WO2021177328A1 - 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
WO2021177328A1
WO2021177328A1 PCT/JP2021/008033 JP2021008033W WO2021177328A1 WO 2021177328 A1 WO2021177328 A1 WO 2021177328A1 JP 2021008033 W JP2021008033 W JP 2021008033W WO 2021177328 A1 WO2021177328 A1 WO 2021177328A1
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WO
WIPO (PCT)
Prior art keywords
electromagnetic wave
layer
conductive adhesive
film
adhesive layer
Prior art date
Application number
PCT/JP2021/008033
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English (en)
French (fr)
Japanese (ja)
Inventor
上農　憲治
森元　昌平
宏 田島
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.)
Filing date
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 JP2022504413A priority Critical patent/JP7506150B2/ja
Priority to CN202180013589.7A priority patent/CN115024029A/zh
Priority to KR1020227024885A priority patent/KR20220148802A/ko
Publication of WO2021177328A1 publication Critical patent/WO2021177328A1/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
    • H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
    • 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
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • 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

Definitions

  • This disclosure relates to an electromagnetic wave shield film.
  • FPCs flexible printed wiring boards
  • the electromagnetic wave shielding film for example, a film including an electromagnetic wave shielding layer such as a metal thin film and a conductive adhesive layer containing conductive particles is known. By heating and pressing the conductive adhesive layer of the electromagnetic wave shielding film on the insulating layer covering the circuit pattern of the printed wiring board, the electromagnetic wave shielding film is adhered to the printed wiring board and the shield printed wiring board. Is produced.
  • the insulating layer is provided with an opening that exposes the ground circuit, and by heat-pressing the electromagnetic wave shield film while it is placed on the printed wiring board, the conductive adhesive layer flows and the opening. Is filled with a conductive adhesive.
  • the electromagnetic wave shield layer and the ground circuit included in the circuit pattern of the printed wiring board are electrically connected via the conductive adhesive, and the electromagnetic wave shield film can exhibit the shielding performance.
  • the parts are mounted on the shield printed wiring board by going through the solder reflow process.
  • solder reflow process it is exposed to a high temperature of, for example, about 270 ° C.
  • an object of the present disclosure is that, while being economically excellent, it has excellent adhesiveness to a printed wiring board, can exhibit excellent shielding performance even after passing through a high thermal environment, and has excellent connection stability between the electromagnetic wave shield layer and the ground circuit.
  • the purpose is to provide an excellent electromagnetic wave shielding film.
  • the inventors of the present disclosure have made an electromagnetic wave shielding film using aluminum for the electromagnetic wave shielding layer and specific nickel particles as conductive particles in the conductive adhesive layer. According to the report, it was found that while being economically excellent, it has excellent adhesion to printed wiring boards, can exhibit excellent shielding performance even after passing through a high thermal environment, and has excellent connection stability between the electromagnetic wave shielding layer and the ground circuit. rice field. This disclosure has been completed based on these findings.
  • the present disclosure includes an electromagnetic wave shield layer and a conductive adhesive layer provided on one surface of the electromagnetic wave shield layer.
  • the electromagnetic wave shield layer contains aluminum as a constituent material and contains aluminum.
  • the electric adhesive layer contains nickel particles as conductive particles, and the average value of the circularity of the nickel particles is 0.85 or less, and the 10% cumulative value of the circularity is 0.65 or less. Provide a shield film.
  • the electromagnetic wave shield film is economically superior by using aluminum, which is cheaper than silver or copper, as a constituent material of the electromagnetic wave shield layer.
  • nickel particles in the conductive adhesive layer nickel particles having an average circularity of 0.85 or less and a 10% cumulative value of circularity of 0.65 or less are used.
  • the circularity is an index indicating the closeness of the two-dimensional shape of nickel particles to a circle. The higher the circularity, the closer the two-dimensional shape is to a circle, and when the circularity is 1.0, the shape is a perfect circle. Is shown.
  • the electromagnetic wave shield film has excellent adhesiveness to the printed wiring board while using aluminum as a constituent material of the electromagnetic wave shield layer, and after passing through a high thermal environment, It can demonstrate excellent shielding performance and has excellent connection stability between the electromagnetic wave shield layer and the ground circuit.
