WO2021172486A1 - 電磁波シールドフィルム - Google Patents

電磁波シールドフィルム Download PDF

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Publication number
WO2021172486A1
WO2021172486A1 PCT/JP2021/007245 JP2021007245W WO2021172486A1 WO 2021172486 A1 WO2021172486 A1 WO 2021172486A1 JP 2021007245 W JP2021007245 W JP 2021007245W WO 2021172486 A1 WO2021172486 A1 WO 2021172486A1
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WO
WIPO (PCT)
Prior art keywords
layer
conductive adhesive
adhesive layer
insulating layer
mass
Prior art date
Application number
PCT/JP2021/007245
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English (en)
French (fr)
Japanese (ja)
Inventor
滋和 梅村
修 磯部
Original Assignee
タツタ電線株式会社
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.)
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Publication date
Application filed by タツタ電線株式会社 filed Critical タツタ電線株式会社
Priority to KR1020227021873A priority Critical patent/KR20220147066A/ko
Priority to CN202180012297.1A priority patent/CN115004875A/zh
Priority to JP2021532328A priority patent/JP7027618B2/ja
Publication of WO2021172486A1 publication Critical patent/WO2021172486A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0086—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single discontinuous metallic layer on an electrically insulating supporting structure, e.g. metal grid, perforated metal foil, film, aggregated flakes, sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/02—Noble metals
    • B32B2311/08—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

  • the present invention relates to an electromagnetic wave shielding film. More specifically, the present invention relates to an electromagnetic wave shielding film used for a printed wiring board.
  • Printed wiring boards are often used in electronic devices such as mobile phones, video cameras, and laptop computers to incorporate circuits into their mechanisms. It is also used to connect a movable part such as a printer head to a control part. Electromagnetic wave shielding measures are indispensable for these electronic devices, and shielded printed wiring boards with electromagnetic wave shielding measures are also used in the printed wiring boards used in the devices.
  • an electromagnetic wave shield film (hereinafter, may be simply referred to as "shield film”) is used for the purpose of electromagnetic wave shielding measures.
  • a shield film used by adhering to a printed wiring board has a shield layer such as a metal layer and a conductive adhesive sheet provided on the surface of the shield layer.
  • shield film having a conductive adhesive sheet for example, those disclosed in Patent Documents 1 and 2 are known.
  • the shield film is used by adhering the exposed surface of the conductive adhesive sheet to the surface of the printed wiring board, specifically, the coverlay surface provided on the surface of the printed wiring board.
  • These conductive adhesive sheets are usually thermocompression bonded under high temperature and high pressure conditions to be bonded and laminated on a printed wiring board.
  • the shield film arranged on the printed wiring board in this way exhibits a performance (shielding performance) of shielding electromagnetic waves from the outside of the printed wiring board.
  • shield films may be required to have the ability to be easily aligned when attached to a printed wiring board. For this reason, the shield film tends to be required to be transparent.
  • a transparent conductive layer having a thin layer thickness as the conductive layer in the shield film.
  • the conductivity is improved as the amount of the conductive particles in the conductive adhesive layer is increased, whereas in the shield film using the transparent conductive layer, the conductive adhesive is used.
  • the electrical connection resistance value increases and the conductivity decreases.
  • the present invention has been made in view of the above, and an object of the present invention is to have excellent transparency and an electrical connection resistance value even when a large amount of conductive particles are blended in the conductive adhesive layer. Is to provide a low electromagnetic wave shielding film.
  • the present inventors have made a transparent electromagnetic wave shield film having a specific layer structure even when a large amount of conductive particles are blended in the conductive adhesive layer. It was found that it was excellent and had a low electrical connection resistance value.
  • the present invention has been completed based on these findings.
  • the first insulating layer, the silver nanowire layer, the second insulating layer, and the conductive adhesive layer are laminated in this order.
  • the thickness of the second insulating layer is 50 to 500 nm, and the thickness of the second insulating layer is 50 to 500 nm.
  • the conductive adhesive layer contains a binder component and spherical or dendritic conductive particles.
  • the content ratio of the conductive particles is 1 to 80% by mass with respect to 100% by mass of the conductive adhesive layer.
  • the second insulating layer and the conductive adhesive layer are directly laminated.
  • the second insulating layer is directly laminated with the conductive adhesive layer on one surface and the silver nanowire layer on the other surface.
