (TCP), a printed wiring board, a semiconductor silicon chip, or the like. The first circuit member 52 has a plurality of bump electrodes 6 on the mounting surface 5 a side of the main body 5. The bump electrode 6 has, for example, a rectangular shape in plan view, and has a thickness of, for example, 3 μm or more and less than 18 μm. For example, Au or the like is used as a material for forming the bump electrode 6, and the bump electrode 6 is more easily deformed than the insulating coated conductive particles 10 included in the cured product 54 of the conductive adhesive (anisotropic conductive film). Note that an insulating layer may be formed on a portion of the mounting surface 5a where the bump electrode 6 is not formed.
　第２の回路部材５３は、例えば液晶ディスプレイに用いられるＩＴＯ、ＩＺＯ、若しくは金属等で回路が形成されたガラス基板又はプラスチック基板、フレキシブルプリント基板（ＦＰＣ）、セラミック配線板などである。第２の回路部材５３は、図６に示すように、本体部７の実装面７ａ側にバンプ電極６に対応する複数の回路電極８を有している。回路電極８は、バンプ電極６と同様に、例えば平面視で矩形状をなしており、厚みは例えば１００ｎｍ程度となっている。回路電極８の表面は、例えば金、銀、銅、錫、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金、インジウム錫酸化物（ＩＴＯ）、及びインジウム亜鉛酸化物（ＩＺＯ）から選ばれる１種或いは２種以上の材料で構成されている。なお、実装面７ａにおいても、回路電極８が形成されていない部分に絶縁層が形成されていてもよい。 The second circuit member 53 is, for example, a glass substrate or a plastic substrate, a flexible printed circuit board (FPC), a ceramic wiring board, or the like on which a circuit is formed of ITO, IZO, or metal used for a liquid crystal display. As shown in FIG. 6, the second circuit member 53 has a plurality of circuit electrodes 8 corresponding to the bump electrodes 6 on the mounting surface 7 a side of the main body 7. The circuit electrode 8 has a rectangular shape, for example, in plan view, like the bump electrode 6, and has a thickness of, for example, about 100 nm. The surface of the circuit electrode 8 is, for example, one selected from gold, silver, copper, tin, ruthenium, rhodium, palladium, osmium, iridium, platinum, indium tin oxide (ITO), and indium zinc oxide (IZO) or It is composed of two or more materials. In the mounting surface 7a, an insulating layer may be formed in a portion where the circuit electrode 8 is not formed.
　硬化物５４は、例えば、図３の（ａ）に示される剥離フィルム付き異方導電フィルム１１を用いて形成され、導電性接着剤層（異方導電フィルム）１３の硬化物とすることができる。なお、本実施形態では、説明の便宜上、絶縁被覆導電粒子１０が分散された層を導電性接着剤層１３と称するが、層を構成している接着剤成分自体は非導電性である。 The cured product 54 is formed using, for example, the anisotropic conductive film 11 with a release film shown in FIG. 3A, and can be a cured product of the conductive adhesive layer (anisotropic conductive film) 13. . In the present embodiment, for convenience of explanation, the layer in which the insulating coated conductive particles 10 are dispersed is referred to as a conductive adhesive layer 13, but the adhesive component itself constituting the layer is non-conductive.
　絶縁被覆導電粒子１０は、第２の回路部材５３側に偏在した状態となっていてもよく、圧着によって僅かに扁平に変形した状態でバンプ電極６と回路電極８との間に介在している。これにより、バンプ電極６と回路電極８との間の電気的な接続が実現されている。また、隣接するバンプ電極６，６間及び隣接する回路電極８，８間では、絶縁被覆導電粒子１０がパターン模様を形成した状態で離間されており、隣接するバンプ電極６，６間及び隣接する回路電極８，８間の電気的な絶縁が実現されている。 The insulating coated conductive particles 10 may be unevenly distributed on the second circuit member 53 side, and are interposed between the bump electrode 6 and the circuit electrode 8 in a state of being slightly flattened by pressure bonding. . Thereby, electrical connection between the bump electrode 6 and the circuit electrode 8 is realized. In addition, between the adjacent bump electrodes 6 and 6 and between the adjacent circuit electrodes 8 and 8, the insulating coating conductive particles 10 are spaced apart in a pattern pattern, and are adjacent to and adjacent to the bump electrodes 6 and 6. Electrical insulation between the circuit electrodes 8, 8 is realized.
［接続構造体の製造方法］
　図９及び図１０は、図８に示した接続構造体の製造工程を示す模式的断面図である。接続構造体５０の形成にあたっては、まず、剥離フィルム付き異方導電フィルム１１から剥離フィルム１２を剥離し、実装面７ａと対向するようにして導電性接着剤層（異方導電フィルム）１３を第２の回路部材５３上にラミネートする。次に、図１０に示すように、バンプ電極６と回路電極８とが対向するように、導電性接着剤層（異方導電フィルム）１３がラミネートされた第２の回路部材５３上に第１の回路部材５２を配置する。そして、導電性接着剤層（異方導電フィルム）１３を加熱しながら第１の回路部材５２と第２の回路部材５３とを厚み方向に加圧する。 [Method of manufacturing connection structure]
9 and 10 are schematic cross-sectional views showing the manufacturing process of the connection structure shown in FIG. In forming the connection structure 50, first, the release film 12 is peeled from the anisotropic conductive film 11 with a release film, and the conductive adhesive layer (anisotropic conductive film) 13 is formed so as to face the mounting surface 7 a. Laminate on the second circuit member 53. Next, as shown in FIG. 10, the first is formed on the second circuit member 53 on which the conductive adhesive layer (anisotropic conductive film) 13 is laminated so that the bump electrode 6 and the circuit electrode 8 face each other. The circuit member 52 is arranged. Then, the first circuit member 52 and the second circuit member 53 are pressed in the thickness direction while heating the conductive adhesive layer (anisotropic conductive film) 13.
　これにより、導電性接着剤層（異方導電フィルム）１３の接着剤成分が流動し、バンプ電極６と回路電極８との距離が縮まって絶縁被覆導電粒子１０が噛合した状態で、導電性接着剤層１３が硬化する。導電性接着剤層１３の硬化により、バンプ電極６と回路電極８とが電気的に接続され、かつ隣接するバンプ電極６，６同士及び隣接する回路電極８，８同士が電気的に絶縁された状態で導電性接着剤層（異方導電フィルム）１３の硬化物５４が形成され、図８に示した接続構造体５０が得られる。得られた接続構造体５０では、導電性接着剤層（異方導電フィルム）１３の硬化物５４によってバンプ電極６と回路電極８との間の距離の経時的変化が充分に防止されると共に、電気的特性の長期信頼性も確保できる。 As a result, the adhesive component of the conductive adhesive layer (anisotropic conductive film) 13 flows, the distance between the bump electrode 6 and the circuit electrode 8 is shortened, and the insulating coated conductive particles 10 are engaged with each other. The agent layer 13 is cured. By curing the conductive adhesive layer 13, the bump electrode 6 and the circuit electrode 8 are electrically connected, and the adjacent bump electrodes 6, 6 and the adjacent circuit electrodes 8, 8 are electrically insulated. In this state, a cured product 54 of the conductive adhesive layer (anisotropic conductive film) 13 is formed, and the connection structure 50 shown in FIG. 8 is obtained. In the obtained connection structure 50, the cured material 54 of the conductive adhesive layer (anisotropic conductive film) 13 sufficiently prevents the change with time in the distance between the bump electrode 6 and the circuit electrode 8, Long-term reliability of electrical characteristics can be secured.
