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WO2006088127A1 - Film adhésif de protection contre les ondes électromagnétiques, procédé de fabrication de celui-ci et procédé de protection d’une partie adhérée contre les ondes électromagnétiques - Google Patents

Film adhésif de protection contre les ondes électromagnétiques, procédé de fabrication de celui-ci et procédé de protection d’une partie adhérée contre les ondes électromagnétiques Download PDF

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Publication number
WO2006088127A1
WO2006088127A1 PCT/JP2006/302825 JP2006302825W WO2006088127A1 WO 2006088127 A1 WO2006088127 A1 WO 2006088127A1 JP 2006302825 W JP2006302825 W JP 2006302825W WO 2006088127 A1 WO2006088127 A1 WO 2006088127A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
adhesive layer
resin
curable
conductive adhesive
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/JP2006/302825
Other languages
English (en)
Japanese (ja)
Inventor
Hidenobu Kobayashi
Yuji Nishiyama
Akifumi Kuwabara
Takahiro Matsuzawa
Mitsuo Umezawa
Shouhei Sakai
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.)
Artience Co Ltd
Original Assignee
Toyo Ink Mfg 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 Toyo Ink Mfg Co Ltd filed Critical Toyo Ink Mfg Co Ltd
Priority to JP2007503742A priority Critical patent/JP4114706B2/ja
Priority to KR1020077021259A priority patent/KR100874302B1/ko
Publication of WO2006088127A1 publication Critical patent/WO2006088127A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C09J2463/00—Presence of epoxy resin
    • 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
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/006—Presence of epoxy resin in the substrate
    • 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
    • C09J2475/00—Presence of polyurethane
    • H10W42/20—

Definitions

  • Electromagnetic wave shielding adhesive film method for producing the same, and electromagnetic wave shielding method for adherend
  • the present invention relates to an electromagnetic wave shielding adhesive film, a method for producing the same, and an electromagnetic wave shielding method for an adherend.
  • the electromagnetic wave shielding adhesive film according to the present invention can be suitably used for the purpose of shielding electromagnetic noise generated from an electric circuit by sticking to a flexible printed wiring board or the like that undergoes repeated bending.
  • This electromagnetic shielding adhesive film itself is required to be thin and have excellent bending resistance, such as not affecting the bending resistance of the entire flexible printed circuit board bonded together, in addition to electromagnetic shielding properties!
  • an electromagnetic wave shielding adhesive film one having a basic structure in which a conductive layer is provided on a thin film substrate film is widely known.
  • a cover film has a shield layer composed of a conductive adhesive layer and, if necessary, a metal thin film layer on one side, and is separated from the adhesive layer on the other surface.
  • a reinforcing shield film in which a mold-type reinforcing film is sequentially laminated (see Patent Document 1).
  • a shield film having a conductive adhesive layer, a shield layer having Z or a metal thin film, and a base film made of an aromatic polyamide resin is known (see Patent Document 2). See).
  • a shielding adhesive film in which a cover film is formed by coating a resin on one side of a separate film, and a shield layer composed of a metal thin film layer and an adhesive layer is provided on the surface of the cover film.
  • the adhesive layer of the conventional electromagnetic wave shielding adhesive film includes a thermoplastic resin such as polystyrene, vinyl acetate, polyester, polyethylene, polypropylene, polyamide, rubber, or acrylic.
  • Thermosetting resin such as fat, phenol, epoxy, urethane, melamine, or alkyd has been used.
  • the conventional adhesive layer does not have sufficient bending resistance and sufficient heat resistance. In particular, it is not completely resistant to repeated bending for use in flexible printed circuit boards.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-298285
  • Patent Document 2 Japanese Patent Laid-Open No. 2004-273577
  • Patent Document 3 Japanese Patent Laid-Open No. 2004-95566
  • the present invention has excellent bending resistance and heat resistance that can withstand high temperatures during lead-free solder reflow in addition to sufficient electromagnetic shielding properties, and is affixed to flexible printed wiring boards and the like. It is an object of the present invention to provide an electromagnetic wave shielding adhesive film that can be suitably used for shielding electromagnetic noise.
  • Another object of the present invention is to provide a method for inexpensively and stably producing an electromagnetic wave shielding adhesive film having such excellent performance.
  • an object of the present invention is to provide a method for shielding an electromagnetic wave of an adherend using the electromagnetic wave shielding adhesive film.
  • the present invention provides:
  • the curable conductive adhesive layer (I) comprises a diol compound (a) having a carboxyl group, a polyol (b) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c Polyurethane polyurethane resin (A), which is obtained by reacting a urethane prepolymer (d) having an isocyanate group at the terminal with a polyamino compound (e).