  • the content ratio of the conductive particles is preferably 30 to 80% by mass with respect to 100% by mass of the conductive adhesive layer.
  • the total light transmittance in the measurement method based on JIS K7361-1 is 10% or more.
  • the present invention also provides a shield-printed wiring board provided with the above-mentioned electromagnetic wave shield film.
  • the electromagnetic wave shielding film of the present invention is excellent in transparency and has a low electrical connection resistance value in both the case where a small amount of conductive particles are mixed and the case where a large amount of conductive particles are mixed in the conductive adhesive layer.
  • the shield film of the present invention has a layer structure in which a first insulating layer, a silver nanowire layer, a second insulating layer, and a conductive adhesive layer are laminated in this order.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the shield film of the present invention.
  • the shield film 1 of the present invention shown in FIG. 1 has a first insulating layer 11, a silver nanowire layer 12, a second insulating layer 13, and a conductive adhesive layer 14 in this order.
  • the first insulating layer is a transparent base material that functions as a protection for the silver nanowire layer and a support for the silver nanowires in the shield film of the present invention.
  • Examples of the first insulating layer include a plastic base material (particularly a plastic film) and a glass plate.
  • the first insulating layer may be a single layer, or may be a laminate of the same type or different types.
  • Examples of the resin constituting the plastic base material include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymerized polypropylene, block copolymerized polypropylene, and homopolyprolene.
  • Polybutene polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene- Polyolefin resins such as butene copolymers and ethylene-hexene copolymers; polyurethane; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate and polybutylene terephthalate (PBT); polycarbonate (PC); polyimide (PI); polyether Etherketone (PEEK); polyetherimide; polyamide such as aramid and total aromatic polyamide; polyphenylsulfide; polysulfone (PS); polyethersulfone (PES); acrylic resin such as polymethylmethacrylate (PMMA); acrylonitrile-butadiene -Styrene copolymer (ABS); fluor
  • polyester and cellulose resins are preferable, and polyethylene terephthalate and triacetyl cellulose are more preferable, from the viewpoint of being more excellent in transparency.
  • the surface of the first insulating layer (particularly, the surface on the silver nanowire layer side) is treated with, for example, corona discharge treatment, plasma treatment, sand mat processing, etc. for the purpose of improving adhesion, retention, etc. with an adjacent layer such as the silver nanowire layer.
  • corona discharge treatment plasma treatment, sand mat processing, etc.
  • an adjacent layer such as the silver nanowire layer.
  • the surface treatment for enhancing the adhesion is applied to the entire surface of the first insulating layer on the silver nanowire layer side.
  • the thickness of the first insulating layer is not particularly limited, but is preferably 1 to 15 ⁇ m, more preferably 3 to 10 ⁇ m. When the thickness is 1 ⁇ m or more, the shield film can be more sufficiently supported and the silver nanowire layer can be protected. When the thickness is 15 ⁇ m or less, the transparency and flexibility are excellent, and it is economically advantageous. When the first insulating layer has a multi-layer structure, the thickness of the first insulating layer is the total of all the layer thicknesses.
  • the silver nanowire layer is an element that functions as a shield layer in the shield film of the present invention.
  • the silver nanowire layer may be a single layer, or may be a laminate of the same type or different types.
  • the thickness of the silver nanowire layer is preferably 20 to 500 nm, more preferably 50 to 150 nm. When the thickness is 20 nm or more, the shielding performance can be maintained high. When the thickness is 500 nm or less, the transparency of the shield film is excellent. When the silver nanowire layer has a multi-layer structure, the thickness of the silver nanowire layer is the total of all the layer thicknesses.
  • the second insulating layer is a transparent layer that protects the silver nanowire layer.
  • the second insulating layer may be either a single layer or a plurality of layers.
  • the second insulating layer preferably contains a binder component.
  • the binder component include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable compound.
  • the thermoplastic resin, the thermosetting resin, and the active energy ray-curable compound include those exemplified as a binder component that can be contained in the conductive adhesive layer described later.
  • the binder component only one kind may be used, or two or more kinds may be used.
  • the content of the binder component in the second insulating layer is not particularly limited, but is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass with respect to 100% by mass of the second insulating layer. % Or more.
