WO2022181570A1 - Film de protection contre les ondes électromagnétiques - Google Patents

Film de protection contre les ondes électromagnétiques Download PDF

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Publication number
WO2022181570A1
WO2022181570A1 PCT/JP2022/007068 JP2022007068W WO2022181570A1 WO 2022181570 A1 WO2022181570 A1 WO 2022181570A1 JP 2022007068 W JP2022007068 W JP 2022007068W WO 2022181570 A1 WO2022181570 A1 WO 2022181570A1
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WIPO (PCT)
Prior art keywords
electromagnetic wave
shielding film
wave shielding
protective layer
layer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/007068
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English (en)
Japanese (ja)
Inventor
慶彦 青柳
憲治 上農
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tatsuta Electric Wire and Cable Co Ltd
Original Assignee
Tatsuta Electric Wire and Cable Co Ltd
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 Tatsuta Electric Wire and Cable Co Ltd filed Critical Tatsuta Electric Wire and Cable Co Ltd
Priority to CN202280004051.4A priority Critical patent/CN115486215B/zh
Priority to JP2022541965A priority patent/JP7206441B1/ja
Priority to KR1020227028896A priority patent/KR102558231B1/ko
Publication of WO2022181570A1 publication Critical patent/WO2022181570A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B15/095—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 comprising polyurethanes
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation

Definitions

  • the present invention relates to an electromagnetic wave shielding film.
  • shield printed wiring also referred to as “plate”
  • the shield layer used in the electromagnetic wave shield film is formed of a thin metal layer formed by vapor deposition, sputtering, plating, or the like, or a conductive paste containing a high content of conductive filler.
  • 5G, etc. will spread in earnest, high frequency and high speed transmission will advance in order to communicate large amounts of data, and noise countermeasures for electronic devices will become even more necessary.
  • an electromagnetic wave shield film consists of a shield layer that serves as a main body that shields electromagnetic waves, and a protective layer (insulating layer) that protects the shield layer from external impacts, chemicals, solvents, water, etc. .
  • Flexibility is required for the electromagnetic shielding film placed on the flexible printed wiring board, and flexibility is also required for the protective layer that is a component thereof.
  • Patent Document 1 discloses a conductive shield layer having unevenness and an adhesive layer covering the unevenness, and the maximum peak height of the unevenness is is greater than the thickness of the adhesive layer.
  • Patent Document 2 discloses an electromagnetic wave shielding film comprising a shield layer and an insulating layer laminated on the shield layer, wherein the insulating layer contains silica fine particles, and the silica fine particles in the insulating layer
  • An electromagnetic wave shielding film is disclosed in which the content is 10 to 50 wt%.
  • a resin composition for a protective layer used in such an electromagnetic wave shielding film contains an amorphous polyester resin, a curing agent, and a white pigment, and the amorphous polyester resin is ,
  • the number average molecular weight Mn is less than 20,000
  • the glass transition point Tg is 40 ° C. or higher
  • the curing agent is a blocked isocyanate, a trimethylolpropane adduct of hexane diisocyanate, and an isocyanurate adduct of cyclohexane diisocyanate
  • a resin composition is disclosed which is at least one selected from the group consisting of:
  • a highly flexible protective layer has a low glass transition point and a low crosslink density. If the glass transition point of the protective layer is low, there is a problem that blocking is likely to occur when the electromagnetic wave shielding film is stored in a roll. In addition, if the cross-linking density of the resin constituting the protective layer is low, the electromagnetic wave shielding film will not be exposed to the steps such as openings provided to expose the ground circuit on the printed wiring board (hereinafter simply referred to as “steps on the printed wiring board”). ), the protective layer tends to have partially thin spots, the physical strength of the protective layer decreases, and moisture easily permeates the protective layer. As a result, there is a problem that the heat resistance and moisture resistance of the electromagnetic wave shielding film tend to deteriorate.
  • the present invention is an invention made to solve the above problems, and an object of the present invention is to provide an electromagnetic wave shielding film that is less likely to cause blocking during roll storage and has excellent moisture resistance and bending resistance.
  • the electromagnetic shielding film of the present invention is an electromagnetic shielding film in which a protective layer and a shielding layer are laminated, and the protective layer is a urethane having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher. and a non-conductive filler having an average particle size of 10 ⁇ m or less, wherein the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight.
  • the urethane resin contained in the protective layer has an acid value of 2000 to 4000 g/eq.
  • the acid value is within the above range, the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. .
  • the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer.
  • the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved. If the acid value is less than 2000 g/eq, the crosslink density becomes high and the protective layer becomes hard.
  • the toughness of the protective layer is lowered, and the bending resistance tends to be lowered. If the acid value exceeds 4000 g/eq, the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
  • the urethane-based resin contained in the protective layer has a Tg of 0° C. or higher. Therefore, when the electromagnetic wave shielding film of the present invention is stored in a roll, blocking is less likely to occur.
  • the protective layer contains a non-conductive filler having an average particle size of 10 ⁇ m or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight. If the protective layer contains a non-conductive filler having an average particle diameter of 10 ⁇ m or less in the above weight ratio, the urethane resin contained in the protective layer is used when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing. can be prevented from flowing and part of the protective layer becoming thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
  • the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease. If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
  • the protective layer preferably further contains an epoxy resin.
  • the protective layer contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film is arranged on the printed wiring board by hot pressing.
  • the urethane-based resin preferably has a Tg of 0 to 60°C.
  • the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board, so that part of the protective layer becomes thin. It is possible to prevent the moisture resistance and bending resistance of the electromagnetic wave shielding film from deteriorating.
  • the urethane resin preferably has a weight average molecular weight of 100,000 to 2,000,000, more preferably 170,000 to 500,000.
  • the weight-average molecular weight of the urethane-based resin is within the above range, the urethane-based resin has appropriate hardness and fluidity, so that the electromagnetic wave shielding film can be improved in heat resistance, moisture resistance, and bending resistance.
  • the non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates. Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
  • the shield layer may be a conductive adhesive layer.