  • An epoxy resin (B) having two or more epoxy groups having two or more epoxy groups
  • the present invention relates to an electromagnetic wave shielding adhesive film.
  • the curable conductive adhesive layer (I) is 100 parts by weight of the polyurethane polyurethane resin (A). 3 to 200 parts by weight of epoxy resin (B), and further 10 to 700 parts by weight of conductive filler for 100 parts by weight of polyurethane polyurethane resin (A) and epoxy resin (B).
  • the curable conductive adhesive layer (I) is 100 parts by weight of the polyurethane polyurethane resin (A). 3 to 200 parts by weight of epoxy resin (B), and further 10 to 700 parts by weight of conductive filler for 100 parts by weight of polyurethane polyurethane resin (A) and epoxy resin (B).
  • the curable conductive adhesive layer (I) having such a composition exhibits a sufficient cushioning property during heating and pressure bonding and flows into the insulating film removal portion on the ground circuit.
  • the conductive cured adhesive layer (II) obtained by the reaction between the carboxyl group in the polyurethane resin (A) and the epoxy group in the epoxy resin (B) by heat and pressure bonding is Heat resistance enough to withstand free solder reflow.
  • the conductive cured adhesive layer ( ⁇ ) has excellent bending resistance, and does not impair the bending resistance of the entire circuit board when it is attached to a flexible printed wiring board.
  • the base film force is a polyester resin having a carboxyl group (C) and an epoxy resin having two or more epoxy groups. It is a curable film-like rosin composition (III) containing fat (D).
  • the base film is such a film-like curable resin composition (III)
  • the carboxyl group in the polyester resin (C) and the epoxy group in the epoxy resin (D) are heated.
  • Cured resin composition with excellent bending resistance, wear resistance, and workability that reacts by pressing and does not easily curl due to thermal shrinkage due to lead-free solder reflow (I V) is obtained and expresses preferable performance as a base material for an electromagnetic wave shielding adhesive film
  • the carboxyl group-containing polyester resin (C) has an acid value of 5 to 40 mgKOHZg, and has a number average molecular weight force. 0000-40000 and a glass transition temperature of 10-50 ° C.
  • the carboxyl group-containing polyester resin (C) force diol (cl) and dibasic acid or dibasic acid anhydride are used.
  • Such a carboxyl group-containing polyester resin (C) has a good cross-linking structure by heat curing reaction with an epoxy resin (D) having two or more epoxy groups, and heat generated by lead-free solder reflow.
  • a film-like cured resin composition (IV) having excellent bending resistance, abrasion resistance, and workability that hardly causes curling due to shrinkage is obtained.
  • the base film contains a flame retardant (E).
  • a slightly pressure-sensitive adhesive is provided on the surface of the base film on which the curable conductive adhesive layer (I) is not provided.
  • a reinforcing film is laminated through a layer or without a slightly adhesive layer.
  • the processability of the electromagnetic wave shielding adhesive film of the present invention is improved and the mounting on a circuit board is facilitated.
  • the reinforcing film and the slightly adhesive layer provided as necessary are removed after the electromagnetic wave shielding adhesive film is heat-pressed on a flexible printed wiring board or the like.
  • a protective film is laminated on the curable conductive adhesive layer (I).
  • the present invention also relates to a method for producing an electromagnetic wave shielding adhesive film.
  • the present invention provides:
  • the present invention also relates to a method for producing an electromagnetic wave shielding adhesive film.
  • the present invention provides:
  • a polyol compound (a) having a carboxyl group and a polyol having a number average molecular weight of 500 to 8000 other than a diol compound containing a ruboxyl group Polyurethane polyurethane prepared by reacting b) with an organic diisocyanate (c) and a urethane prepolymer (d) having an isocyanate group at the terminal and a polyamino compound (e).
  • the base film in which the reinforcing film is laminated on the curable conductive adhesive layer (I) is overlapped so that the base film and the curable conductive adhesive layer (I) are in contact with each other.
  • the present invention also relates to a method for producing an electromagnetic wave shielding adhesive film.
  • the present invention provides:
  • a resin composition containing a polyester resin having a carboxyl group (C) and an epoxy resin having two or more epoxy groups (D) is applied and dried.