  • the shape of the nickel particles is preferably filamentous.
  • the average aspect ratio of the nickel particles is preferably 0.70 or less.
  • the 10% cumulative value of the aspect ratio of the nickel particles is preferably 0.50 or less.
  • the median diameter of the nickel particles is preferably 1 to 30 ⁇ m.
  • the electromagnetic wave shield film of the present disclosure is economically excellent, has excellent adhesiveness to a printed wiring board, can exhibit excellent shielding performance even after passing through a high thermal environment, and has excellent connection stability between the electromagnetic wave shield layer and the ground circuit. Excellent for.
  • the electromagnetic wave shield film of the present disclosure includes at least an electromagnetic wave shield layer and a conductive adhesive layer provided on at least one surface of the electromagnetic wave shield layer.
  • the electromagnetic wave shielding film may include a layer other than the electromagnetic wave shielding layer and the conductive adhesive layer. As the other layer, an insulating layer may be provided on the side of the electromagnetic wave shielding layer opposite to the conductive adhesive layer.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the electromagnetic wave shielding film.
  • the electromagnetic wave shield film 1 shown in FIG. 1 is adjacent to the electromagnetic wave shield layer 2, the conductive adhesive layer 3 provided adjacent to one surface of the electromagnetic wave shield layer 2, and the other surface of the electromagnetic wave shield layer 2.
  • the insulating layer 4 provided is provided.
  • the electromagnetic wave shielding film 1 includes a conductive adhesive layer 3, an electromagnetic wave shielding layer 2, and an insulating layer 4 in this order.
  • the electromagnetic wave shield layer contains aluminum as a constituent material.
  • the electromagnetic wave shielding layer containing aluminum as a constituent material includes a metal layer made of a metal such as an aluminum layer (a layer made of aluminum) or an alloy layer made of an alloy of aluminum and another metal, and these layers are other layers (a layer made of other metals). Examples thereof include those formed on the surface of a film or other metal layer (metal-plated layer, etc.).
  • the method for forming the metal layer such as the aluminum layer and the alloy layer is not particularly limited, and for example, electrolysis, vapor deposition (for example, vacuum vapor deposition), sputtering, chemical vapor deposition (CVD), and organic metal deposition (CVD). MO) method, plating, rolling, etc. can be mentioned.
  • the electromagnetic wave shield layer may be either a single layer or a plurality of layers (for example, a metal-plated layer).
  • the thickness of the electromagnetic wave shield layer is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. When the thickness is 0.01 ⁇ m or more, the shielding performance becomes better.
  • the thickness is preferably 12 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 3 ⁇ m or less, from the viewpoint of excellent flexibility, excellent transmission characteristics of high frequency signals of 10 MHz or more, and excellent electromagnetic wave shielding performance. Further, it is preferable that the thickness of the aluminum layer is within the above range.
  • the conductive adhesive layer has adhesiveness and conductivity for adhering the electromagnetic wave shielding film to a printed wiring board, for example.
  • the conductive adhesive layer is preferably formed adjacent to the electromagnetic wave shielding layer.
  • the conductive adhesive layer may be either a single layer or a plurality of layers.
  • the conductive adhesive layer contains nickel particles as conductive particles.
  • Nickel particles Aluminum used for the electromagnetic wave shield layer easily oxidizes to form an oxide film on the surface, but nickel particles can break through the oxide film due to the effect of its hardness, etc., and maintain stable and good electrical connection. It becomes possible to do. In the case of other soft metal particles, it is difficult to break through the oxide film even if the shape has protrusions or the like, and it is difficult to obtain a good electrical connection.
  • the nickel particles only one kind may be used, or two or more kinds may be used as long as the object of the present disclosure is not impaired.
  • the average value of the circularity of the nickel particles is 0.85 or less, preferably 0.84 or less, and more preferably 0.83 or less.
  • the average value of the circularity is preferably small, but from the viewpoint of obtaining better conductivity in the thickness direction and the surface direction of the conductive adhesive layer, for example, 0.60 or more, preferably 0.70. Above, more preferably 0.75 or more.
  • the 10% cumulative value of the circularity of the nickel particles is 0.65 or less, preferably 0.64 or less, and more preferably 0.63 or less.