  • the shield layer may be a metal layer, and an adhesive layer may be further laminated on the side of the shield layer on which the protective layer is not laminated.
  • the electromagnetic wave shielding film of the present invention can suitably shield electromagnetic waves in any aspect. In addition, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll, and the heat resistance, moisture resistance, and bending resistance of the electromagnetic wave shielding film are sufficiently increased.
  • the protective layer contains a urethane resin having an acid value of 2000 to 4000 g/eq and a Tg of 0° C. or higher, and a non-conductive filler having an average particle size of 10 ⁇ m or less.
  • the weight ratio of the non-conductive filler to the total weight of the protective layer is 10 to 40% by weight. Therefore, the cross-linking density of the urethane-based resin is in an appropriate range, and the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
  • the Tg of the urethane-based resin is 0° C. or higher, blocking hardly occurs when the electromagnetic wave shielding film is stored in a roll.
  • the protective layer contains a predetermined non-conductive filler, when the electromagnetic wave shielding film is placed on the printed wiring board by heat pressing, the urethane resin contained in the protective layer flows and part of the protective layer thinning can be prevented. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
  • FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
  • FIG. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
  • FIG. 2B is a cross-sectional view schematically showing an electromagnetic shielding film placement step in the method for manufacturing a shield printed wiring board using the electromagnetic shielding film of the present invention.
  • FIG. 2C is a cross-sectional view schematically showing a hot press step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
  • FIG. 2D is a cross-sectional view schematically showing an example of a shield printed wiring board manufactured using the electromagnetic wave shielding film of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
  • FIG. 4A is a schematic diagram showing a resistance value test method.
  • FIG. 4B is a schematic diagram showing a resistance value test method.
  • FIG. 5 is a diagram schematically showing a flex resistance test.
  • FIG. 6 is a diagram schematically showing a blocking test.
  • the electromagnetic wave shielding film of the present invention will be specifically described below.
  • the present invention is not limited to the following embodiments, and can be appropriately modified and applied without changing the gist of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
  • the electromagnetic wave shielding film 10 shown in FIG. 1 is an electromagnetic wave shielding film in which a protective layer 20, a metal layer 30, and a conductive adhesive layer 40 are laminated in order.
  • the metal layer 30 functions as a shield layer for shielding electromagnetic waves. Each configuration will be described below.
  • the protective layer 20 contains urethane-based resin and non-conductive filler.
  • the urethane-based resin contained in the protective layer 20 has an acid value of 2000 to 4000 g/eq.
  • the acid value is preferably 2100-3900 g/eq, more preferably 2500-3500 g/eq.
  • the cross-linking density is within a suitable range, so that when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer is less likely to have partially thin portions. .
  • the physical strength of the protective layer is reduced, and moisture does not easily permeate the protective layer.
  • the flex resistance and moisture resistance of the electromagnetic wave shielding film are improved.
  • the acid value is less than 2000 g/eq
  • the crosslink density becomes high and the protective layer becomes hard.
  • the toughness of the protective layer is lowered, and the bending resistance tends to be lowered.
  • the acid value exceeds 4000 g/eq
  • the cross-linking density becomes low, and when the electromagnetic wave shielding film is placed on the stepped portion of the printed wiring board by hot pressing, the protective layer tends to be partially thinned. As a result, the moisture resistance tends to be extremely lowered.
  • the urethane-based resin contained in the protective layer 20 has a Tg of 0° C. or higher.
  • Tg is preferably 0 to 60°C, more preferably 30 to 60°C.
  • the protective layer has appropriate fluidity when the electromagnetic wave shielding film of the present invention is hot-pressed onto a printed wiring board.
  • a protective layer may be formed in a transfer film. At this time, the adhesion between the protective layer and the transfer film is improved.
  • the Tg of the urethane-based resin means a value measured according to differential scanning calorimetry (DSC) in JIS K7121.
  • the weight average molecular weight of the urethane resin is preferably 100,000 to 2,000,000, more preferably 170,000 to 500,000.
  • the urethane-based resin has appropriate hardness and fluidity, so that the heat resistance, moisture resistance, and flex resistance of the protective layer can be improved.
  • the weight average molecular weight of the urethane-based resin can be measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring instrument Alliance GPC System (manufactured by Waters) Column: Shodex GPC KF-806L (Showa Denko) Column temperature: 40°C Sample concentration: 0.05 wt%/THF Injection volume: 10 ⁇ L Standard sample: Tosoh: standard PS 500, Shodex standard PS SM-105 (set)
  • the non-conductive filler contained in the protective layer 20 has an average particle diameter of 10 ⁇ m or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer 20 is 10 to 40% by weight. Also, the weight ratio of the non-conductive filler is preferably 10 to 35% by weight, more preferably 10 to 25% by weight.
  • the protective layer 20 contains the non-conductive filler in the above weight ratio, the urethane-based resin contained in the protective layer flows when the electromagnetic wave shielding film is placed on the printed wiring board by hot pressing, and a part of the protective layer is partially removed. It can prevent thinning. Therefore, the protective layer is less likely to have partially thin portions. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