  • a diolic compound (a) having a carboxyl group On the film-like curable resin composition (III) layer, a diolic compound (a) having a carboxyl group, a polyol (b) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic Polyurethane polyurethane resin (A) obtained by reacting diisocyanate (c) and prepared by reacting urethane prepolymer (d) having an isocyanate group at the terminal with polyamino compound (e), Apply curable conductive adhesive composition containing epoxy resin (B) having two or more epoxy groups and conductive filler, and dry to form curable conductive adhesive layer (I) And the process of
  • the present invention also relates to a method for producing an electromagnetic wave shielding adhesive film.
  • the present invention provides:
  • a resin composition containing a polyester resin having a carboxyl group (C) and an epoxy resin having two or more epoxy groups (D) is applied and dried.
  • a polyol compound (a) having a carboxyl group and a polyol having a number average molecular weight of 500 to 8000 other than a diol compound containing a ruboxyl group Polyurethane polyurethane prepared by reacting b) with an organic diisocyanate (c) and a urethane prepolymer (d) having an isocyanate group at the terminal and a polyamino compound (e).
  • the present invention also relates to a method for producing an electromagnetic wave shielding adhesive film.
  • the present invention provides:
  • a base film provided on the surface of the slightly adhesive layer,
  • the protective film is peeled, and the exposed curable conductive adhesive layer (I) is superimposed on an adherend and heated to cure the curable conductive adhesive layer (I).
  • the present invention also relates to an electromagnetic wave shielding method for an adherend including peeling a reinforcing film together with the slightly adhesive layer.
  • the present invention provides:
  • Polyester having a carboxyl group provided on one surface of the reinforcing film A film-like curable resin composition (coffin) layer containing the resin (C) and an epoxy resin (D) having two or more epoxy groups,
  • the protective film is peeled off, and the exposed curable conductive adhesive layer (I) is overlaid on the adherend and heated, and the film-like curable resin composition (III) layer and the curable conductive layer are heated.
  • the present invention also relates to an electromagnetic wave shielding method for an adherend, which comprises peeling off the reinforcing film after the adhesive layer (I) is cured.
  • the electromagnetic wave shielding adhesive film of the present invention has only a conductive adhesive layer containing a specific polyurethane polyurethane resin and epoxy resin as a shielding layer, and a metal film layer and the like are laminated. Therefore, it is thin and excellent in bending resistance, and can exhibit heat resistance that can withstand lead-free solder reflow.
  • a reinforcing film having a pressure-sensitive adhesive layer having both heat resistance and removability is laminated to the base film at an early stage of the production process of the electromagnetic wave shielding adhesive film. By doing, it can be set as the support material of the base film which is a thin film, and lamination
  • the base film is a film-like curable resin composition (coffin) containing a specific polyester resin and epoxy resin
  • the resulting electromagnetic wave shielding adhesive film is curled by lead-free solder reflow. Excellent bending resistance, wear resistance, and workability can be exhibited without causing the occurrence of slag.
  • the film-form curable resin composition (III) as a base film
  • the film-form curable resin composition (polyester) containing a polyester resin and an epoxy resin on a reinforcing film.
  • a film-like curable resin composition ( ⁇ ) layer is formed on the reinforcing film, a curable conductive adhesive layer (I) is formed on the protective film, and the curable conductive adhesive layer (I )
  • An electromagnetic wave shielding adhesive film can be produced by a method in which a film-like curable resin composition (III) layer on which the reinforcing film is laminated is laminated. Since it is not necessary to provide an agent layer, the manufacturing method is simplified.
  • FIG. 1 is an explanatory view schematically showing an outline of a process of a method for producing an electromagnetic wave shielding adhesive film of the present invention.
  • FIG. 2 is an explanatory view schematically showing the steps of one embodiment of the method for producing an electromagnetic wave shielding adhesive film of the present invention.
  • FIG. 3 is an explanatory view schematically showing steps of different embodiments of the method for producing an electromagnetic wave shielding adhesive film of the present invention.
  • FIG. 4 is an explanatory view schematically showing the steps of one embodiment of the method for producing an electromagnetic wave shielding adhesive film of the present invention when a film-like curable resin composition (III) is used as a substrate. is there.
  • FIG. 5 is an explanatory view schematically showing the steps of different embodiments of the method for producing an electromagnetic wave shielding adhesive film of the present invention when a film-like curable resin composition (III) is used as a substrate. It is.
  • FIG. 6 is an explanatory view schematically showing the steps of one embodiment of the method for using the electromagnetic wave shielding adhesive film of the present invention.
  • FIG. 7 is an explanatory view schematically showing the steps of one embodiment of the method for using the electromagnetic wave shielding adhesive film of the present invention when the film-like curable resin composition (III) is used as a substrate. is there.