  • the content is 70% by mass or more, the flexibility is excellent, the embedding property in a hole having a small diameter is excellent, and the connection stability is excellent.
  • the second insulating layer may contain other components other than the binder component as long as the effects of the present invention are not impaired.
  • the other components include a curing agent, a curing accelerator, a plasticizer, a flame retardant, a defoaming agent, a viscosity modifier, an antioxidant, a diluent, an antioxidant, a filler, a leveling agent, and a coupling agent. , UV absorbers, tackifier resins, antiblocking agents and the like.
  • the above other components only one kind may be used, or two or more kinds may be used.
  • the thickness of the second insulating layer is 50 to 500 nm, preferably 100 to 300 nm. When the thickness is 50 nm or more, the shielding performance and the connection stability are excellent. When the thickness is 500 nm or less, the transparency and connection stability are excellent. When the second insulating layer has a multi-layer structure, the thickness of the second insulating layer is the total of all the layer thicknesses.
  • the second insulating layer is preferably directly laminated with the conductive adhesive layer, with the conductive adhesive layer on one side and the silver on the other side. It is particularly preferable that each is directly laminated with the nanowire layer.
  • the conductive adhesive layer has, for example, adhesiveness for adhering the shield film of the present invention to a printed wiring board and conductivity for electrically connecting to the silver nanowire layer. It also functions as a shield layer that exhibits shielding performance together with the silver nanowire layer.
  • the conductive adhesive layer may be either a single layer or a plurality of layers.
  • the conductive adhesive layer contains a binder component and spherical or dendritic (dendrite-like) conductive particles.
  • binder component examples include thermoplastic resins, thermosetting resins, active energy ray-curable compounds, and the like.
  • the binder component only one kind may be used, or two or more kinds may be used.
  • thermoplastic resin examples include polystyrene-based resin, vinyl acetate-based resin, polyester-based resin, polyolefin-based resin (for example, polyethylene-based resin, polypropylene-based resin composition, etc.), polyimide-based resin, acrylic-based resin, and the like. Be done.
  • thermoplastic resin only one kind may be used, or two or more kinds may be used.
  • thermosetting resin examples include both a thermosetting resin (thermosetting resin) and a resin obtained by curing the thermosetting resin.
  • thermosetting resin examples include phenolic resin, epoxy resin, urethane resin, urethane urea resin, melamine resin, alkyd resin and the like. As the thermosetting resin, only one kind may be used, or two or more kinds may be used.
  • epoxy resin examples include bisphenol type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, terpen type epoxy resin, glycidyl ether type epoxy resin, and glycidyl amine type.
  • examples thereof include epoxy-based resins and novolak-type epoxy-based resins.
  • Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabrom bisphenol A type epoxy resin and the like.
  • Examples of the glycidyl ether type epoxy resin include tris (glycidyloxyphenyl) methane and tetrakis (glycidyloxyphenyl) ethane.
  • Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane.
  • Examples of the novolak type epoxy resin include cresol novolac type epoki resin, phenol novolac type epoxy resin, ⁇ -naphthol novolac type epoxy resin, brominated phenol novolac type epoxy resin and the like.
  • the active energy ray-curable compound examples include both a compound that can be cured by irradiation with active energy rays (active energy ray curable compound) and a compound obtained by curing the active energy ray curable compound.
  • the active energy ray-curable compound is not particularly limited, and examples thereof include a polymerizable compound having at least two radical reactive groups (for example, (meth) acryloyl group) in the molecule.
  • the active energy ray-curable compound only one kind may be used, or two or more kinds may be used.
  • thermosetting resin is preferable.
  • the binder component can be cured by pressurization and heating, and the adhesiveness with the printed wiring board is good. Become.
  • a curing agent for accelerating the heat curing reaction may be contained as a component constituting the binder component.
  • the curing agent can be appropriately selected depending on the type of the thermosetting resin. As the curing agent, only one kind may be used, or two or more kinds may be used.
  • the content ratio of the binder component in the conductive adhesive layer is not particularly limited, but is preferably 20 to 99% by mass, more preferably 30 to 80% by mass, based on 100% by mass of the total amount of the conductive adhesive layer. More preferably, it is 40 to 70% by mass. When the content ratio is 20% by mass or more, the adhesion to the printed wiring board is more excellent. When the content ratio is 99% by mass or less, the conductive particles can be sufficiently contained.