　なお、接続時の加熱温度は、硬化剤において重合活性種が発生し、重合モノマーの重合が開始される温度以上であることが好ましい。この加熱温度は、例えば８０℃～２００℃であり、好ましくは１００℃～１８０℃である。また、加熱時間は、例えば０．１秒～３０秒、好ましくは１秒～２０秒である。加熱温度が８０℃未満であると硬化速度が遅くなり、２００℃を超えると望まない副反応が進行しやすい。また、加熱時間が０．１秒未満では硬化反応が充分に進行せず、３０秒を超えると硬化物５４の生産性が低下し、さらに、望まない副反応も進みやすい。 In addition, it is preferable that the heating temperature at the time of connection is equal to or higher than a temperature at which polymerization active species are generated in the curing agent and polymerization of the polymerization monomer is started. The heating temperature is, for example, 80 ° C. to 200 ° C., preferably 100 ° C. to 180 ° C. The heating time is, for example, 0.1 second to 30 seconds, preferably 1 second to 20 seconds. When the heating temperature is less than 80 ° C., the curing rate is slow, and when it exceeds 200 ° C., unwanted side reactions tend to proceed. In addition, when the heating time is less than 0.1 seconds, the curing reaction does not proceed sufficiently, and when it exceeds 30 seconds, the productivity of the cured product 54 decreases, and undesired side reactions easily proceed.
　本実施形態の接続構造体の製造方法によれば、絶縁被覆導電粒子１０を含む導電性接着剤層（異方導電フィルム）１３を用いることにより、対向する電極間の接続信頼性と回路部材内の隣り合う電極同士の絶縁性とを両立できる接続構造体を得ることができる。 According to the manufacturing method of the connection structure of the present embodiment, by using the conductive adhesive layer (anisotropic conductive film) 13 including the insulating coated conductive particles 10, the connection reliability between the opposing electrodes and the inside of the circuit member It is possible to obtain a connection structure that can achieve both insulating properties of adjacent electrodes.
　以下、実施例及び比較例によって、本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.
［接着剤層の形成］
　以下に示す方法で接着剤層をそれぞれ形成した。 [Formation of adhesive layer]
Each adhesive layer was formed by the following method.
（接着剤層１）
　ジムロート冷却管、塩化カルシウム管、及び攪拌モーターに接続されたポリテトラフルオロエチレン製の攪拌棒を装着した３０００ｍＬの３つ口フラスコ中で、４，４’－（９－フルオレニリデン）－ジフェノール４５ｇ（シグマアルドリッチジャパン株式会社製）、及び３，３’，５，５’－テトラメチルビフェノールジグリシジルエーテル５０ｇ（三菱化学株式会社製：ＹＸ－４０００Ｈ）を、Ｎ－メチルピロリドン１０００ｍＬに溶解して反応液とした。これに炭酸カリウム２１ｇを加え、マントルヒーターで１１０℃に加熱しながら攪拌した。３時間攪拌後、１０００ｍＬのメタノールが入ったビーカーに反応液を滴下し、生成した沈殿物を吸引ろ過することによってろ取した。ろ取した沈殿物を３００ｍＬのメタノールで３回洗浄して、フェノキシ樹脂ａを７５ｇ得た。 (Adhesive layer 1)
45 g of 4,4 ′-(9-fluorenylidene) -diphenol in a 3000 mL three-necked flask equipped with a Dimroth condenser, a calcium chloride tube, and a stirring bar made of polytetrafluoroethylene connected to a stirring motor ( Sigma Aldrich Japan Co., Ltd.) and 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether 50 g (Mitsubishi Chemical Co., Ltd .: YX-4000H) were dissolved in 1000 mL of N-methylpyrrolidone to obtain a reaction solution. It was. To this, 21 g of potassium carbonate was added and stirred while heating to 110 ° C. with a mantle heater. After stirring for 3 hours, the reaction solution was dropped into a beaker containing 1000 mL of methanol, and the produced precipitate was collected by suction filtration. The precipitate collected by filtration was washed three times with 300 mL of methanol to obtain 75 g of phenoxy resin a.
　なお、フェノキシ樹脂ａの分子量及び分散度について、下記の条件に従って、ゲル浸透クロマトグラフ（ＧＰＣ）より測定したところ、標準ポリスチレンによる検量線を用いたポリスチレン換算で、Ｍｎ＝１５７６９、Ｍｗ＝３８０４５、Ｍｗ／Ｍｎ＝２．４１３であった。
（測定条件）
　装置：東ソー株式会社製　ＧＰＣ－８０２０
　検出器：東ソー株式会社製　ＲＩ－８０２０
　カラム：日立化成株式会社製　Ｇｅｌｐａｃｋ　ＧＬＡ１６０Ｓ＋ＧＬＡ１５０Ｓ
　試料濃度：１２０ｍｇ／３ｍＬ
　溶媒：テトラヒドロフラン
　注入量：６０μＬ
　圧力：２．９４×１０６Ｐａ（３０ｋｇｆ／ｃｍ２）
　流量：１．００ｍＬ／ｍｉｎ The molecular weight and dispersity of the phenoxy resin a were measured by gel permeation chromatography (GPC) according to the following conditions. As a result of polystyrene conversion using a standard polystyrene calibration curve, Mn = 15769, Mw = 38045, Mw /Mn=2.413.
(Measurement condition)
Equipment: GPC-8020 manufactured by Tosoh Corporation
Detector: RI-8020 manufactured by Tosoh Corporation
Column: Hitachi Chemical Co., Ltd. Gelpack GLA160S + GLA150S
Sample concentration: 120 mg / 3 mL
Solvent: Tetrahydrofuran Injection volume: 60 μL
Pressure: 2.94 × 106 Pa (30 kgf / cm 2 )
Flow rate: 1.00 mL / min
　また、フェノキシ樹脂ａのガラス転移温度について、下記の条件に従って、測定したところ、１６０℃であった。
（測定条件）
　示差走査熱量測定装置（株式会社パーキンエルマージャパン製、Ｐｙｅｉｓ）を用いて、窒素雰囲気下にて昇温速度：１０℃／ｍｉｎ、３０～２５０℃の範囲にて２回測定し、２度目の測定結果をガラス転移温度とした。 Moreover, it was 160 degreeC when it measured according to the following conditions about the glass transition temperature of the phenoxy resin a.
(Measurement condition)
Using a differential scanning calorimeter (manufactured by PerkinElmer Japan Co., Ltd., Pyeis), the temperature was increased twice in the range of 10 ° C./min and 30 to 250 ° C. in a nitrogen atmosphere, and the second measurement. The result was taken as the glass transition temperature.
　次に、ビスフェノールＡ型エポキシ樹脂（三菱化学社製：ｊＥＲ８２８）を５０質量部、硬化剤として４－ヒドロキシフェニルメチルベンジルスルホニウムヘキサフルオロアンチモネートを５質量部、及びフィルム形成材としてフェノキシ樹脂ａを５０質量部、をメチルエチルケトンに溶解、混合し、接着剤ペーストを調製した。 Next, 50 parts by mass of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation: jER828), 5 parts by mass of 4-hydroxyphenylmethylbenzylsulfonium hexafluoroantimonate as a curing agent, and 50 parts of phenoxy resin a as a film forming material. Part by mass was dissolved and mixed in methyl ethyl ketone to prepare an adhesive paste.
　得られた接着剤ペーストを、厚み５０μｍのＰＥＴ樹脂フィルム上に、コータを用いて塗布し、７０℃で５分間熱風乾燥することにより、厚みが１５μｍの接着剤層１を形成した。 The obtained adhesive paste was applied onto a PET resin film having a thickness of 50 μm using a coater and dried with hot air at 70 ° C. for 5 minutes to form an adhesive layer 1 having a thickness of 15 μm.