  • the 10% cumulative value of the circularity is preferably small, but from the viewpoint of obtaining better conductivity in the thickness direction and the surface direction of the conductive adhesive layer, for example, 0.40 or more, preferably 0. It is .45 or more, more preferably 0.50 or more.
  • the circularity is the value obtained by dividing the perimeter of a circle having the same area as the projected image of the particle by the perimeter of the projected image of the particle. Further, the 10% cumulative value of circularity is a value corresponding to 10% cumulative value when the frequency cumulative value is 100%.
  • the various values related to the circularity can be measured by the method described in the examples.
  • the electromagnetic wave shield film is economically superior by using aluminum, which is cheaper than silver or copper, as a constituent material of the electromagnetic wave shield layer.
  • nickel particles having an average circularity of 0.85 or less and a 10% cumulative value of the circularity of 0.65 or less are used.
  • the circularity is an index indicating the closeness of the projected image (two-dimensional shape) of nickel particles to a circle. The higher the circularity, the closer the two-dimensional shape is to a circle, and when the circularity is 1.0, the shape is true. Indicates that it is a circle.
  • the electromagnetic wave shield film has excellent adhesiveness to the printed wiring board while using aluminum as a constituent material of the electromagnetic wave shield layer, and after passing through a high thermal environment, It can demonstrate excellent shielding performance and has excellent connection stability between the electromagnetic wave shield layer and the ground circuit.
  • the average aspect ratio of the nickel particles is preferably 0.70 or less, more preferably 0.69 or less.
  • the average aspect ratio is, for example, 0.60 or more, preferably 0.65 or more.
  • the 10% cumulative value of the aspect ratio of the nickel particles is preferably 0.50 or less, more preferably 0.49 or less.
  • the 10% cumulative value of the aspect ratio is, for example, 0.35 or more, preferably 0.40 or more.
  • the aspect ratio is the ratio (aspect ratio) of the length and width of the circumscribed rectangle when the minimum rectangle when the particle figure of the nickel particles in the projected image is surrounded by a rectangle is the circumscribed rectangle.
  • the fact that the average aspect ratio is 0.70 or less indicates that the length is somewhat longer than the width in the minimum rectangle, and that the 10% cumulative value of the aspect ratio is 0.50 or less. It shows that the proportion of nickel particles with a small aspect ratio is large to some extent. When such nickel particles are used as the conductive particles, the conductive particles extending in the thickness direction come into contact with each other in the conductive adhesive layer, so that the conductivity in the thickness direction becomes more excellent.
  • the number of connection points between the electromagnetic wave shield layer and the ground circuit is increased, so that excellent shielding performance is exhibited even after passing through a high thermal environment. It is presumed that this is due to the fact that the resistance value can be stabilized.
  • Various values related to the aspect ratio can be measured by the method described in the examples.
  • the shape of the nickel particles is preferably filamentous.
  • the filament-shaped nickel particles are, for example, nickel-based particles in which about 10 to 1000 primary particles are connected in a chain to form filament-like secondary particles.
  • the nickel particles are in the form of filaments, as an effect of the shape, it becomes easier to break through the oxide film, and the connection stability after passing through a high thermal environment is further improved.
  • the median diameter (D50) of the nickel particles is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 3 to 13 ⁇ m.
  • the median diameter is 1 ⁇ m or more, the resistance value described later becomes low, and the shielding performance becomes better.
  • the median diameter is 30 ⁇ m or less (particularly, 13 ⁇ m or less), the nickel particles are more dispersed in the conductive adhesive layer, the adhesiveness to the printed wiring board is more excellent, and electromagnetic waves are emitted after passing through a high thermal environment. The connection stability between the shield layer and the ground circuit is better.
  • the median diameter is a circle-equivalent diameter measured by a laser diffraction type particle size distribution measuring device.
  • the content ratio of the nickel particles in the conductive adhesive layer is not particularly limited, but is preferably 2 to 60% by mass, more preferably 3 to 50% by mass, based on 100% by mass of the total amount of the conductive adhesive layer. It is more preferably 4 to 40% by mass, further preferably 4.5 to 30% by mass, and particularly preferably 5 to 25% by mass.
  • the content ratio is 2% by mass or more, the conductivity becomes better.