  • FIG. 8 is a view showing a method for evaluating the heat resistance of the electromagnetic wave shielding adhesive film of the present invention. Explanation of symbols
  • the electromagnetic wave shielding adhesive film of the present invention carries the curable conductive adhesive layer (I) on one surface of the base film, and impairs the bending resistance of the entire electromagnetic wave shielding adhesive film. Do not have a causative metal film.
  • the conductive curable adhesive layer ( ⁇ ) formed by curing the curable conductive adhesive layer (I) has a function of shielding electromagnetic waves and fixes the electromagnetic shielding adhesive film to the adherend.
  • it when affixed to a flexible printed circuit board and used, it is stably connected to the ground circuit of the printed circuit board, and the generated electromagnetic noise is released to the outside. This can be effectively shielded. Furthermore, it is possible to shield electromagnetic noise generated outside from entering the printed wiring board.
  • the curable conductive adhesive composition constituting the curable conductive adhesive layer (I) of the electromagnetic wave shielding adhesive film of the present invention comprises a polyurethane polyurethane resin (A) and two or more resins. It contains an epoxy resin (B) having a alkoxy group and a conductive filler.
  • Polyurethane Polyurea resin (A) is prepared by reacting urethane prepolymer (d) having an isocyanate group at the terminal with polyamino compound (e). Further, the urethane prepolymer (d) is:
  • the curable adhesive resin composition containing the polyurethane polyurethane resin (A) and the epoxy resin (B) can disperse the conductive filler satisfactorily and contains the conductive filler. Even if it is, it exhibits sufficient adhesive strength.
  • the curable conductive adhesive layer (I) composed of a curable conductive adhesive composition containing polyurethane polyurethane resin (A), epoxy resin (B), and conductive filler, Less exudation of the adhesive layer during thermocompression bonding Excellent heat resistance that can withstand lead-free solder reflow, and even better resistance to conductive cured adhesive layers ( ⁇ ) Can do.
  • the polyurethane polyurethane resin (A) contained in the curable conductive adhesive composition comprises a urethane prepolymer (d) having an isocyanate group at the terminal and a polyamino compound (e). Obtained by reaction.
  • the urethane prepolymer (d) comprises a carboxyl group-containing diol compound (a), a polyol (b) other than the carboxyl group-containing diol compound having a number average molecular weight of 500 to 8000, and an organic diisocyanate (c). Obtained by reaction.
  • Examples of the carboxyl group-containing diol compound (a) include dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, or dimethylolpentanoic acid (wherein the alkanoic acid is a carbon atom) 2 to 8), dihydroxy aliphatic dicarboxylic acids such as dihydroxysuccinic acid (wherein the aliphatic dicarboxylic acids preferably have 4 to 8 carbon atoms), or dihydroxy And dihydroxy aromatic carboxylic acids such as benzoic acid (wherein the aromatic carboxylic acid preferably has 7 to 11 carbon atoms). Especially from the point of reactivity and solubility, Methylolpropionic acid or dimethylolbutanoic acid is preferred.
  • the carboxyl group-containing diol compound (a) may be used alone or in combination of two or more.
  • the polyol (b) other than the carboxyl group-containing diol compound having a number average molecular weight of 500 to 8000 is a polyol generally known as a polyol component constituting a polyurethane resin (however, a carboxyl group-containing diol compound) Excluding things).
  • the number average molecular weight (Mn) of the polyol (b) is appropriately determined in consideration of the heat resistance, adhesive strength, solubility, etc. of the resulting polyurethane polyurethane resin (A), preferably 1000 to 500 0.
  • the resulting polyurethane polyurethane resin (A) will have too many urethane bonds, reducing the flexibility of the polymer skeleton and adhering to flexible printed circuit boards.
  • the number average molecular weight (Mn) exceeds 8000, the number of carboxyl groups derived from diol compound (a) in polyurethane polyurethane resin (A) decreases. As a result, the reaction point with the epoxy resin decreases, so that the resistance to dryness and reflow resistance of the resulting conductive cured adhesive layer tends to decrease.
  • Examples of the polyol (b) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound include various polyether polyols, polyester polyols, polycarbonate polyols, or polybutadiene glycols. Etc. can be used.
  • polyether polyols examples include polymers or copolymers such as ethylene oxide, propylene oxide, or tetrahydrofuran.
  • polyester polyols include ethylene glycol, 1,2 propanediol, 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, neopentyl glycol, pentanediol, 3-methyl-1, 5 Saturated or unsaturated low molecular weight diols such as pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol or dimer diol, adipic acid, phthalate Dicarboxylic acids such as acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, or anhydrous Polyester obtained by reacting Polyol
  • polycarbonate polyols examples include:
  • reaction product of glycol or bisphenol and carbonate 1) reaction product of glycol or bisphenol and carbonate, or
  • Etc. can be used.