（接着剤層２）
　接着剤層１の形成と同様にして、厚みが０．８μｍの接着剤層２を形成した。 (Adhesive layer 2)
Similarly to the formation of the adhesive layer 1, an adhesive layer 2 having a thickness of 0.8 μm was formed.
（接着剤層３）
　ビスフェノールＦ型エポキシ樹脂（三菱化学社製：ｊＥＲ８０７）を４５質量部、硬化剤として４－ヒドロキシフェニルメチルベンジルスルホニウムヘキサフルオロアンチモネートを５質量部、及びフィルム形成材としてフェノキシ樹脂ＹＰ－７０（新日鉄住金化学社製）を５５質量部混合し、接着剤ペーストを調製した。 (Adhesive layer 3)
45 parts by mass of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: jER807), 5 parts by mass of 4-hydroxyphenylmethylbenzylsulfonium hexafluoroantimonate as a curing agent, and phenoxy resin YP-70 (Nippon Steel & Sumitomo Metal) as a film forming material 55 parts by mass of Chemical Co.) was mixed to prepare an adhesive paste.
　得られた接着剤ペーストを、厚み５０μｍのＰＥＴ樹脂フィルム上に、コータを用いて塗布し、７０℃で５分間熱風乾燥することにより、厚みが１５μｍの接着剤層３を形成した。 The obtained adhesive paste was applied onto a PET resin film having a thickness of 50 μm using a coater and dried with hot air at 70 ° C. for 5 minutes to form an adhesive layer 3 having a thickness of 15 μm.
［複合粒子の調製］
　以下に示す方法で複合粒子をそれぞれ調製した。 [Preparation of composite particles]
Composite particles were prepared by the following methods.
（基材粒子）
　平均粒径３．０μｍの架橋ポリスチレン粒子（樹脂微粒子）３ｇを、アルカリ脱脂の後、酸で中和した。次いで、樹脂微粒子を、ｐＨ６．０に調整したカチオン性高分子液１００ｍＬに添加し、６０℃で１時間攪拌した後、直径３μｍのメンブレンフィルタ（ミリポア社製）で濾過し、水洗を行った。パラジウム触媒であるアトテックネオガント８３４（アトテックジャパン（株）製、商品名）を８質量％含有するパラジウム触媒化液１００ｍＬに水洗後の樹脂微粒子を添加し、３５℃で３０分攪拌した後濾過し、水洗を行った。 (Base particle)
3 g of crosslinked polystyrene particles (resin fine particles) having an average particle size of 3.0 μm were neutralized with acid after alkaline degreasing. Next, the resin fine particles were added to 100 mL of a cationic polymer solution adjusted to pH 6.0, stirred at 60 ° C. for 1 hour, filtered through a membrane filter (Millipore) having a diameter of 3 μm, and washed with water. The resin fine particles after washing with water are added to 100 mL of palladium-catalyzed solution containing 8% by mass of Atotech Neogant 834 (trade name, manufactured by Atotech Japan Co., Ltd.), which is a palladium catalyst, and the mixture is stirred at 35 ° C. for 30 minutes and then filtered. , Washed with water.
　次に、水洗後の樹脂微粒子を３ｇ／Ｌの次亜リン酸ナトリウム液に添加し、表面が活性化された樹脂微粒子（樹脂コア粒子）を得た。この樹脂コア粒子と、水１０００ｍＬと、リンゴ酸ナトリウム（濃度２０ｇ／Ｌ）とを２０００ｍＬのガラスビーカーに投入し、超音波分散させた。続いて、フッ素製攪拌羽根により攪拌（６００ｒｐｍ）を行いながらｐＨを５．５以下に調整し、分散液を８０℃に加温した。そこに、無電解ニッケルめっき液であるＳＥＫ６７０（日本カニゼン株式会社、製品名）を（ＳＥＫ６７０－０）／（ＳＥＫ６７０－１）＝１．８の割合で混合した初期薄膜めっき液を、定量ポンプを用いて７ｍｌ／分で添加したところ、約３０秒後に還元反応が開始し、浴中から気泡が発生して浴全体が灰色から黒色になった。その後、初期薄膜形成を終了した後、間をあけずに硫酸ニッケル（濃度２２４ｇ／Ｌ）、及びリンゴ酸ナトリウム（濃度３０５ｇ／Ｌ）を混合した厚付けめっき液と、次亜リン酸ナトリウム（濃度５３４ｇ／Ｌ）、及び水酸化ナトリウム（濃度３４ｇ／Ｌ）で混合した厚付けめっき液を１３ｍｌ／分で２液同時に添加した。その後、気泡の発生が停止するまで攪拌を行ったところ、浴全体が黒色から灰色に変化した。このめっき処理により、樹脂コア粒子を被覆するニッケルめっき層が形成された。基材粒子の直径をＳＥＭにより測定したところ、直径３．３μｍであった。 Next, the resin fine particles after washing with water were added to a 3 g / L sodium hypophosphite solution to obtain resin fine particles (resin core particles) whose surface was activated. The resin core particles, 1000 mL of water, and sodium malate (concentration 20 g / L) were put into a 2000 mL glass beaker and ultrasonically dispersed. Subsequently, the pH was adjusted to 5.5 or lower while stirring (600 rpm) with a fluorine stirring blade, and the dispersion was heated to 80 ° C. Then, an initial electroless nickel plating solution SEK670 (Nippon Kanigen Co., Ltd., product name) mixed at a ratio of (SEK670-0) / (SEK670-1) = 1.8 was added to the metering pump. When added at a rate of 7 ml / min, the reduction reaction started after about 30 seconds, bubbles were generated from the bath, and the entire bath turned from gray to black. Then, after finishing the initial thin film formation, a thick plating solution in which nickel sulfate (concentration 224 g / L) and sodium malate (concentration 305 g / L) were mixed with no gap, and sodium hypophosphite (concentration). 534 g / L) and a thick plating solution mixed with sodium hydroxide (concentration 34 g / L) were added simultaneously at 13 ml / min. Thereafter, stirring was performed until the generation of bubbles stopped, and the entire bath changed from black to gray. By this plating treatment, a nickel plating layer covering the resin core particles was formed. The diameter of the substrate particles was measured by SEM and found to be 3.3 μm.