  • the conductive particles spherical conductive particles and / or dendritic conductive particles are used.
  • the conductive particles are dendritic conductive particles from the viewpoint of being more excellent in connection stability.
  • the conductive particles are preferably spherical conductive particles.
  • Examples of the conductive particles include metal particles, metal-coated resin particles, carbon fillers, and the like. As the conductive particles, only one kind may be used, or two or more kinds may be used.
  • Examples of the metal constituting the coating portion of the metal particles and the metal-coated resin particles include gold, silver, copper, nickel, zinc and the like. Only one kind of the above metal may be used, or two or more kinds may be used.
  • the metal particles include copper particles, silver particles, nickel particles, silver-coated copper particles, gold-coated copper particles, silver-coated nickel particles, gold-coated nickel particles, and silver-coated alloy particles.
  • the silver-coated alloy particles include silver-coated copper alloy particles in which alloy particles containing copper (for example, copper alloy particles made of an alloy of copper, nickel, and zinc) are coated with silver.
  • the metal particles can be produced by an electrolysis method, an atomizing method, a reduction method or the like.
  • silver particles silver particles, silver-coated copper particles, and silver-coated copper alloy particles are preferable.
  • Silver-coated copper particles and silver-coated copper alloy particles are particularly preferable from the viewpoints of excellent conductivity, suppression of oxidation and aggregation of metal particles, and reduction of cost of metal particles.
  • the median diameter (D50) of the conductive particles is not particularly limited, but is preferably 5 to 15 ⁇ m, more preferably 5 to 10 ⁇ m.
  • the median diameter is the median diameter of all the spherical conductive particles and / or the dendritic conductive particles in the conductive adhesive layer, and is an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method. It shall refer to the particle size.
  • the median diameter is within the above range, the connection stability is more excellent in the present invention using conductive particles.
  • the median diameter can be measured by, for example, a laser diffraction type particle size distribution measuring device (trade name “SALD-2200”, manufactured by Shimadzu Corporation).
  • the content ratio of the conductive particles in the conductive adhesive layer is 1 to 80% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass with respect to 100% by mass of the conductive adhesive layer. It is mass%.
  • the connection resistance value is low and the connection stability is low even when the conductive adhesive layer contains the conductive particles in a small amount of about 1% by mass or as much as 80% by mass. Excellent for.
  • the conductive adhesive layer may contain other components other than the above-mentioned components as long as the effects of the present invention are not impaired.
  • the other components include components contained in known or conventional adhesive layers.
  • the other components include curing accelerators, plasticizers, flame retardants, defoamers, viscosity modifiers, antioxidants, diluents, anti-settling agents, fillers, leveling agents, coupling agents, and UV absorption. Examples thereof include agents, tackifier resins, and antiblocking agents.
  • the above other components only one kind may be used, or two or more kinds may be used.
  • the content of the conductive particles other than the spherical conductive particles and the dendritic conductive particles is, for example, less than 10 parts by mass, preferably 5 with respect to 100 parts by mass of the spherical conductive particles and / or the dendritic conductive particles. Less than parts by mass, more preferably less than 1 part by mass.
  • the thickness of the conductive adhesive layer is not particularly limited, but is preferably 3 to 20 ⁇ m, more preferably 5 to 15 ⁇ m. When the thickness is 3 ⁇ m or more, the shielding performance is more excellent. When the thickness is 20 ⁇ m or less, the surface of the conductive particles tends to be closer to or exposed from the surface of the layer, and the connection stability is more excellent.
  • the ratio of the conductive adhesive layer thickness to the D50 of the conductive particles is not particularly limited, but is preferably 0.2 to 1.5, and more preferably 0.5. ⁇ 1.0. When the above ratio is 0.2 or more, the adhesiveness to an adherend such as a printed wiring board becomes better. When the above ratio is 1.5 or less, the amount of conductive particles exposed from the surface of the conductive adhesive layer increases, and the connection stability is more excellent.
  • the shield film of the present invention may have a separator (release film) on the conductive adhesive layer side.
  • the separators are laminated so that they can be peeled off from the shield film of the present invention.
  • the separator is an element for coating and protecting the conductive adhesive layer, and is peeled off when the shield film of the present invention is used.