  • glycols used in the preparation of the reaction product of 1) or 2) above include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1, 5 Pentanediol, 2-methyl-1,8 octanediol, 3,3 'dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3 butanediol, 1,4 butanediol, 1,5 pentanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9 bis (1,1-dimethylolate 2 Hydroxychinole
  • the bisphenol used in the preparation of the reaction product of 1) or 2) above includes, for example, bisphenols such as bisphenol ⁇ and bisphenol F, and ethylene oxide in these bisphenols. Or the compound etc. which added alkylene oxides, such as a propylene oxide, can be mentioned.
  • Examples of the carbonic acid ester used for the preparation of the reaction product 1) include dimethylolate carbonate, jetinole carbonate, diphenolate carbonate, ethylene carbonate, and propylene carbonate.
  • the various polyols exemplified as Reol (b) may be used alone or in combination of two or more.
  • the number average of compounds other than the force lpoxyl group-containing diol compound (a) and the carboxyl group-containing diol compound When reacting with the polyol (b) having a molecular weight of 500 to 8000 and the organic diisocyanate (c), in addition to these components (a), (b) and (c), a carboxyl group-containing diol compound Other low molecular diols may be used in combination.
  • low molecular diols examples include various low molecular diols used for the production of polyols (b) having a number average molecular weight of 500 to 8000 other than carboxyl group-containing diol compounds (for example, the number of carbon atoms is 4 To 12 diols).
  • the carboxyl group-containing diol compound (a) and the polyol (b) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound are: It is preferable to use the diol compound (a) at a ratio of 0.1 mol to 4.0 mol with respect to 1 mol of the polyol (b). More preferably.
  • the amount of the diol compound (a) used relative to 1 mol of the polyol (b) is less than 0.1 mol, the epoxy resin (B) and the crosslinkable carboxyl groups are reduced, and the conductive cured adhesive layer There is a tendency that the resistance to nodule and reflow resistance of (ii) is lowered. On the other hand, if it exceeds 4.0 mol, the adhesive property of the conductive cured adhesive layer (II) tends to be lowered.
  • organic diisocyanate (c) for example, an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable! /.
  • aromatic diisocyanate for example, a diisocyanate of an aromatic compound having 6 to 20 carbon atoms can be used, and specifically, 1, 5 naphthylene diisocyanate, 4, 4'-diphenylmethane diester.
  • Isocyanate 4,4'-diphenyldimethylmethane diisocyanate, 4,4 'monobenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diester Isocyanate, 1,3-phenolic diisocyanate, 1,4-phenolic diisocyanate, tolylene diisocyanate, or xylylene diisocyanate Examples include sulfonate.
  • aliphatic diisocyanate for example, a diisocyanate of an aliphatic compound having 4 to 20 carbon atoms can be used, and specifically, butane 1,4-diisocyanate, hexamethylene diisocyanate. Examples thereof include cyanate, 2, 2, 4 trimethylhexamethylene diisocyanate, and lysine diisocyanate.
  • alicyclic diisocyanate for example, a diisocyanate of an alicyclic compound having 6 to 20 carbon atoms can be used, and specifically, cyclohexane mono-1,4 diisocyanate, isophorone diisocyanate, Examples include dicyclohexylenomethane 4,4′-diisocyanate, 1,3 bis (isocyanate methyl) cyclohexane, methylcyclohexane diisocyanate, and the like.
  • the urethane prepolymer (d) having an isocyanate group at the terminal comprises a carboxyl group-containing diol compound (a), a polyol (b) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate. It can be obtained by reacting with (c).
  • the conditions for synthesizing the urethane prepolymer (d) having an isocyanate group at the terminal are not particularly limited except that the isocyanate group becomes excessive, but the equivalent ratio of the isocyanate group Z hydroxyl group is 1.
  • the reaction temperature is usually from ordinary temperature to 120 ° C.
  • the production time or surface force for controlling side reactions is preferably 60 to 100 ° C.
  • the polyurethane polyurethane resin (A) can be obtained by reacting a urethane prepolymer (d) having an isocyanate group at the terminal with a polyamino compound (e).
  • polyamino compound (e) examples include an aliphatic compound having 2 to 20 carbon atoms, an alicyclic compound having 6 to 20 carbon atoms, or a diamine or aromatic compound having 6 to 20 carbon atoms.