  • the weight ratio of the non-conductive filler when the weight ratio of the non-conductive filler is 10 to 25% by mass, the flex resistance of the electromagnetic wave shielding film becomes better. If the weight ratio of the non-conductive filler is less than 10% by weight, it becomes difficult to obtain the effect of containing the non-conductive filler, and moisture resistance tends to decrease. If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the bending resistance tends to decrease.
  • the non-conductive filler preferably has an average particle size of 100 nm to 10 ⁇ m.
  • the average particle diameter of the non-conductive filler is 100 nm or more, it is possible to suitably prevent the urethane-based resin contained in the protective layer from flowing and partially thinning the protective layer.
  • the average particle size of the non-conductive filler is 10 ⁇ m or less, the thickness of the entire protective layer can be reduced.
  • the non-conductive filler is preferably at least one selected from the group consisting of silica and organic phosphates. Among these, silica is preferred. Non-conductive fillers made of these materials can favorably improve the moisture resistance and bending resistance of the electromagnetic wave shielding film.
  • non-conductive filler is silica, colloidal silica, fumed silica, wet silica synthesized by wet method, dry silica synthesized by dry method, porous silica, non-porous silica, hydrophobic silica, various surfaces It may be treated hydrophilic silica.
  • Hydrophobic silica is obtained, for example, by subjecting the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method to a surface treatment for imparting hydrophobicity.
  • a surface treatment for imparting hydrophobicity can be manufactured.
  • Examples of such surface treatment include treatment of coating the surface of amorphous silica with waxes such as paraffin wax, carnauba wax, amide wax, and polyethylene wax.
  • the resulting hydrophobic silica exhibits hydrophobicity because the silanol groups on the surface of the amorphous silica are covered with a wax layer.
  • amorphous silica is modified by hydrolysis or the like by adding organosilicon compounds such as tetramethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, epoxy group-containing silane, or dimethyldichlorosilane, or amino group-containing organic compounds. Processing is also included. Hydrophobic silica thus obtained is obtained by chemically reacting silanol groups on the surface of amorphous silica with an organic silicon compound or the like, and has hydrophobic groups such as alkyl groups on its surface.
  • hydrophobic silica examples include AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R80, Nippon Aerosil Co., Ltd.), Cyrophobic 200, Cyrophobic 704, Cyrophobic 505, and Cyrophobic 603 (manufactured by Fuji Silysia Chemical Co., Ltd.).
  • Hydrophilic silica can be produced, for example, by not chemically modifying the silanol groups present on the surface of amorphous silica synthesized by a dry method or amorphous silica synthesized by a wet method.
  • hydrophilic silica include AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600 (manufactured by Nippon Aerosil Co., Ltd.), Silysia 250, Silysia 350, Silicia 450, Silicia 550, Silicia 740 (manufactured by Fuji Silysia Chemical Co., Ltd.) and the like.
  • the non-conductive filler is an organic phosphate
  • polyphosphates, metal phosphinates, and the like are included.
  • the phosphinic acid metal salt aluminum salt, sodium salt, potassium salt, magnesium salt, calcium salt and the like can be used, among which aluminum salt is preferable.
  • polyphosphates melamine salts, methylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, pyridine salts, triazine salts, ammonium salts and the like can be used, with melamine salts being preferred.
  • the thickness of the protective layer 20 is not particularly limited, it is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m. If the thickness of the protective layer is less than 1 ⁇ m, the protective layer is too thin and is easily damaged. If the thickness of the protective layer exceeds 100 ⁇ m, the electromagnetic wave shielding film as a whole becomes thick and difficult to handle. Also, the flexibility of the protective layer is reduced.
  • the protective layer 20 preferably further contains an epoxy resin.
  • the protective layer 20 contains an epoxy resin, it is possible to suppress the flow of the urethane resin contained in the protective layer when the electromagnetic wave shielding film 10 is arranged on the printed wiring board by hot pressing.
  • the acid value of the epoxy resin is preferably 100-500 g/eq, more preferably 150-450 g/eq.
  • the protective layer 20 may optionally contain a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, and a viscosity adjuster. agents, anti-blocking agents and the like may also be included.
  • the metal layer 30 of the electromagnetic wave shielding film 10 is not particularly limited as long as it can shield electromagnetic waves, and is preferably made of at least one selected from the group consisting of a copper layer, a silver layer and an aluminum layer. These metal layers have high conductivity and can suitably shield electromagnetic waves.
  • the thickness of the metal layer 30 is not particularly limited, it is preferably 0.01 to 10 ⁇ m. If the thickness of the metal layer is less than 0.01 ⁇ m, it is difficult to obtain a sufficient shielding effect. If the thickness of the metal layer exceeds 10 ⁇ m, the electromagnetic wave shielding film becomes difficult to bend.
  • the metal layer 30 may have through holes.
  • the electromagnetic wave shielding film 10 is hot-pressed onto the printed wiring board.
  • volatile components may occur between the conductive adhesive layer 40 and the metal layer 30 . If the metal layer 30 does not have through-holes, the volatile component expands due to heat and may separate the metal layer 30 and the conductive adhesive layer 40 from each other. However, if the metal layer 30 has through-holes, volatile components can pass through the through-holes, so that the metal layer 30 and the conductive adhesive layer 40 can be prevented from peeling off.
  • the conductive adhesive layer 40 contains an adhesive resin composition and metal particles.
  • the conductive adhesive layer 40 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
  • the material of the adhesive resin composition contained in the conductive adhesive layer 40 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene.
  • Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine
  • a thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
  • the polyester-based resin composition is preferable.
  • the material of the adhesive resin composition may be one of these alone or a combination of two or more.
  • metal particles contained in the conductive adhesive layer 40 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver. Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive adhesive layer 40 . These metal particles may be contained singly in the conductive adhesive layer 40, or may be contained in a plurality of types.
  • the size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 ⁇ m.
  • the weight ratio of the metal particles contained in the conductive adhesive layer 40 is preferably 2-60 wt %, more preferably 10-40 wt %. If the weight ratio of the metal particles is less than 2 wt %, the shielding properties of the electromagnetic wave shielding film tend to deteriorate. If the weight ratio of the metal particles exceeds 60 wt %, the conductive adhesive layer becomes brittle and the electromagnetic wave shielding film tends to break. Moreover, when the weight ratio of the metal particles is 40 wt % or less, the conductive adhesive layer can obtain anisotropic conductivity.
  • the conductive adhesive layer 40 may have isotropic conductivity or anisotropic conductivity.
  • the printed wiring board on which the electromagnetic wave shielding film 10 is arranged has good high-frequency signal transmission characteristics.
  • the thickness of the conductive adhesive layer 40 is not particularly limited and can be appropriately set as necessary, but is preferably 0.5 to 30.0 ⁇ m. If the thickness of the conductive adhesive layer is less than 0.5 ⁇ m, it becomes difficult to obtain good conductivity. If the thickness of the conductive adhesive layer exceeds 30.0 ⁇ m, the thickness of the entire electromagnetic wave shielding film becomes thick and difficult to handle.
  • An anchor coat layer may be formed between the protective layer 20 and the metal layer 30 in the electromagnetic wave shielding film 10 .
  • Materials for the anchor coat layer include urethane resin, acrylic resin, core-shell type composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, and urea-formaldehyde resin. , blocked isocyanate obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
  • the electromagnetic wave shielding film 10 has the conductive adhesive layer 40, but the electromagnetic wave shielding film of the present invention may have a non-conductive adhesive layer instead of the conductive adhesive layer.
  • FIG. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
  • a printed wiring board 50 comprising a base film 51, a printed circuit 52 including a ground circuit 52a disposed on the base film 51, and a coverlay 53 covering the printed circuit 52 is prepared.
  • the coverlay 53 has an opening 53a that exposes the ground circuit 52a.
  • FIG. 2B is a cross-sectional view schematically showing an electromagnetic shielding film placement step in the method for manufacturing a shield printed wiring board using the electromagnetic shielding film of the present invention.
  • the electromagnetic shielding film 10 is arranged on the printed wiring board 50 so that the conductive adhesive layer 40 of the electromagnetic shielding film 10 is in contact with the coverlay 53 of the printed wiring board 50 .
  • FIG. 2C is a cross-sectional view schematically showing a hot press step in the method for manufacturing a shield printed wiring board using the electromagnetic wave shielding film of the present invention.
  • the electromagnetic wave shielding film 10 is heat-pressed onto the printed wiring board 50 by heat-pressing the printed wiring board 50 on which the electromagnetic wave shielding film 10 is arranged in the direction of the arrow.
  • the protective layer 20 contains a non-conductive filler having an average particle size of 10 ⁇ m or less, and the weight ratio of the non-conductive filler to the total weight of the protective layer 20 is 10 to 40% by weight. It is possible to prevent the urethane-based resin contained in the protective layer 20 from flowing and partially thinning the protective layer. Therefore, the protective layer 20 is less likely to be partially thin. As a result, the electromagnetic wave shielding film has good moisture resistance and bending resistance.
  • the conductive adhesive layer 40 fills the opening 53a, and the conductive adhesive layer 40 and the ground circuit 52a are brought into contact with each other. Therefore, the metal layer 30 and the ground circuit 52a are electrically connected, and the electromagnetic wave shielding property is improved.
  • Conditions for hot pressing are not particularly limited, but include, for example, conditions of 150 to 200° C., 2 to 5 MPa, and 1 to 60 minutes.
  • FIG. 2D is a cross-sectional view schematically showing an example of a shield printed wiring board manufactured using the electromagnetic wave shielding film of the present invention. Through the above steps, as shown in FIG. 2D, the shield printed wiring board 1 using the electromagnetic wave shielding film 10 can be manufactured.
  • FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
  • the electromagnetic wave shielding film 110 shown in FIG. 3 is an electromagnetic wave shielding film in which a protective layer 120 and a conductive adhesive layer 140 are laminated in order.
  • the conductive adhesive layer 140 has isotropic conductivity and functions as a shield layer that shields electromagnetic waves.
  • the preferred aspects of the protective layer 120 are the same as those of the protective layer 120 of the electromagnetic wave shielding film 10 described above.
  • Conductive adhesive layer 140 includes an adhesive resin composition and metal particles.
  • the conductive adhesive layer 140 further includes a flame retardant, a flame retardant aid, a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling agent. , fillers, viscosity modifiers and the like.
  • the material of the adhesive resin composition contained in the conductive adhesive layer 140 is not particularly limited, but may be a styrene-based resin composition, a vinyl acetate-based resin composition, a polyester-based resin composition, a polyethylene-based resin composition, or polypropylene.