  • separator examples include polyethylene terephthalate (PET) film, polyethylene film, polypropylene film, plastic film and paper surface-coated with a release agent such as a fluorine-based release agent and a long-chain alkyl acrylate-based release agent. ..
  • PET polyethylene terephthalate
  • a release agent such as a fluorine-based release agent and a long-chain alkyl acrylate-based release agent.
  • the thickness of the separator is preferably 10 to 200 ⁇ m, more preferably 15 to 150 ⁇ m. When the thickness is 10 ⁇ m or more, the protection performance is more excellent. When the thickness is 200 ⁇ m or less, the separator can be easily peeled off during use.
  • the shield film of the present invention may have a first insulating layer, a silver nanowire layer, a second insulating layer, and other layers other than the conductive adhesive layer.
  • the other layers include other insulating layers, antireflection layers, antiglare layers, antifouling layers, hard coat layers, ultraviolet absorbing layers, anti-Newton ring layers, and the like.
  • the shield film of the present invention has excellent transparency.
  • the total light transmittance of the shield film of the present invention in the measurement method based on JIS K7361-1 is preferably 10% or more, more preferably 20% or more, further preferably 50% or more, and particularly preferably 65% or more. be.
  • the total light transmittance can be measured using a known spectrophotometer.
  • the total light transmittance is measured for a laminate having the first insulating layer and the conductive adhesive layer as both end layers.
  • the haze value of the shield film of the present invention in the measurement method based on JIS K7361-1 is preferably 95% or less, more preferably 92% or less, still more preferably 90% or less.
  • the haze value can be measured using a known spectrophotometer.
  • the haze value is measured for a laminate having the first insulating layer and the conductive adhesive layer as both end layers.
  • the shield film of the present invention is preferably used for a printed wiring board, and particularly preferably for a flexible printed wiring board (FPC).
  • the shield film of the present invention has a low electrical connection resistance value when both a small amount of conductive particles and a large amount of conductive particles are added to the conductive adhesive layer. In addition, it has excellent transparency and is easy to align on the printed wiring board. Therefore, the shield film of the present invention can be preferably used as an electromagnetic wave shield film for a flexible printed wiring board.
  • a silver nanowire layer 12 is formed on the first insulating layer 11.
  • the silver nanowire layer 12 can be formed by laminating the silver nanowire layer 12 on the surface of the first insulating layer 11.
  • a resin composition for forming the second insulating layer 13 is applied (coated) on the surface of the formed silver nanowire layer 12, and if necessary, it is formed by removing the solvent and / or partially curing it. can do.
  • the resin composition contains, for example, a solvent (solvent) in addition to each component contained in the second insulating layer described above.
  • a solvent solvent
  • examples of the solvent include toluene, acetone, methyl ethyl ketone, methanol, ethanol, propanol, ethyl acetate, propyl acetate, butyl acetate, dimethylformamide and the like.
  • the solid content concentration of the resin composition is appropriately set according to the thickness of the second insulating layer to be formed and the like.
  • a known coating method may be used for coating the above resin composition.
  • a coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a lip coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, a direct coater, or a slot die coater may be used.
  • an adhesive composition for forming the conductive adhesive layer 14 is applied (coated) on the surface of the formed second insulating layer, and if necessary, the solvent is removed and / or partially cured to form the adhesive composition. can do.
  • the adhesive composition contains, for example, a solvent in addition to each component contained in the conductive adhesive layer described above.
  • the solvent include those exemplified as the solvent that can be contained in the above-mentioned resin composition.
  • the solid content concentration of the adhesive composition is appropriately set according to the thickness of the conductive adhesive layer to be formed and the like.
  • a known coating method may be used for applying the adhesive composition.
  • those exemplified as a coater used for coating the above-mentioned resin composition can be mentioned.
  • each layer has been described, but the method is not limited to such a method, and is not limited to such a method, for example, on a temporary base material such as a separate film or a base material. It may be produced by a method (lamination method) in which individually formed layers are laminated and sequentially bonded.
  • a printed wiring board can be produced using the shield film of the present invention.
  • a printed wiring board for example, a coverlay
  • the conductive adhesive layer may be thermoset.
  • the content ratio of the conductive particles in the table indicates the ratio in the conductive adhesive layer.