  • Specific examples include tetramine, specifically ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophorone diamine, dicyclohexylmethane-1,4,4,1diamin, 2- (2 aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenedi Amines having a hydroxyl group such as amine, di2-hydroxyethylethylenediamine, di-2-hydroxypropylethylenediamine can also be used. Of these, isophorone diamine is preferably used.
  • a reaction terminator is used to adjust the molecular weight.
  • a reaction terminator dialkylamines such as di-n-ptylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.
  • Conditions for the reaction of the urethane prepolymer (d) having an isocyanate group at the terminal, the polyamino compound (e) and the reaction terminator as required are not particularly limited, but the urethane prepolymer (d) It is preferable that the total equivalent ratio of the amino group in the polyamino compound (e) and the reaction terminator (amino group Z isocyanate group) to the isocyanate group possessed is in the range of 0.5 to 1.3.
  • the equivalent ratio is less than 0.5, the non-reflow resistance of the conductive cured adhesive layer (II) becomes insufficient, and if it is more than 1.3, the polyamino compounds (e) and Z Alternatively, the reaction terminator remains unreacted, and the odor tends to remain.
  • Solvents used for synthesizing the polyurethane polyurethane resin (A) include aromatic solvents such as benzene, toluene, and xylene, alcohol solvents such as methanol, ethanol, isopropanol, and n-butanol. And ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as ethyl acetate and butyl acetate. These solvents can be used alone or in combination of two or more.
  • aromatic solvents such as benzene, toluene, and xylene
  • alcohol solvents such as methanol, ethanol, isopropanol, and n-butanol.
  • ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • ester solvents such as ethyl acetate and butyl
  • the weight average molecular weight of the obtained polyurethane polyurethane resin (A) is preferably in the range of 5,000 to 100,000. When the weight average molecular weight is less than 5000, the non-reflow resistance of the conductive cured adhesive layer ( ⁇ ) tends to be inferior. When it exceeds 100,000, the adhesion of the conductive cured adhesive layer ( ⁇ ) Tend to decrease.
  • the epoxy resin (B) contained in the curable conductive adhesive composition is a resin having two or more epoxy groups, and may be liquid or solid.
  • epoxy resin (B) epoxy resin having an epoxy equivalent of 170 to 1000 (g / eq) is used. I prefer to do that!
  • Examples of the epoxy resin (B) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenol. -Type epoxy resin, terpene type epoxy resin, glycidyl ether type epoxy resin such as tris (glycidyloxyphenyl) methane or tetrakis (glycidyloxyphenyl) ethane, tetraglycidyldiaminodiphenyl Glycidylamine type epoxy resin, such as enyl methane, tetrabromobisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, a naphthol novolac type epoxy resin, or brominated phenol A novolac type epoxy resin can be used.
  • epoxy resins can be used singly or in combination of two or more.
  • bisphenol A type epoxy resin is used as cresol novolac type epoxy resin or tetrax (glycidyloxyphenol) ethane type epoxy resin.
  • cresol novolac type epoxy resin or tetrax (glycidyloxyphenol) ethane type epoxy resin.
  • tetrax (glycidyloxyphenol) ethane type epoxy resin Prefer U ,.
  • the blending ratio of the epoxy resin (B) and the polyurethane polyurethane resin (A) is determined by the polyurethane polyurethane resin ( A)
  • the epoxy resin (B) is preferably 3 to 200 parts by weight with respect to 100 parts by weight. 5 to more preferably LOO parts by weight.
  • the epoxy resin (B) is less than 3 parts by weight, and the solder reflow resistance of the electrically conductive cured adhesive layer ( ⁇ ) tends to be low. is there.
  • the epoxy resin (B) is more than 200 parts by weight, the adhesive property of the conductive cured adhesive layer ( ⁇ ) tends to be lowered.
  • the curable conductive adhesive composition includes a phenolic resin, a silicone resin, a urea resin, an acrylic resin, as long as the performance such as heat resistance and flex resistance is not impaired.
  • Polyester-based resin, polyamide-based resin, Z or polyimide-based resin can be included.
  • the conductive filler contained in the curable conductive adhesive composition imparts conductivity to the conductive hardening adhesive layer.
  • Examples of the conductive filler include: Metal fillers, carbon fillers and mixtures thereof are used.
  • metal fillers metal powder such as silver, copper or nickel, alloy powder such as solder, silver Examples include plated copper powder, metal-plated glass fiber, and carbon filler. Among these, a silver filler having a specific surface area of 0.5 to 2.5 m 2 Zg, which is easy to obtain contact between fillers, is preferred, and a silver filler having high conductivity is preferred.