  • the electromagnetic wave shield film can exhibit adhesiveness to the printed wiring board even after passing through a high thermal environment.
  • the binder component can be sufficiently contained, and the adhesiveness to the printed wiring board becomes better.
  • the electromagnetic wave shield film has excellent shielding performance and stable connection between the electromagnetic wave shield layer and the ground circuit even after being subjected to a high thermal environment. Can exert sex.
  • the conductive adhesive layer preferably contains a binder component that can function as an adhesive.
  • the binder component include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable compound.
  • 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 phenol-based resins, epoxy-based resins, urethane-based resins, melamine-based resins, and alkyd-based resins. 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, and tetrabrom bisphenol A type epoxy resin.
  • 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 epoxy 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 for example, a polymerizable compound having one or more (preferably two or more) radical reactive groups (for example, (meth) acryloyl group) in the molecule is used. Can be mentioned.
  • 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 after arranging the electromagnetic wave shield film on the printed wiring board, the binder component can be cured by pressurization and heating, and the adhesiveness becomes better.
  • 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 40 to 98% by mass, more preferably 50 to 97% by mass, based on 100% by mass of the total amount of the conductive adhesive layer. It is more preferably 60 to 96% by mass, further preferably 70 to 95.5% by mass, and particularly preferably 75 to 95% by mass.
  • the content ratio is 40% by mass or more, the adhesiveness to the printed wiring board is more excellent.
  • the content ratio is 98% by mass or less, the conductive particles can be sufficiently contained.
  • the conductive adhesive layer can be a layer having isotropic conductivity or anisotropic conductivity, if necessary.
  • the conductive adhesive layer preferably has anisotropic conductivity from the viewpoint of improving the transmission characteristics of the high frequency signal transmitted by the signal circuit of the printed wiring board.
  • the conductive adhesive layer may contain other components other than the above components as long as the effects of the present disclosure 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, colorants, leveling agents, and coupling agents. , 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 proportion of nickel particles in which the average value of circularity and the 10% cumulative value are within the above ranges is preferably 90% by mass or more, more preferably 90% by mass or more, among all the conductive particles contained in the conductive adhesive layer. It is 95% by mass or more, more preferably 98% by mass or more.
  • the thickness of the conductive adhesive layer is preferably 3 to 20 ⁇ m, more preferably 5 to 15 ⁇ m. In order to give the conductive adhesive layer anisotropy, the thickness of the conductive adhesive layer is preferably not less than the median diameter of the nickel particles. In this case, the electrical connection between the electromagnetic wave shield film and the printed wiring board is good.
  • the insulating layer has a function of protecting the conductive adhesive layer and / or the electromagnetic wave shielding layer in the electromagnetic wave shielding film.
  • the 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 the binder component that can be contained in the conductive adhesive layer described above.
  • the binder component only one kind may be used, or two or more kinds may be used.
  • the insulating layer may contain other components other than the binder component as long as the effects of the present disclosure 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 coloring agent, and a leveling agent.
  • examples thereof include a coupling agent, an ultraviolet absorber, a tackifier resin, and an antiblocking agent.
  • only one kind may be used, or two or more kinds may be used.
  • the insulating layer may be a single layer or a plurality of layers.
  • the insulating layer may be a laminate of two or more layers having different physical properties such as material, hardness, and elastic modulus.
  • the pressure applied to the electromagnetic wave shield layer can be relaxed in the step of heating and pressurizing the electromagnetic wave shield film on the printed wiring board. Therefore, it is possible to prevent the electromagnetic wave shield layer from being destroyed by the step provided on the printed wiring board.
  • the thickness of the insulating layer is not particularly limited and can be appropriately set as needed, but is preferably 1 to 20 ⁇ m, more preferably 2 to 15 ⁇ m, and even more preferably 3 to 10 ⁇ m. When the thickness is 1 ⁇ m or more, the electromagnetic wave shielding layer and the conductive adhesive layer can be more sufficiently protected. When the thickness is 20 ⁇ m or less, the flexibility and flexibility are excellent, and it is economically advantageous.
  • the electromagnetic wave shield film may be provided with a separator (release film) on the insulating layer side and / or the conductive adhesive layer side.
  • the separators are laminated so as to be peelable from the electromagnetic wave shielding film.