  • Thermoplastic resin compositions such as resin compositions, imide resin compositions, amide resin compositions, acrylic resin compositions, phenol resin compositions, epoxy resin compositions, urethane resin compositions, melamine
  • a thermosetting resin composition such as an alkyd-based resin composition or an alkyd-based resin composition can be used.
  • the polyester-based resin composition is preferred.
  • the material of the adhesive resin composition may be one of these alone or a combination of two or more.
  • Examples of the metal particles contained in the conductive adhesive layer 140 include silver, copper, nickel, aluminum, and silver-coated copper obtained by plating copper with silver. Since these metal particles have excellent conductivity, they can suitably impart conductivity to the conductive adhesive layer 140 . These metal particles may be contained singly in the conductive adhesive layer 140, or may be contained in a plurality of types.
  • the size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 ⁇ m.
  • the weight ratio of the metal particles contained in the conductive adhesive layer 140 is preferably 40% by weight or more, more preferably 40 to 60% by weight. When the weight ratio of the metal particles is 40% by weight or more, the conductive adhesive layer 140 can obtain isotropic conductivity.
  • Example 1 Urethane resin A (manufacturer: manufactured by Toyobo Co., Ltd., weight average molecular weight: 200,000) having an acid value of 3300 g/eq and a Tg of 40°C, an epoxy resin (acid value: 170 g/eq), and silica as a non-conductive filler Particles (average particle diameter: 2 ⁇ m) were kneaded at the ratio shown in Table 1 to prepare a protective layer composition.
  • the numerical value of the composition in Table 1 means the weight%.
  • a transfer film a polyethylene terephthalate film having one side subjected to release treatment was prepared.
  • the release-treated surface of the transfer film was coated with the protective layer composition and heated at 100° C. for 2 minutes in an electric oven to prepare a protective layer having a thickness of 5 ⁇ m.
  • a copper layer of 2 ⁇ m was formed on the protective layer by electroless plating. The copper layer becomes a shield layer.
  • thermoplastic polyester resin as an adhesive resin composition
  • silver-coated copper powder average particle diameter: 12 ⁇ m
  • a conductive filler 60 parts by weight of silver-coated copper powder (average particle diameter: 12 ⁇ m) as a conductive filler are kneaded to prepare a conductive adhesive.
  • the produced conductive adhesive was applied onto the copper layer and heated at 100° C. for 2 minutes using an electric oven to produce a conductive adhesive layer with a thickness of 20 ⁇ m.
  • An electromagnetic wave shielding film according to Example 1 was produced through the above steps.
  • Example 2 and 3 and Comparative Example were carried out in the same manner as in Example 1, except that the urethane resin of the type shown in Table 1 was used as the urethane resin used for the protective layer, and the composition of the protective layer was changed as shown in Table 1. Electromagnetic wave shielding films according to 1 to 8 were produced.
  • Table 1 shows the acid value, weight average molecular weight, and Tg of the urethane resins B to E in Examples and Comparative Examples.
  • FIG. 4A and 4B are schematic diagrams showing a resistance value test method.
  • a test substrate 55 was prepared in which a metal pad 52b was formed on a base film 51 and a coverlay 53 having two openings 53a for exposing the metal pad 52b was arranged. The diameter of the opening 53a was set to 1 mm.
  • the electromagnetic wave shielding film 10 according to each example and each comparative example was placed on the test substrate 55 so that the conductive adhesive layer 40 was in contact with the coverlay 53 .
  • a pressing machine was used to heat-press under the conditions of 170° C., 3 MPa, and 30 min, thereby fabricating the test shield substrate 2 shown in FIG. 4B.
  • a resistance measuring device R is connected to the two metal pads 52b, and the electrical resistance value (the electrical resistance in the thickness direction) of the conductive adhesive layer 40 of the test shield substrate 2 immediately after manufacturing is measured. value) is shown in Table 1.
  • the test shield substrate 2 was subjected to thermal shock five times under conditions of 260° C. and 1 minute, and then the electric resistance value (thickness direction) of the conductive adhesive layer 40 of the test shield substrate 2 was measured in the same manner.
  • Table 1 shows the results of measuring the electrical resistance value).
  • the test shield substrate 2 was left in a high-temperature and high-humidity environment of 85° C. and 85% RH for 500 hours. Table 1 shows the results of measuring the electrical resistance value in the vertical direction.
  • FIG. 5 is a diagram schematically showing a flex resistance test. The bending resistance of the electromagnetic wave shielding film was evaluated by the following method.
  • ⁇ Operation (i)> three copper foil patterns (copper foil thickness 12 ⁇ m, line width 8 mm) forming a circuit imitating a wiring board are formed on a base member made of a polyimide film of 25 ⁇ m, and an insulating adhesive layer is formed thereon. and a coverlay (insulating film thickness: 37.5 ⁇ m) made of a polyimide film were laminated.
  • a jig was prepared by fixing two rectangular glass epoxy plates 72 with a thickness of 0.4 mm on a baking plate 71 with a thickness of 2 mm so as to be parallel to each other. Then, the laminated body 61 was held between two glass epoxy plates 72 in a jig while being bent so that the electromagnetic wave shielding film 10 was on the outside.
  • FIG. 6 is a diagram schematically showing a blocking test.
  • the blocking resistance of the protective layer was evaluated by the following method.
  • a polyethylene terephthalate film 80 having a thickness of 50 ⁇ m, a vertical dimension of 40 mm, and a horizontal dimension of 40 mm was coated with the protective layer composition according to each example and each comparative example, and was heated at 100° C. for 2 minutes using an electric oven.
  • a specimen 81 for blocking test was produced by heating and producing a protective layer having a thickness of 5 ⁇ m.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Surgical Instruments (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

