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WO2018139552A1 - Particules conductrices recouvertes d'isolant, film conducteur anisotrope et son procédé de production, et structure de connexion et son procédé de production - Google Patents

Particules conductrices recouvertes d'isolant, film conducteur anisotrope et son procédé de production, et structure de connexion et son procédé de production 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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WIPO (PCT)
Prior art keywords
particles
insulating
adhesive layer
particle
conductive
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PCT/JP2018/002350
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English (en)
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
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN201880008563.1A priority Critical patent/CN110214353B/zh
Priority to CN202110274170.9A priority patent/CN113053562B/zh
Priority to JP2018564633A priority patent/JP7077963B2/ja
Priority to KR1020197024263A priority patent/KR102422589B1/ko
Publication of WO2018139552A1 publication Critical patent/WO2018139552A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • 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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  • Adhesives Or Adhesive Processes (AREA)

Abstract

Selon la présente invention, chacune des particules conductrices recouvertes d'isolant comprend une particule de matériau de base conductrice et des particules fines isolantes qui recouvrent la surface de la particule de matériau de base, et présente une région creuse où le nombre de fines particules isolantes par unité de surface est faible ou égal à 0, et une région dense où le nombre de particules fines isolantes par unité de surface est supérieur à celui de la région creuse.
PCT/JP2018/002350 2017-01-27 2018-01-25 Particules conductrices recouvertes d'isolant, film conducteur anisotrope et son procédé de production, et structure de connexion et son procédé de production WO2018139552A1 (fr)

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CN201880008563.1A CN110214353B (zh) 2017-01-27 2018-01-25 绝缘被覆导电粒子、各向异性导电膜、各向异性导电膜的制造方法、连接结构体和连接结构体的制造方法
CN202110274170.9A CN113053562B (zh) 2017-01-27 2018-01-25 绝缘被覆导电粒子、各向异性导电膜及其制造方法、连接结构体及其制造方法
JP2018564633A JP7077963B2 (ja) 2017-01-27 2018-01-25 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
KR1020197024263A KR102422589B1 (ko) 2017-01-27 2018-01-25 절연 피복 도전 입자, 이방 도전 필름, 이방 도전 필름의 제조 방법, 접속 구조체 및 접속 구조체의 제조 방법

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TW201834091A (zh) 2018-09-16
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JPWO2018139552A1 (ja) 2019-11-14
KR20190109471A (ko) 2019-09-25
CN113053562B (zh) 2023-03-31
CN110214353A (zh) 2019-09-06
JP7077963B2 (ja) 2022-05-31
TW202326880A (zh) 2023-07-01
TWI804485B (zh) 2023-06-11
CN110214353B (zh) 2021-04-02

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