（絶縁性微粒子）
　５００ｍＬ三ツ口フラスコに、ラジカル重合性二重結合及びアルコキシシリル基を有するシランカップリング剤（３－アクリロキシプロピルトリメトキシシラン、信越化学工業（株）製：ＫＢＭ－５１０３）７．５ｇと、メタクリル酸（和光純薬工業（株）製）６．９ｇと、アクリル酸メチル（和光純薬工業（株）製）４．１ｇと、２，２’－アゾビス（イソブチロニトリル）０．３６ｇと、アセトニトリル３５０ｇとを入れてこれらを混合した。窒素（１００ｍＬ／分）により１時間かけて溶存酸素を置換した後、８０℃に加熱しながら６時間重合反応を進行させて、一次粒子径３００ｎｍの有機無機ハイブリッド粒子を得た。この有機無機ハイブリッド粒子を含む分散液を２０ｍＬの容器に入れ、３０００ｒ．ｐ．ｍ．で３０分間の遠心分離（株式会社コクサン製：Ｈ－１０３Ｎ）により、未反応のモノマーを除去した。更にメタノールを２０ｍＬ追加し、超音波分散させ再度遠心分離を行った。そこに、硬化触媒として、カルボキシル基の量に対して等モルのトリエチルアミンを入れ、メタノールを追加して超音波分散させて、架橋反応を進行させた。再度の遠心分離後、トリエチルアミンを除去し、得られた絶縁性微粒子をメタノールに分散させた。 (Insulating fine particles)
In a 500 mL three-necked flask, 7.5 g of a silane coupling agent having a radical polymerizable double bond and an alkoxysilyl group (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) and methacrylic acid 6.9 g (manufactured by Wako Pure Chemical Industries, Ltd.), 4.1 g of methyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.36 g of 2,2′-azobis (isobutyronitrile), Acetonitrile (350 g) was added and mixed. After replacing dissolved oxygen with nitrogen (100 mL / min) over 1 hour, the polymerization reaction was allowed to proceed for 6 hours while heating to 80 ° C. to obtain organic-inorganic hybrid particles having a primary particle size of 300 nm. The dispersion containing the organic-inorganic hybrid particles is placed in a 20 mL container, and 3000 r. p. m. The unreacted monomer was removed by centrifugation for 30 minutes (manufactured by Kokusan Co., Ltd .: H-103N). Further, 20 mL of methanol was added, and the mixture was ultrasonically dispersed and centrifuged again. Thereto, as a curing catalyst, equimolar amount of triethylamine with respect to the amount of carboxyl groups was added, and methanol was added and ultrasonically dispersed to proceed the crosslinking reaction. After centrifugation again, triethylamine was removed, and the resulting insulating fine particles were dispersed in methanol.
（複合粒子１）
＜基材粒子に表面官能基を形成する工程＞
　メルカプト酢酸（和光純薬工業株式会社製、商品名）８ｍｍｏｌをメタノール２００ｍｌに溶解し、そこに上記で用意した基材粒子を１０ｇ加えた。直径４５ｍｍの攪拌羽を取り付けたスリーワンモーター（新東科学株式会社製、商品名：ＢＬ３０００）を用いて室温（２５℃）で２時間攪拌し、メタノールで洗浄したφ３μｍのメンブレンフィルタ（ミリポア社製　：コーテッドタイプメンブレンフィルター）で濾過して、表面官能基としてカルボキシル基を有する基材粒子１０ｇを得た。 (Composite particle 1)
<Step of forming surface functional groups on substrate particles>
8 mmol of mercaptoacetic acid (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 ml of methanol, and 10 g of the substrate particles prepared above were added thereto. A φ3 μm membrane filter (manufactured by Millipore), which was stirred for 2 hours at room temperature (25 ° C.) using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., trade name: BL3000) equipped with a stirring blade having a diameter of 45 mm and washed with methanol The resultant was filtered through a coated type membrane filter) to obtain 10 g of base particles having a carboxyl group as a surface functional group.
＜高分子電解質を基材粒子に吸着させる工程＞
　重量平均分子量７００００のポリエチレンイミンを含む３０質量％ポリエチレンイミン水溶液（和光純薬工業株式会社製、商品名：３０％ポリエチレンイミン　Ｐ－７０溶液）を超純水で希釈して０．３質量％ポリエチレンイミン水溶液を得た。この０．３質量％ポリエチレンイミン水溶液に、上述のカルボキシル基が導入された基材粒子１０ｇを加えた。室温（２５℃）で１５分間攪拌し、φ３μｍのメンブレンフィルタで濾過して、高分子電解質であるポリエチレンイミンが表面に吸着した粒子を得た。この粒子を、超純水２００ｇに混合して室温（２５℃）で５分攪拌し、濾過を行った。濾過して得られた粒子を該メンブレンフィルタ上で２００ｇの超純水で２回洗浄して、粒子に吸着していないポリエチレンイミンを除去した。 <Step of adsorbing polymer electrolyte to substrate particles>
A 30% by mass polyethyleneimine aqueous solution (trade name: 30% polyethyleneimine P-70 solution, manufactured by Wako Pure Chemical Industries, Ltd.) containing polyethyleneimine having a weight average molecular weight of 70,000 is diluted with ultrapure water to obtain 0.3% by mass polyethylene. An aqueous imine solution was obtained. To this 0.3% by mass polyethyleneimine aqueous solution, 10 g of the above-mentioned base particles into which the carboxyl group was introduced were added. The mixture was stirred at room temperature (25 ° C.) for 15 minutes and filtered through a membrane filter of φ3 μm to obtain particles in which polyethyleneimine as a polymer electrolyte was adsorbed on the surface. The particles were mixed with 200 g of ultrapure water, stirred at room temperature (25 ° C.) for 5 minutes, and filtered. The particles obtained by filtration were washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine not adsorbed on the particles.
＜絶縁性微粒子によって基材粒子を被覆する工程＞
　ポリエチレンイミンが吸着した基材粒子１０ｇを、上記で用意した絶縁性微粒子を２－プロパノール（和光純薬工業（株）製）で希釈して得られた２質量％の絶縁性微粒子分散液５０ｇを滴下しながら室温（２５℃）で３０分間攪拌して、基材粒子及びこれを被覆する絶縁性微粒子から構成される複合粒子１を得た。濾過により取り出した複合粒子１を、重量平均分子量１０００のシリコーンオリゴマー（日立化成コーテッドサンド株式会社製：ＳＣ－６０００）５０ｇとメタノール１５０ｇの混合液に入れて、室温（２５℃）で１時間攪拌して濾過を行った。最後に、複合粒子をトルエン（和光純薬工業（株）製）に入れて３分攪拌し、濾過を行った。 <Process for coating substrate particles with insulating fine particles>
50 g of a 2% by mass insulating fine particle dispersion obtained by diluting 10 g of base material particles adsorbed with polyethyleneimine with 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), the insulating fine particles prepared above, was obtained. While dripping, it stirred for 30 minutes at room temperature (25 degreeC), and obtained the composite particle 1 comprised from the base particle and the insulating fine particle which coat | covers this. The composite particles 1 taken out by filtration were put into a mixed solution of 50 g of silicone oligomer having a weight average molecular weight of 1000 (manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000) and 150 g of methanol, and stirred at room temperature (25 ° C.) for 1 hour. And filtered. Finally, the composite particles were placed in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 3 minutes, and filtered.
＜分級工程＞
　得られた複合粒子１を１５０℃、１時間の条件で真空乾燥した。その後、旋回気流式ふるい分け分級機（株式会社セイシン企業）で凝集物を取り除いた。 <Classification process>
The obtained composite particles 1 were vacuum-dried at 150 ° C. for 1 hour. Thereafter, aggregates were removed with a swirling air flow classifier (Seishin Enterprise Co., Ltd.).
（複合粒子２）
　複合粒子１と同様にして、表面官能基としてカルボキシル基を有する基材粒子１０ｇを得た。 (Composite particle 2)
In the same manner as in the composite particle 1, 10 g of a base particle having a carboxyl group as a surface functional group was obtained.