L'invention concerne un film de protection contre les ondes électromagnétiques qui est moins susceptible de provoquer un blocage lorsqu'il est stocké sous une forme enroulée, et qui présente une excellente résistance à l'humidité et une excellente résistance à la flexion. Un film de protection contre les ondes électromagnétiques selon la présente invention dans lequel une couche de protection et une couche de protection sont stratifiées est caractérisé en ce que : la couche de protection comprend une résine d'uréthane ayant une valeur acide de 2 000 à 4 000 g/éq et une Tg d'au moins 0 °C, et une charge non conductrice ayant un diamètre moyen de particule d'au plus 10 µm ; et le pourcentage en poids de la charge non conductrice par rapport au poids total de la couche de protection est de 10 à 40 % en poids.
PCT/JP2022/007068 2021-02-24 2022-02-22 Film de protection contre les ondes électromagnétiques Ceased WO2022181570A1 (fr)

Priority Applications (3)

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CN202280004051.4A CN115486215B (zh) 2021-02-24 2022-02-22 电磁波屏蔽膜
JP2022541965A JP7206441B1 (ja) 2021-02-24 2022-02-22 電磁波シールドフィルム
KR1020227028896A KR102558231B1 (ko) 2021-02-24 2022-02-22 전자파 차폐 필름