  • the separator is an element for coating and protecting the insulating layer and the conductive adhesive layer, and is peeled off when the electromagnetic wave shielding film 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 electromagnetic wave shield film may further have an anchor coat layer formed between the insulating layer and the electromagnetic wave shield layer. With such a configuration, the adhesiveness between the electromagnetic wave shielding layer and the insulating layer becomes better.
  • the material for forming the anchor coat layer is a core-shell type composite resin having a urethane resin, an acrylic resin, a urethane resin as a shell and an acrylic resin as a core, an epoxy resin, a polyimide resin, and a polyamide resin.
  • a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone and the like.
  • the resistance value (initial resistance value) of the electromagnetic wave shielding film obtained by the following conductivity test is not particularly limited, but is preferably 500 m ⁇ or less, more preferably 400 m ⁇ or less, and further preferably less than 300 m ⁇ . When the initial resistance value is 500 m ⁇ or less, the continuity between the electromagnetic wave shield film and the ground circuit becomes good.
  • Conductivity test As a printed wiring board, two copper foil patterns simulating a ground circuit are formed on a base member made of a polyimide film, and a coverlay made of an insulating adhesive layer and a polyimide film having a thickness of 25 ⁇ m is formed on the two copper foil patterns. Use the printed wiring board on which is formed.
  • the coverlay is formed with a circular opening simulating a ground connection portion having a diameter of 1 mm. Then, the electromagnetic wave shield film and the printed wiring board are evacuated for 60 seconds under the conditions of temperature: 170 ° C. and pressure: 3.0 MPa using a press machine, then heated and pressed for 180 seconds to bond them, and 150 in an oven. It is heated at ° C. for 60 minutes, and the electric resistance value between the two copper foil patterns is measured with a resistance meter to obtain the resistance value.
  • the resistance value (resistance value after reflow) obtained by the conductivity test after passing through the reflow process of the electromagnetic wave shield film set to a temperature profile set to a temperature profile of 265 ° C. for 5 seconds for 3 cycles is determined. Although not particularly limited, it is preferably 1000 m ⁇ or less, more preferably 700 m ⁇ or less, and further preferably less than 500 m ⁇ . When the resistance value is 1000 m ⁇ or less, the continuity between the electromagnetic wave shield film and the ground circuit after passing through a high temperature environment becomes good.
  • the resistance value after reflow is measured in the same manner as in the conductivity test of the initial resistance value of the electromagnetic wave shield film after passing through the reflow step for 3 cycles.
  • the adhesive strength of the electromagnetic wave shielding film required by the following adhesive test is not particularly limited, but is preferably 3.0 N / 10 mm or more, more preferably 3.5 N / 10 mm or more, and further preferably more than 4.0 N / 10 mm. Is. When the adhesive strength is 3.0 N / 10 mm or more, the adhesive strength with the printed wiring board after passing through a high temperature environment is excellent.
  • Adhesion test A polyimide film with a thickness of 25 ⁇ m is attached to the conductive adhesive layer surface of the electromagnetic wave shield film, evacuated for 60 seconds under the conditions of temperature: 170 ° C. and pressure: 3.0 MPa using a press machine, and then heated for another 180 seconds. Pressurize and bond.
  • the electromagnetic wave shield film is preferably used for a printed wiring board, and particularly preferably for a flexible printed wiring board (FPC).
  • FPC flexible printed wiring board
  • the insulating layer 4 is coated (coated) with a resin composition for forming the insulating layer 4 on a temporary base material such as a separate film or a base material, and is removed as necessary. It can be formed by curing the solvent and / or partly.
  • the resin composition contains, for example, a solvent (solvent) in addition to each component contained in the above-mentioned insulating layer.
  • a solvent solvent
  • examples of the solvent include toluene, acetone, methyl ethyl ketone, methanol, ethanol, propanol, dimethylformamide and the like.
  • the solid content concentration of the resin composition is appropriately set according to the thickness of the 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.
  • the electromagnetic wave shield layer 2 is formed on the surface of the insulating layer 4 formed on the separator.
  • the electromagnetic wave shield layer 2 is preferably formed by a vapor deposition method or a sputtering method. As the vapor deposition method and the sputtering method, known or commonly used methods can be adopted. In this way, a laminate of the insulating layer 4 / electromagnetic wave shielding layer 2 is produced.