　重量平均分子量７００００のポリエチレンイミンを含む３０質量％ポリエチレンイミン水溶液（和光純薬工業株式会社製、商品名：３０％ポリエチレンイミン　Ｐ－７０溶液）を超純水で希釈して０．３質量％ポリエチレンイミン水溶液を得た。この０．３質量％ポリエチレンイミン水溶液に、上述のカルボキシル基が導入された基材粒子を１０ｇ加えた。室温（２５℃）で１５分間攪拌し、φ５μｍのメンブレンフィルタで濾過して、高分子電解質であるポリエチレンイミンが表面に吸着した粒子を得た。この粒子を、超純水２００ｇに混合して室温（２５℃）で５分攪拌し、濾過を行った。濾過して得られた粒子を該メンブレンフィルタ上で２００ｇの超純水で２回洗浄して、粒子に吸着していないポリエチレンイミンを除去した。 A 30% by mass polyethyleneimine aqueous solution (trade name: 30% polyethyleneimine P-70 solution, manufactured by Wako Pure Chemical Industries, Ltd.) containing polyethyleneimine having a weight average molecular weight of 70,000 is diluted with ultrapure water to obtain 0.3% by mass polyethylene. An aqueous imine solution was obtained. To the 0.3% by mass aqueous polyethyleneimine solution, 10 g of the above-described substrate particles having the carboxyl group introduced were added. The mixture was stirred at room temperature (25 ° C.) for 15 minutes and filtered through a membrane filter having a diameter of 5 μm to obtain particles having polyethyleneimine as a polymer electrolyte adsorbed on the surface. The particles were mixed with 200 g of ultrapure water, stirred at room temperature (25 ° C.) for 5 minutes, and filtered. The particles obtained by filtration were washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine not adsorbed on the particles.
　ポリエチレンイミンが吸着した１０ｇの基材粒子を、上記で用意した絶縁性微粒子を２－プロパノール（和光純薬工業（株）製）で希釈して得られた２質量％の絶縁性微粒子分散液５０ｇを滴下しながら室温（２５℃）で３０分間攪拌して、導電粒子及びこれを被覆する絶縁性微粒子１から構成される複合粒子２を得た。濾過により取り出した複合粒子２を、重量平均分子量１０００のシリコーンオリゴマー（日立化成コーテッドサンド株式会社製：ＳＣ－６０００）５０ｇとメタノール１５０ｇの混合液に入れて、室温（２５℃）で１時間攪拌して濾過を行った。最後に、複合粒子をトルエン（和光純薬工業（株）製）に入れて３分攪拌し、濾過を行った。 50 g of a 2% by weight insulating fine particle dispersion obtained by diluting 10 g of base material particles adsorbed with polyethyleneimine with 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) with the insulating fine particles prepared above. Was added at room temperature (25 ° C.) for 30 minutes to obtain composite particles 2 composed of conductive particles and insulating fine particles 1 covering the conductive particles. The composite particles 2 taken out by filtration are put into a mixed solution of 50 g of a silicone oligomer having a weight average molecular weight of 1000 (manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000) and 150 g of methanol and stirred at room temperature (25 ° C.) for 1 hour. And filtered. Finally, the composite particles were placed in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 3 minutes, and filtered.
　得られた複合粒子２を１５０℃、１時間の条件で真空乾燥した。その後、旋回気流式ふるい分け分級機（株式会社セイシン企業）で凝集物を取り除いた。 The obtained composite particles 2 were vacuum dried at 150 ° C. for 1 hour. Thereafter, aggregates were removed with a swirling air flow classifier (Seishin Enterprise Co., Ltd.).
（複合粒子３）
　複合粒子１と同様にして、表面官能基としてカルボキシル基を有する基材粒子１０ｇを得た。 (Composite particle 3)
In the same manner as in the composite particle 1, 10 g of a base particle having a carboxyl group as a surface functional group was obtained.
　重量平均分子量７００００のポリエチレンイミンを含む３０質量％ポリエチレンイミン水溶液（和光純薬工業株式会社製、商品名：３０％ポリエチレンイミン　Ｐ－７０溶液）を超純水で希釈して０．３質量％ポリエチレンイミン水溶液を得た。この０．３質量％ポリエチレンイミン水溶液に、上述のカルボキシル基が導入された基材粒子を１０ｇ加えた。室温（２５℃）で１５分間攪拌し、φ６μｍのメンブレンフィルタで濾過して、高分子電解質であるポリエチレンイミンが表面に吸着した粒子を得た。この粒子を、超純水２００ｇに混合して室温（２５℃）で５分攪拌し、濾過を行った。濾過して得られた粒子を該メンブレンフィルタ上で２００ｇの超純水で２回洗浄して、粒子に吸着していないポリエチレンイミンを除去した。 A 30% by mass polyethyleneimine aqueous solution (trade name: 30% polyethyleneimine P-70 solution, manufactured by Wako Pure Chemical Industries, Ltd.) containing polyethyleneimine having a weight average molecular weight of 70,000 is diluted with ultrapure water to obtain 0.3% by mass polyethylene. An aqueous imine solution was obtained. To the 0.3% by mass aqueous polyethyleneimine solution, 10 g of the above-described substrate particles having the carboxyl group introduced were added. The mixture was stirred at room temperature (25 ° C.) for 15 minutes and filtered through a membrane filter having a diameter of 6 μm to obtain particles in which polyethyleneimine as a polymer electrolyte was adsorbed on the surface. The particles were mixed with 200 g of ultrapure water, stirred at room temperature (25 ° C.) for 5 minutes, and filtered. The particles obtained by filtration were washed twice with 200 g of ultrapure water on the membrane filter to remove polyethyleneimine not adsorbed on the particles.
　ポリエチレンイミンが吸着した１０ｇの基材粒子を、絶縁性微粒子を２－プロパノール（和光純薬工業（株）製）で希釈して得られた２質量％の絶縁性微粒子分散液５０ｇを滴下しながら室温（２５℃）で３０分間攪拌して、導電粒子及びこれを被覆する絶縁性微粒子１から構成される複合粒子３を得た。濾過により取り出した複合粒子３を、重量平均分子量１０００のシリコーンオリゴマー（日立化成コーテッドサンド株式会社製：ＳＣ－６０００）５０ｇとメタノール１５０ｇの混合液に入れて、室温（２５℃）で１時間攪拌して濾過を行った。最後に、複合粒子をトルエン（和光純薬工業（株）製）に入れて３分攪拌し、濾過を行った。 While adding 10 g of base material particles adsorbed with polyethyleneimine and diluting insulating fine particles with 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), 50 g of a 2 mass% insulating fine particle dispersion obtained by dropwise addition was added. The mixture was stirred at room temperature (25 ° C.) for 30 minutes to obtain composite particles 3 composed of conductive particles and insulating fine particles 1 covering the conductive particles. The composite particles 3 taken out by filtration were put into a mixed solution of 50 g of a silicone oligomer having a weight average molecular weight of 1000 (manufactured by Hitachi Chemical Coated Sand Co., Ltd .: SC-6000) and 150 g of methanol and stirred at room temperature (25 ° C.) for 1 hour. And filtered. Finally, the composite particles were placed in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), stirred for 3 minutes, and filtered.
　得られた複合粒子３を１５０℃、１時間の条件で真空乾燥した。その後、旋回気流式ふるい分け分級機（株式会社セイシン企業）で凝集物を取り除いた。 The obtained composite particles 3 were vacuum dried at 150 ° C. for 1 hour. Thereafter, aggregates were removed with a swirling air flow classifier (Seishin Enterprise Co., Ltd.).
［粒子収容部材の用意］
　以下に示す粒子収容部材をそれぞれ用意した。 [Preparation of particle container]
The following particle accommodating members were prepared.
（粒子収容部材１）
　厚み５．０μｍのメタクリレートの重合によって得られた板に、閉鎖端面（底面）を有する円筒形状（直径４．０μｍ、深さ３．８μｍ）の孔を、正三角形型に２９０００個／ｍｍ２の密度で配列するように設けた。 (Particle containing member 1)
Cylindrical holes (diameter: 4.0 μm, depth: 3.8 μm) having a closed end surface (bottom surface) on a plate obtained by polymerization of a 5.0 μm-thick methacrylate, 29000 holes / mm 2 in an equilateral triangle shape. It arranged so that it might arrange with density.