  • the shape of the conductive filler is not particularly limited, and may be, for example, spherical, flaky, dendritic, or fibrous.
  • the content of the conductive filler in the curable conductive adhesive composition varies depending on the required degree of electromagnetic shielding effect.
  • the polyurethane polyurethane resin (A) and the epoxy resin (B) It is preferable to use 10 to 700 parts by weight of conductive filler with respect to 100 parts by weight in total.
  • the content of the conductive filler is less than 10 parts by weight, the conductive fillers are not sufficiently in contact with each other, high conductivity cannot be obtained, and the electromagnetic wave shielding effect tends to be insufficient.
  • the surface resistance value of the conductive cured adhesive layer does not decrease, the conductivity reaches a saturated state, and the conductive filler in the conductive adhesive As a result, the adhesiveness and adhesive strength of the conductive cured adhesive layer to the base film are reduced.
  • the curable conductive adhesive composition has a purpose of accelerating the reaction between the polyurethane polyurethane resin (A) and the epoxy resin (B) or the epoxy resin (B) alone.
  • a curing accelerator, and Z or a curing agent for example, a tertiary amine compound, a phosphine compound, or an imidazole compound can be used, and as the curing agent, for example, dicyandiamide, carboxylic acid, etc. Hydrazide, acid anhydride, or the like can be used.
  • tertiary amine compounds include, for example, triethylamine, benzyl dimethylamine, 1,8 diazabicyclo (5.4.0) undecene-7, or 1,5 diazabicyclo (4. 3. 0) Nonene 5 etc.
  • phosphine compound include triphenylphosphine and tributylphosphine.
  • imidazole compound include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenol 4-methylimidazole, 2,4-dimethylimidazole, and 2-phenolimidazole.
  • latent curing accelerators with improved storage stability, such as a type in which an imidazole compound is encapsulated in microcapsules. Among these, latent curing accelerators are preferred.
  • Examples of the carboxylic acid hydrazide as the hardener include succinic hydrazide and adipic hydrazide.
  • Examples of the acid anhydride include hexahydrophthalic anhydride, trimellitic anhydride, and the like.
  • curing accelerators or curing agents may be used in combination of two or more, and the total amount used (including the case where only one of the curing accelerator or the curing agent is used)
  • the range of 0.1 to 30 parts by weight per 100 parts by weight of the resin (B) is preferred.
  • the curable conductive adhesive composition includes a silane coupling agent, an acid, and an acid as long as the conductivity, adhesiveness, and / or non-node reflow resistance of the conductive cured adhesive layer (i) is not deteriorated. It can contain anti-bacterial agents, pigments, dyes, tackifiers, plasticizers, ultraviolet absorbers, antifoaming agents, leveling modifiers, fillers, Z or flame retardants, and the like.
  • the electromagnetic wave shielding adhesive film of the present invention has a curable conductive adhesive layer (I) on one surface of a base film as a basic structure.
  • the base film gives mechanical strength to the electromagnetic wave shielding adhesive film and also serves as an insulating layer.
  • various plastic films such as polyimide, polyamideimide, polyetherimide, polyethylene sulfide, polysulfone, or polyphenylene sulfide can be used. In view of heat resistance, flame retardancy, or cost, polyphenylene sulfide is preferably used.
  • the thickness of the base film is preferably 3 to 50 ⁇ m, more preferably 5 to 30 ⁇ m.
  • the film strength is lowered, and it is difficult to play a role as an insulating support for the conductive adhesive layer.
  • corrugation of the to-be-adhered body surface of an electromagnetic wave shielding adhesive film will fall, and it will become difficult to acquire sufficient shielding effect.
  • the base film comprises a carboxyl group-containing polyester resin (C) and an epoxy resin (D) having two or more epoxy groups.
  • the film-like curable resin composition (111) contained that is, it can be in an uncured state.
  • the base film is such a film-like curable resin composition ( ⁇ )
  • heat shrinkage due to lead-free solder reflow that has heat resistance that can withstand lead-free solder reflow is the cause.
  • the film-like cured resin composition (IV) can be obtained without the occurrence of curling.
  • it is suitable as a substrate for an electromagnetic wave shielding adhesive film.
  • the carboxyl group-containing polyester resin (C) contained in the film-like curable resin composition (III) preferably has an acid value of 5 to 40 mg KOHZg and 10 to 30 mg KOH Zg. It is more preferable.
  • the acid value is less than 5 mg KOHZg, the amount of carboxyl groups capable of crosslinking with the epoxy resin (D) decreases, and the solder reflow resistance of the film-shaped cured resin composition (IV) tends to decrease.