  • an adhesive composition for forming the conductive adhesive layer 3 is applied onto a temporary base material such as a separate film or a base material ( It can be formed by coating) and, if necessary, desolvating and / or partially curing.
  • 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.
  • the electromagnetic wave shield film 1 may be manufactured by a method of sequentially laminating each layer as another embodiment other than the above laminating method (direct coating method). For example, in the electromagnetic wave shield film 1 shown in FIG. 1, an adhesive composition for forming a conductive adhesive layer 3 is applied (coated) on the surface of the electromagnetic wave shield layer 2 of the above-mentioned laminated body, and the film is removed as necessary. It can be produced by forming a conductive adhesive layer 3 by curing the solvent and / or a part thereof.
  • a shield printed wiring board can be manufactured using the above electromagnetic wave shield film. For example, by adhering the conductive adhesive layer of the electromagnetic wave shield film to a printed wiring board (for example, a coverlay), a shield printed wiring board to which the electromagnetic wave shield film is attached to the printed wiring board can be obtained.
  • the conductive adhesive layer may be thermoset by, for example, a subsequent heat and pressure treatment.
  • electromagnetic wave shielding film of the present disclosure will be described in more detail based on the examples, but the electromagnetic wave shielding film of the present disclosure is not limited to these examples.
  • Example 1 (Formation of insulating layer) 100 parts by mass of bisphenol A type epoxy resin (trade name “jER1256", manufactured by Mitsubishi Chemical Co., Ltd.) and curing agent (trade name “ST14", Mitsubishi Chemical Co., Ltd.) in toluene so that the solid content is 20% by mass.
  • the resin composition was prepared by blending 0.1 parts by mass and stirring and mixing.
  • the obtained resin composition was applied to the release-treated surface of a polyethylene terephthalate (PET) film whose surface was release-treated, and the solvent was removed by heating to form an insulating layer (thickness 6 ⁇ m).
  • PET polyethylene terephthalate
  • An aluminum layer having a thickness of 0.1 ⁇ m was formed on the surface of the obtained insulating layer by a thin-film deposition method to obtain a laminate of the insulating layer and the electromagnetic wave shielding layer.
  • a PET film having an insulating layer formed therein is placed in a batch-type vacuum vapor deposition apparatus (trade name "EBH-800", manufactured by ULVAC Co., Ltd.), and a vacuum reachability of 5 ⁇ is placed in an argon gas atmosphere.
  • a magnetron sputtering method DC power output: 3.0 kW.
  • Formation of conductive adhesive layer 95 parts by mass of bisphenol A type epoxy resin (trade name "jER1256", manufactured by Mitsubishi Chemical Co., Ltd.), curing agent (trade name "ST14", Mitsubishi Chemical Co., Ltd.) in toluene so that the solid content is 20% by mass.
  • An adhesive composition was prepared by blending 0.1 parts by mass of (manufactured by the company) and 5 parts by mass of conductive particles composed of filamentous nickel particles (No. 1) and stirring and mixing. The properties of the conductive particles used are as shown in Table 2. The obtained adhesive composition was applied to the release-treated surface of the PET film whose surface was release-treated, and the solvent was removed by heating to form a conductive adhesive layer (thickness 12 ⁇ m).
  • Example 1 (Making an electromagnetic wave shield film)
  • the obtained conductive adhesive layer is bonded to the electromagnetic wave shield layer surface of the laminate composed of the insulating layer and the electromagnetic wave shield layer, and has a configuration of a conductive adhesive layer / electromagnetic wave shield layer / insulating layer.
  • An electromagnetic wave shield film was produced.
  • Examples 2-4 and Comparative Examples 1-8 An electromagnetic wave shielding film was produced in the same manner as in Example 1 except that the types and content ratios of nickel particles in the conductive adhesive layer were changed as shown in Table 1. The properties of the conductive particles used in each example are as shown in Table 2.