（粒子収容部材２）
　厚み５．０μｍのメタクリレートの重合によって得られた板に、閉鎖端面（底面）を有する円筒形状（直径４．０μｍ、深さ３．８μｍ）の孔を、正方形型に２００００個／ｍｍ２の密度で配列するように設けた。 (Particle containing member 2)
A plate obtained by polymerization of methacrylate having a thickness of 5.0 μm has a cylindrical shape (4.0 μm in diameter and 3.8 μm in depth) having a closed end surface (bottom surface) and a density of 20000 / mm 2 in a square mold. It was provided so that it might be arranged in.
（粒子収容部材３）
　厚み５．０μｍのメタクリレートの重合によって得られた板に、閉鎖端面（底面）を有する円筒形状（直径４．６μｍ、深さ３．８μｍ）の孔を、正三角形型に２５０００個／ｍｍ２の密度で配列するように設けた。 (Particle containing member 3)
Cylindrical holes (diameter: 4.6 μm, depth: 3.8 μm) having a closed end surface (bottom surface) are formed in a plate obtained by polymerization of 5.0 μm-thick methacrylate in an equilateral triangle shape with 25000 holes / mm 2 . It arranged so that it might arrange with density.
（粒子収容部材４）
　厚み５．０μｍのメタクリレートの重合によって得られた板に、閉鎖端面（底面）を有する円筒形状（直径５．２μｍ、深さ３．８μｍ）の孔を、正三角形型に２００００個／ｍｍ２の密度で配列するように設けた。 (Particle containing member 4)
Cylindrical holes (diameter: 5.2 μm, depth: 3.8 μm) having a closed end surface (bottom surface) on a plate obtained by polymerization of a 5.0 μm-thick methacrylate, are 20000 / mm 2 in an equilateral triangle shape. It arranged so that it might arrange with density.
（粒子収容部材５）
　厚み５．０μｍのメタクリレートの重合によって得られた板に、閉鎖端面（底面）を有する円筒形状（直径３．７μｍ、深さ３．８μｍ）の孔を、正三角形型に２９０００個／ｍｍ２の密度で配列するように設けた。 (Particle containing member 5)
Cylindrical holes (diameter 3.7 μm, depth 3.8 μm) having a closed end surface (bottom surface) on a plate obtained by polymerization of 5.0 μm-thick methacrylate, an equilateral triangle shape with 29000 holes / mm 2 . It arranged so that it might arrange with density.
［異方導電フィルムの作製］ [Production of anisotropic conductive film]
（実施例１）
　図４の（ａ）及び（ｂ）に示される方法と同様にして、粒子収容部材１の孔に複合粒子１を収容し、端面が水平なウレタンゴム製のスキージを用いて、孔から露出する複合粒子の球冠領域にある絶縁性微粒子を除去した。なお、この操作により、複合粒子の球冠領域には、絶縁性微粒子数が０個である領域が５４．７μｍ２設けられたことをＳＥＭによる観察によって確認した。 Example 1
Similar to the method shown in FIGS. 4A and 4B, the composite particles 1 are accommodated in the holes of the particle accommodating member 1, and the end surfaces are exposed from the holes using a horizontal urethane rubber squeegee. The insulating fine particles in the spherical crown region of the composite particles were removed. By this operation, it was confirmed by observation with an SEM that a region where the number of insulating fine particles was 0 was provided in the spherical region of the composite particle by 54.7 μm 2 .
　次に、図５の（ａ）及び（ｂ）に示される方法と同様にして、接着剤層１上に正三角形型に２９０００個／ｍｍ２の粒子密度で配置された絶縁被覆導電粒子を設けた。なお、このとき、粒子収容部材１の孔の底面に絶縁性微粒子が付着することにより、絶縁被覆導電粒子の接着剤層１と接する部分とは反対側には、絶縁性微粒子数が０個である領域が４７．９μｍ２設けられたことをＳＥＭによる観察によって確認した。 Next, in the same method shown in (a) and (b) of FIG. 5, an equilateral triangle type disposed in particle density of 29000 pieces / mm 2 an insulated coating conductive particles provided on the adhesive layer 1 It was. At this time, since the insulating fine particles adhere to the bottom surface of the hole of the particle containing member 1, the number of the insulating fine particles is 0 on the side opposite to the portion of the insulating coated conductive particles that contacts the adhesive layer 1. It was confirmed by observation by SEM that a certain region was provided with 47.9 μm 2 .
　次に、４０℃に加熱したホットロールラミネータで、接着剤層１の絶縁被覆導電粒子が配されている側に接着剤層２を貼り合せて、２つのＰＥＴ樹脂フィルム間に導電性接着剤層が設けられた異方導電フィルムを得た。 Next, with a hot roll laminator heated to 40 ° C., the adhesive layer 2 is bonded to the side of the adhesive layer 1 where the insulating coating conductive particles are arranged, and the conductive adhesive layer is sandwiched between the two PET resin films. An anisotropic conductive film provided with was obtained.
（実施例２）
　粒子収容部材２を用いて、接着剤層１上に正方形型に２００００個／ｍｍ２の粒子密度で配置された絶縁被覆導電粒子を設けたこと以外は実施例１と同様にして、異方導電フィルムを得た。 (Example 2)
Using a particle containing member 2, except the provision of the square type disposed in particle density of 20000 / mm 2 an insulated coating conductive particles on the adhesive layer 1 in the same manner as in Example 1, different Hoshirubeden A film was obtained.
（実施例３）
　複合粒子１に代えて複合粒子２を、また、粒子収容部材１に代えて粒子収容部材３を用いたこと以外は実施例１と同様にして、異方導電フィルムを得た。この場合も、複合粒子の球冠領域には、絶縁性微粒子数が０個である領域が５０．２μｍ２設けられたことを確認でき、絶縁被覆導電粒子の接着剤層１と接する部分とは反対側には、絶縁性微粒子数が０個である領域が４８．７μｍ２設けられたことを確認できた。 (Example 3)
An anisotropic conductive film was obtained in the same manner as in Example 1 except that the composite particle 2 was used instead of the composite particle 1 and the particle storage member 3 was used instead of the particle storage member 1. Also in this case, it can be confirmed that 50.2 μm 2 is provided in the spherical region of the composite particle in the region where the number of insulating fine particles is 0, and what is the portion in contact with the adhesive layer 1 of the insulating coated conductive particle? On the opposite side, it was confirmed that 48.7 μm 2 of a region having 0 insulating fine particles was provided.
（実施例４）
　複合粒子１に代えて複合粒子３を、また、粒子収容部材１に代えて粒子収容部材４を用いたこと以外は実施例１と同様にして、異方導電フィルムを得た。この場合も、複合粒子の球冠領域には、絶縁性微粒子数が０個である領域が５３．３μｍ２設けられたことを確認でき、絶縁被覆導電粒子の接着剤層１と接する部分とは反対側には、絶縁性微粒子数が０個である領域が４８．７μｍ２設けられたことを確認できた。 Example 4
An anisotropic conductive film was obtained in the same manner as in Example 1 except that the composite particle 3 was used instead of the composite particle 1 and the particle storage member 4 was used instead of the particle storage member 1. Also in this case, it can be confirmed that the area where the number of insulating fine particles is 0 is provided in the spherical crown area of the composite particle, which is 53.3 μm 2, and the portion in contact with the adhesive layer 1 of the insulating coated conductive particles is On the opposite side, it was confirmed that 48.7 μm 2 of a region having 0 insulating fine particles was provided.