  • Comparative Example 1 A silver nanowire layer (wire diameter 30 nm, wire length 20 ⁇ m, thickness about 70 nm) was laminated and laminated on the surface of a PET film (thickness 6 ⁇ m). Then, the adhesive composition obtained by blending and mixing the epoxy resin solution and the conductive particles A is applied to the surface of the silver nanowire layer using a wire bar and heated at 120 ° C. for 1 minute to conduct conductivity. A sex adhesive layer (thickness 5 ⁇ m) was formed. As described above, the shield film of Comparative Example 1 was produced. The blending amount of the epoxy resin solution and the conductive particles A was such that the proportion of the epoxy resin in the conductive adhesive layer was 70% by mass and the proportion of the conductive particles A was 30% by mass.
  • Comparative Examples 2 and 3 Each shield film was prepared in the same manner as in Comparative Example 1 except that the types and content ratios of the conductive particles were changed as shown in Table 1.
  • Example 1 A silver nanowire layer (wire diameter 30 nm, wire length 20 ⁇ m, thickness about 70 nm) was laminated and laminated on the surface of a PET film (thickness 6 ⁇ m). Next, a polyester-based resin composition was applied to the surface of the silver nanowire layer using a wire bar, and heated at 100 ° C. for 1 minute to form a resin layer (thickness 50 nm). Then, the adhesive composition obtained by blending and mixing the epoxy resin solution and the conductive particles A is applied to the surface of the resin layer using a wire bar, and heated at 120 ° C. for 1 minute to be conductive. An adhesive layer (thickness 5 ⁇ m) was formed. As described above, the shield film of Example 1 was produced. The blending amount of the epoxy resin solution and the conductive particles A was such that the proportion of the epoxy resin in the conductive adhesive layer was 70% by mass and the proportion of the conductive particles A was 30% by mass.
  • Example 4 A shield film was produced in the same manner as in Example 11 except that the content ratio of the conductive particles was changed as shown in Table 1.
  • Example 7 A shield film was produced in the same manner as in Example 1 except that the types of conductive particles were changed as shown in Table 1.
  • connection resistance value Two copper foil patterns (4 mm width, 1 mm pitch) simulating a ground pattern are formed on a base member made of a polyimide film, and an insulating adhesive layer and a polyimide film are formed on the two copper foil patterns (4 mm width, 1 mm pitch).
  • a printed wiring board on which a coverlay (insulating film) made of the material was formed was prepared.
  • a gold plating layer was provided as a surface layer on the surface of the copper foil pattern.
  • the coverlay was formed with a circular opening simulating a ground connection portion having a diameter of 0.8 mm.
  • the shield film produced in each Example and Comparative Example and the printed wiring board were adhered using a press under the conditions of temperature: 170 ° C., time: 30 minutes, and pressure: 2 to 3 MPa. After adhering the shield film, the electric resistance value between the two copper foil patterns was measured with an ohmmeter, and the connectivity between the copper foil pattern and the conductive adhesive sheet was evaluated and used as the connection resistance value.
  • the shield film of the present invention has high total light transmittance and excellent transparency even when a large amount of conductive particles of 30 to 50% by mass is blended.
  • the connection resistance value was low and the connection stability was excellent (Examples 1 to 9).
  • spherical conductive particles are used (Examples 1 to 6) and when dendritic conductive particles are used (Examples 7 to 9), the total light transmittance tends to be high and the transparency tends to be excellent. there were.
  • connection resistance value tends to be low and the connection stability tends to be excellent. there were.
  • the resin layer was not provided between the silver nanowire layer and the conductive adhesive layer (Comparative Examples 1 to 3)
  • the same type of conductive particles were used in the same proportion under a large amount of compounding condition of 30% by mass or more. The connection resistance value was higher than that of the cases (Examples 1 to 9).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Laminated Bodies (AREA)
PCT/JP2021/007245 2020-02-26 2021-02-26 電磁波シールドフィルム WO2021172486A1 (ja)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006035773A (ja) * 2004-07-29 2006-02-09 Takiron Co Ltd 粘接着性導電成形体

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JP5672201B2 (ja) 2011-09-07 2015-02-18 デクセリアルズ株式会社 異方性導電フィルム及び接続構造体の製造方法
WO2015068611A1 (ja) 2013-11-07 2015-05-14 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、配線デバイス、および配線デバイスの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006035773A (ja) * 2004-07-29 2006-02-09 Takiron Co Ltd 粘接着性導電成形体

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