  • Circularity, Aspect Ratio, and Median Diameter For the circularity, aspect ratio, and median diameter of conductive particles, use a flow-type particle image analyzer (trade name "FPIA-3000", manufactured by Sysmex Co., Ltd.). It was measured. Specifically, it was measured with a conductive particle dispersion adjusted to a concentration of 4000 to 20000 particles / ⁇ l in the LPF measurement mode in a bright field optical system using an objective lens 10 times. For the above conductive particle dispersion, 0.1 to 0.5 ml of a surfactant is added to an aqueous solution of sodium hexametaphosphate adjusted to 0.2% by mass, and 0.1 ⁇ 0.01 g of conductive particles as a measurement sample is added.
  • FPIA-3000 flow-type particle image analyzer
  • the suspension in which the conductive particles were dispersed was subjected to a dispersion treatment for 1 to 3 minutes with an ultrasonic disperser and used for measurement.
  • Table 2 shows the average value of the circularity, the 10% cumulative value of the circularity, the average aspect ratio, the 10% cumulative value of the aspect ratio, and the median diameter of the conductive particles obtained by the measurement.
  • the electromagnetic wave shield film produced in Examples and Comparative Examples was laminated on a printed wiring board for evaluation, and then using a press machine, the temperature was 170 ° C. and the pressure was 3.0 MPa. After vacuuming for 1 second, the mixture was further heated and pressed for 180 seconds for adhesion. Then, the PET film on the insulating layer was peeled off and heated in an oven at 150 ° C. for 60 minutes to prepare an evaluation substrate.
  • the printed wiring board has two copper foil patterns extending in parallel with each other at intervals, and an insulating protective layer (thickness: 25 ⁇ m) made of polyimide while covering the copper foil patterns.
  • the insulating protective layer is provided with an opening (diameter: 1 mm) for exposing each copper foil pattern.
  • a heat treatment was performed assuming a reflow treatment, and the electric resistance value after the reflow was measured (resistance value after the reflow). This heat treatment and measurement of the electric resistance value were repeated three times. Assuming the use of lead-free solder for the heat treatment, a temperature profile was set so that the electromagnetic wave shielding film on the evaluation substrate was exposed to 265 ° C. for 5 seconds. Then, the initial resistance value and the resistance value after reflow were evaluated based on the following evaluation criteria, respectively.
  • Adhesiveness A 25 ⁇ m-thick polyimide film (trade name “Kapton 100EN”, manufactured by Toray DuPont Co., Ltd.) is attached to the conductive adhesive layer surface of the electromagnetic wave shielding film produced in Examples and Comparative Examples, and a press machine is used. After vacuuming for 60 seconds under the conditions of temperature: 170 ° C. and pressure: 3.0 MPa, the film was further heated and pressed for 180 seconds for adhesion. Then, it was heat-treated in an oven at 150 ° C. for 60 minutes to prepare a measurement sample.
  • this measurement sample was cut to a width of 10 mm, and a tensile tester (trade name "AGS-X50N", manufactured by Shimadzu Corporation) was used to peel off at a peeling speed of 50 mm / min and a peeling angle of 180 °. Under the conditions, the adhesive strength was measured by peeling off the interface between the conductive adhesive layer and the polyimide film.
  • the electromagnetic wave shield film of the example had excellent adhesiveness when an aluminum layer was used as the electromagnetic wave shield layer, had a low initial resistance value, and had a low resistance value after the reflow treatment. Therefore, the electromagnetic wave shielding film of the embodiment is economically excellent, has excellent adhesiveness to the printed wiring board, and can exhibit excellent shielding performance even after passing through a high thermal environment, and the electromagnetic wave shielding layer and the ground circuit can exhibit excellent shielding performance. It was judged to have excellent connection stability. On the other hand, when nickel particles having an average circularity value and a 10% cumulative value exceeding a specific value are used as the conductive particles in the conductive adhesive layer (comparative example), the content ratio of the conductive particles is changed. However, it was not possible to obtain a material that has both adhesiveness and resistance value after the reflow treatment.
  • Electromagnetic wave shield film 1 Electromagnetic wave shield film 2 Electromagnetic wave shield layer 3 Conductive adhesive layer 4 Insulation layer

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
PCT/JP2021/008033 2020-03-03 2021-03-03 電磁波シールドフィルム WO2021177328A1 (ja)

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CN116669410B (zh) * 2023-07-03 2024-02-20 广州方邦电子股份有限公司 一种电磁屏蔽罩和线路板

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