（実施例５）
　粒子収容部材１に代えて粒子収容部材５を用いたこと以外は実施例１と同様にして、異方導電フィルムを得た。この場合も、複合粒子の球冠領域には、絶縁性微粒子数が０個である領域が５２．６μｍ２設けられたことを確認でき、絶縁被覆導電粒子の接着剤層１と接する部分とは反対側には、絶縁性微粒子数が０個である領域が４７．９μｍ２設けられたことを確認できた。 (Example 5)
An anisotropic conductive film was obtained in the same manner as in Example 1 except that the particle containing member 5 was used instead of the particle containing member 1. Also in this case, it can be confirmed that the area where the number of insulating fine particles is 0 is provided in the spherical crown area of the composite particle is 52.6 μm 2, and the portion of the insulating coated conductive particle that contacts the adhesive layer 1 is On the opposite side, it was confirmed that 47.9 μm 2 of regions having 0 insulating fine particles were provided.
（実施例６）
　接着剤層１に代えて接着剤層３を用いたこと以外は実施例１と同様にして、異方導電フィルムを得た。 (Example 6)
An anisotropic conductive film was obtained in the same manner as in Example 1 except that the adhesive layer 3 was used in place of the adhesive layer 1.
［異方導電フィルムの評価］
　実施例１～６の異方導電フィルムについて、ＦＩＢ－ＳＥＭにて断面加工及び断面観察を行った。なお、断面観察は、絶縁被覆導電粒子の基材粒子の中心を通り且つ導電性接着剤層の厚み方向に平行な面において行い、このときの絶縁被覆導電粒子の、導電性接着剤層の厚み方向に平行な方向における粒子径Ｘと、導電性接着剤層の厚み方向と直交する方向における粒子径Ｙとを測定するとともに、絶縁被覆導電粒子と、導電性接着剤層の一方面との最短距離Ｄを測定した。結果を表１に示す。 [Evaluation of anisotropic conductive film]
The anisotropic conductive films of Examples 1 to 6 were subjected to cross-section processing and cross-section observation using FIB-SEM. The cross-sectional observation is performed on a surface passing through the center of the base particle of the insulating coated conductive particle and parallel to the thickness direction of the conductive adhesive layer, and the thickness of the conductive adhesive layer of the insulating coated conductive particle at this time The particle diameter X in a direction parallel to the direction and the particle diameter Y in a direction orthogonal to the thickness direction of the conductive adhesive layer are measured, and the shortest distance between the insulating coated conductive particles and one surface of the conductive adhesive layer The distance D was measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［接続構造体の作製］
　第１の回路部材として、バンプ電極を一列に配列したストレート配列構造を有するＩＣチップ（外形２ｍｍ×２０ｍｍ、厚み０．５５ｍｍ、バンプ電極の大きさ１００μｍ×３０μｍ、バンプ電極間距離８μｍ、バンプ電極厚み１５μｍ）を準備した。また、第２の回路部材として、ガラス基板（コーニング社製：＃１７３７、３８ｍｍ×２８ｍｍ、厚み０．３ｍｍ）の表面にＩＴＯの配線パターン（パターン幅２１μｍ、電極間スペース１７μｍ）を形成したものを準備した。 [Production of connection structure]
As a first circuit member, an IC chip having a straight arrangement structure in which bump electrodes are arranged in a row (outer dimensions 2 mm × 20 mm, thickness 0.55 mm, bump electrode size 100 μm × 30 μm, distance between bump electrodes 8 μm, bump electrode thickness 15 μm) was prepared. As the second circuit member, an ITO wiring pattern (pattern width 21 μm, interelectrode space 17 μm) formed on the surface of a glass substrate (Corning Inc .: # 1737, 38 mm × 28 mm, thickness 0.3 mm) is used. Got ready.
　実施例１～６に係る異方導電フィルム（２．５ｍｍ×２５ｍｍ）の一方のＰＥＴ樹脂フィルムを剥離し、導電性接着剤層をガラス基板上に、セラミックヒータからなるステージ（１５０ｍｍ×１５０ｍｍ）及びツール（３ｍｍ×２０ｍｍ）から構成される熱圧着装置を用いて８０℃、０．９８ＭＰａ（１０ｋｇｆ／ｃｍ２）の条件で２秒間加熱及び加圧して貼り付けた。 One PET resin film of the anisotropic conductive films (2.5 mm × 25 mm) according to Examples 1 to 6 was peeled off, and a conductive adhesive layer was placed on a glass substrate with a stage (150 mm × 150 mm) composed of a ceramic heater, and Using a thermocompression bonding apparatus composed of a tool (3 mm × 20 mm), it was attached by heating and pressing for 2 seconds at 80 ° C. and 0.98 MPa (10 kgf / cm 2 ).
　次に、異方導電フィルムの他方のＰＥＴ樹脂フィルムを剥離し、ＩＣチップのバンプ電極とガラス基板の回路電極との位置合わせを行った後、セラミックヒータからなるステージ（１５０ｍｍ×１５０ｍｍ）及びツール（３ｍｍ×２０ｍｍ）から構成される熱圧着装置を用いて、導電性接着剤層の実測最高到達温度１７０℃、及びバンプ電極での面積換算圧力７０ＭＰａの条件で５秒間加熱及び加圧して、接続構造体を得た。 Next, after peeling the other PET resin film of the anisotropic conductive film and aligning the bump electrode of the IC chip and the circuit electrode of the glass substrate, a stage (150 mm × 150 mm) comprising a ceramic heater and a tool ( 3 mm × 20 mm) using a thermocompression bonding apparatus, and heating and pressurizing for 5 seconds under the conditions of an actually measured maximum reached temperature of 170 ° C. of the conductive adhesive layer and an area conversion pressure of 70 MPa at the bump electrode. Got the body.
［接続構造体の評価］
　得られた接続構造体について、バンプ電極と回路電極との間の接続抵抗、及び隣り合う回路電極間の絶縁抵抗を評価した。なお、接続抵抗の評価は、四端子測定法にて実施し、１４箇所の測定の平均値を用いた。また、絶縁抵抗の評価は、接続構造体に５０Ｖの電圧を印加し、計１４４０か所の回路電極間の絶縁抵抗を一括で測定した。結果を表２に示す。 [Evaluation of connection structure]
About the obtained connection structure, the connection resistance between a bump electrode and a circuit electrode and the insulation resistance between adjacent circuit electrodes were evaluated. The connection resistance was evaluated by a four-terminal measurement method, and the average value of 14 measurements was used. In addition, the insulation resistance was evaluated by applying a voltage of 50 V to the connection structure and measuring the insulation resistance between a total of 1440 circuit electrodes in a lump. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、実施例１～６の異方導電フィルムを用いて作製した接続構造体は、接続抵抗値が１．２Ω以下であり、かつ充分な絶縁抵抗を有していた。 As shown in Table 2, the connection structures produced using the anisotropic conductive films of Examples 1 to 6 had a connection resistance value of 1.2Ω or less and sufficient insulation resistance.
　１…基材粒子、２…絶縁性微粒子、３…球冠領域、６…バンプ電極、８…回路電極、１０…絶縁被覆導電粒子、１１…剥離フィルム付き異方導電フィルム、１２…剥離フィルム、１３…導電性接着剤層（異方導電フィルム）、１３ａ…第１の接着剤層、１３ｂ…第２の接着剤層、２０…複合粒子、３０…粒子収容部材、３２…孔、５０…接続構造体、５２…第１の回路部材、５３…第２の回路部材、５４…硬化物。 DESCRIPTION OF SYMBOLS 1 ... Base particle, 2 ... Insulating fine particle, 3 ... Spherical crown area | region, 6 ... Bump electrode, 8 ... Circuit electrode, 10 ... Insulation coating electrically conductive particle, 11 ... Anisotropic conductive film with a release film, 12 ... Release film, DESCRIPTION OF SYMBOLS 13 ... Conductive adhesive layer (anisotropic conductive film), 13a ... 1st adhesive layer, 13b ... 2nd adhesive layer, 20 ... Composite particle, 30 ... Particle accommodating member, 32 ... Hole, 50 ... Connection Structure 52, first circuit member, 53 ... second circuit member, 54 ... cured product.