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JP2021027524 2021-02-24
JP2021-027524 2021-02-24

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KR (1) KR102558231B1 (fr)
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WO2024166843A1 (fr) * 2023-02-07 2024-08-15 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques et carte de circuit imprimé blindée
WO2024190578A1 (fr) * 2023-03-10 2024-09-19 タツタ電線株式会社 Film de blindage électromagnétique
JPWO2025197763A1 (fr) * 2024-03-21 2025-09-25
JPWO2025197764A1 (fr) * 2024-03-21 2025-09-25

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WO2026070710A1 (fr) * 2024-09-30 2026-04-02 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques et carte de circuit imprimé blindée

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WO2019012590A1 (fr) * 2017-07-10 2019-01-17 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques, tableau de connexions imprimé blindé
WO2020218507A1 (fr) * 2019-04-24 2020-10-29 三菱ケミカル株式会社 Élastomère à base de résine de polyuréthane thermoplastique

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TW201943330A (zh) * 2018-03-29 2019-11-01 日商拓自達電線股份有限公司 電磁波屏蔽膜之保護層用樹脂組成物、電磁波屏蔽膜、及電磁波屏蔽膜之製造方法
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WO2016088381A1 (fr) * 2014-12-05 2016-06-09 タツタ電線株式会社 Film de protection contre les ondes électromagnétiques
WO2018047957A1 (fr) * 2016-09-09 2018-03-15 タツタ電線株式会社 Composition adhésive conductrice
WO2019012590A1 (fr) * 2017-07-10 2019-01-17 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques, tableau de connexions imprimé blindé
WO2020218507A1 (fr) * 2019-04-24 2020-10-29 三菱ケミカル株式会社 Élastomère à base de résine de polyuréthane thermoplastique

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WO2024166843A1 (fr) * 2023-02-07 2024-08-15 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques et carte de circuit imprimé blindée
WO2024190578A1 (fr) * 2023-03-10 2024-09-19 タツタ電線株式会社 Film de blindage électromagnétique
JPWO2025197763A1 (fr) * 2024-03-21 2025-09-25
JPWO2025197764A1 (fr) * 2024-03-21 2025-09-25
WO2025197763A1 (fr) * 2024-03-21 2025-09-25 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques et carte de circuit imprimé blindée
WO2025197764A1 (fr) * 2024-03-21 2025-09-25 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques et carte de circuit imprimé blindée

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JPWO2022181570A1 (fr) 2022-09-01
TWI862884B (zh) 2024-11-21
TW202234982A (zh) 2022-09-01
KR102558231B1 (ko) 2023-07-20
JP7206441B1 (ja) 2023-01-17
CN115486215A (zh) 2022-12-16
KR20220123474A (ko) 2022-09-06
CN115486215B (zh) 2023-08-11

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