Claims (11)

  1. 　導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子と、を備え、
    　単位面積当たりの絶縁性微粒子数が少ない若しくは０である粗領域と、前記粗領域よりも単位面積当たりの絶縁性微粒子数が多い密領域と、を有する、絶縁被覆導電粒子。     Comprising substrate particles having conductivity, and insulating fine particles covering the surface of the substrate particles,
    An insulating coated conductive particle comprising: a rough region having a small or zero number of insulating fine particles per unit area; and a dense region having a larger number of insulating fine particles per unit area than the rough region.
  2. 　前記基材粒子の中心を通る中心軸が通る前記粗領域を２つ有する、請求項１に記載の絶縁被覆導電粒子。 The insulation-coated conductive particles according to claim 1, comprising two rough regions through which a central axis passing through the center of the substrate particles passes.
  3. 　導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子と、を備える複合粒子の、前記基材粒子を二つの平行な平面で切ったときの２つの球冠領域にある前記絶縁性微粒子の一部又は全部を除去してなる、絶縁被覆導電粒子。 A composite particle comprising conductive base particles and insulating fine particles covering the surface of the base particles, in two spherical regions when the base particles are cut in two parallel planes. Insulating coated conductive particles obtained by removing some or all of the insulating fine particles.
  4. 　導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子と、を備え、
    　前記基材粒子を二つの平行な平面で切ったときの球帯領域に前記絶縁性微粒子が偏在している、絶縁被覆導電粒子。     Comprising substrate particles having conductivity, and insulating fine particles covering the surface of the substrate particles,
    Insulating coated conductive particles in which the insulating fine particles are unevenly distributed in a spherical zone region when the substrate particles are cut by two parallel planes.
  5. 　請求項１～４のいずれか一項に記載の絶縁被覆導電粒子と、接着剤成分と、が含まれる導電性接着剤層、を備える、異方導電フィルム。 An anisotropic conductive film comprising a conductive adhesive layer containing the insulating coated conductive particles according to any one of claims 1 to 4 and an adhesive component.
  6. 　請求項２に記載の絶縁被覆導電粒子を含み、
    　前記絶縁被覆導電粒子は、前記基材粒子の中心を通り且つ前記導電性接着剤層の厚み方向に平行な軸が２つの前記粗領域を通るように配されている、請求項５に記載の異方導電フィルム。     Insulating coated conductive particles according to claim 2,
    The insulating coating conductive particles are arranged so that an axis passing through the center of the base particle and parallel to the thickness direction of the conductive adhesive layer passes through the two rough regions. Anisotropic conductive film.
  7. 　請求項３に記載の絶縁被覆導電粒子を含み、
    　前記絶縁被覆導電粒子は、前記基材粒子の中心を通り且つ前記導電性接着剤層の厚み方向に平行な軸が２つの前記球冠領域を通るように配されている、請求項５に記載の異方導電フィルム。     Insulating coated conductive particles according to claim 3,
    The insulating coating conductive particles are arranged so that an axis passing through the center of the base particle and parallel to the thickness direction of the conductive adhesive layer passes through the two crown regions. Anisotropic conductive film.
  8. 　請求項３又は４に記載の絶縁被覆導電粒子を含み、
    　前記絶縁被覆導電粒子は、前記基材粒子の中心を通り且つ前記導電性接着剤層の厚み方向に平行な軸と前記二つの平行な平面とが直交するように、配されている、請求項５に記載の異方導電フィルム。     Insulating coated conductive particles according to claim 3 or 4,
    The insulating coated conductive particles are arranged so that an axis parallel to the thickness direction of the conductive adhesive layer and the two parallel planes are orthogonal to each other through the center of the base particle. 5. An anisotropic conductive film according to 5.
  9. 　導電性を有する基材粒子と、該基材粒子の表面を被覆する絶縁性微粒子と、を備える複合粒子を用意するステップと、
    　閉鎖端面を有する孔が設けられた粒子収容部材の前記孔に前記複合粒子を収容するステップと、
    　前記孔から露出する前記複合粒子の球冠領域にある前記絶縁性微粒子の一部又は全部を除去するステップと、
    　第１の接着剤層上に、球冠領域の絶縁性微粒子が除去された前記複合粒子を、前記球冠領域側が前記第１の接着剤層に接するように前記粒子収容部材から移しつつ、前記複合粒子の前記絶縁性微粒子の一部を前記粒子収容部材の前記閉鎖端面に付着させて除去することにより、前記第１の接着剤層上に絶縁被覆導電粒子を設けるステップと、
    　前記第１の接着剤層の前記絶縁被覆導電粒子が配されている側に第２の接着剤層を貼り合せるステップと、
    を備える、異方導電フィルムの製造方法。     Preparing composite particles comprising conductive base particles and insulating fine particles covering the surface of the base particles;
    Containing the composite particles in the holes of the particle containing member provided with a hole having a closed end surface;
    Removing part or all of the insulating fine particles in the spherical region of the composite particles exposed from the holes;
    On the first adhesive layer, the composite particles from which the insulating fine particles in the spherical crown region have been removed are moved from the particle containing member so that the spherical crown region side is in contact with the first adhesive layer, Providing insulating coated conductive particles on the first adhesive layer by attaching and removing a part of the insulating fine particles of the composite particles to the closed end surface of the particle containing member;
    Bonding a second adhesive layer to the side of the first adhesive layer on which the insulating coated conductive particles are disposed;
    A method for producing an anisotropic conductive film.
  10. 　バンプ電極を有する第１の回路部材と、
    　前記バンプ電極に対応する回路電極を有する第２の回路部材と、
    　前記バンプ電極及び前記回路電極の間に介在して前記バンプ電極及び前記回路電極を電気的に接続する請求項１～４のいずれか一項に記載の絶縁被覆導電粒子と、
    を備える、接続構造体。     A first circuit member having a bump electrode;
    A second circuit member having a circuit electrode corresponding to the bump electrode;
    The insulating coated conductive particles according to any one of claims 1 to 4, wherein the insulating film is electrically connected between the bump electrode and the circuit electrode, and interposed between the bump electrode and the circuit electrode.
    A connection structure comprising:
  11. 　バンプ電極を有する第１の回路部材と、前記バンプ電極に対応する回路電極を有する第２の回路部材との間に、請求項５～８のいずれか一項に記載の異方導電フィルム又は請求項９の方法によって得られる異方導電フィルムを介在させ、前記第１の回路部材と前記第２の回路部材とを熱圧着するステップを有する、接続構造体の製造方法。
          The anisotropic conductive film according to any one of Claims 5 to 8, or between the first circuit member having a bump electrode and the second circuit member having a circuit electrode corresponding to the bump electrode. The manufacturing method of a connection structure which has the step which carries out the thermocompression bonding of the said 1st circuit member and the said 2nd circuit member by interposing the anisotropic conductive film obtained by the method of claim | item 9.
PCT/JP2018/002350 2017-01-27 2018-01-25 Insulation covered conductive particles, anisotropic conductive film, method for producing anisotropic conductive film, connection structure and method for producing connection structure WO2018139552A1 (en)

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CN201880008563.1A CN110214353B (en) 2017-01-27 2018-01-25 Insulation-coated conductive particles, anisotropic conductive film, method for producing anisotropic conductive film, bonded structure, and method for producing bonded structure
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