  • the acid value power exceeds OmgKOHZg, the flexibility of the film-shaped cured resin composition (IV) tends to be lowered.
  • the number average molecular weight (Mn) of the polyester resin (C) is preferably from 10,000 to 40,000, more preferably from 15,000 to 30000, more preferably from the force S.
  • Mn number average molecular weight
  • the heat resistance or flexibility of the film-shaped cured resin composition (IV) tends to decrease.
  • it exceeds 40,000 The coatability is significantly reduced, making handling difficult.
  • the glass transition temperature of the polyester resin (C) is preferably 10 to 50 ° C, more preferably 15 to 45 ° C.
  • the glass transition temperature is less than 10 ° C, the heat resistance or abrasion resistance of the film-shaped cured resin composition (IV) tends to decrease.
  • the glass transition temperature exceeds 50 ° C, the film-shaped cured resin composition (IV) tends to decrease.
  • flexibility of fat composition (IV) There exists a tendency for the softness
  • the polyester resin (C) as described above is preferably a hydroxyl group-containing polyester resin (c4), a polybasic acid having three or more carboxyl groups in the molecule, or an anhydride thereof (c5).
  • the hydroxyl group-containing polyester resin (c4) can be obtained by reacting diol (cl) with dibasic acid or dibasic acid anhydride (c2) or dibasic acid dialkyl ester (c3). Can be obtained by reaction.
  • diol (cl) for example, a diol of a linear or branched aliphatic compound having 2 to 12 carbon atoms, specifically, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol.
  • Examples of the dibasic acid or dibasic acid anhydride (c2) to be reacted with the diol (cl) include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and anhydrides thereof. You can list things.
  • aromatic dicarboxylic acid or its anhydride examples include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 5 sodium sulfoisophthalic acid, and (anhydrous) phthalic acid.
  • (anhydrous) phthalic acid collectively means phthalic acid and phthalic anhydride.
  • Examples of the alicyclic dicarboxylic acid or its anhydride include tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, 1,4-cyclohexanedicarboxylic acid, and the like.
  • Examples of the aliphatic dicarboxylic acid or anhydride thereof include (anhydrous) succinic acid, fumaric acid, (anhydrous) maleic acid, adipic acid, sebacic acid, azelaic acid, and hymic acid.
  • Examples of the dibasic acid dialkyl ester (c3) to be reacted with the diol (cl) include, for example, the dibasic acid and a linear or branched alkyl alcohol having 1 to 18 carbon atoms. Can be mentioned.
  • linear or branched alkyl alcohols having 1 to 18 carbon atoms examples include methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n butyl alcohol, sec butyl alcohol, tert butyl alcohol, n-a Mill alcohol, acetyl isopropyl alcohol List cornore, neohexenoreanoleconole, isohexenoreanoreconole, n-hexenoureanolol, heptyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, or octadecyl alcohol Can do.
  • dialkyl ester (c3) of dibasic acid! / The compound is dimethylphthalic acid or dimethylisophthalic acid.
  • the dibasic acid or dibasic acid anhydride (c2) and the dialkyl ester of dibasic acid (c3) are the most effective in terms of the hardness and flexibility of the obtained film-form cured resin composition (IV). It can be appropriately selected and used.
  • Carboxyl group-containing polyester resin (C) is a polyester resin having a hydroxyl group (c
  • Examples of the polybasic acid having 3 or more carboxyl groups in the molecule or its anhydride (c5) include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, or ethylene glycol An anhydride etc. can be mentioned.
  • the proportion of the carboxyl group-containing polyester resin (c4) and the polybasic acid having 3 or more carboxyl groups in the molecule or its anhydride (c5) is appropriately determined in consideration of the molecular weight and acid value of both.
  • the acid value of the polyester resin (C) obtained by reacting both is 5
  • the reaction is preferably carried out at a rate such that the temperature is 0 ° C.
  • the epoxy resin (D) having two or more epoxy groups contained in the film-like curable resin composition (III) should be the same as the epoxy resin (B). Can do.
  • the film-like curable resin composition ( ⁇ ) containing the polyester resin (C) and the epoxy resin (D) is a film-like cured resin composition (IV) obtained by curing. It contains phenolic resin, silicone resin, urea resin, acrylic resin, polyamide resin, or polyimide resin as long as it does not impair performance such as heat resistance. It can be done.
  • the base film used in the electromagnetic wave shielding adhesive film of the present invention preferably contains a flame retardant (E). Accordingly, it is preferable that the film-like curable resin composition (III) containing the polyester resin (C) and the epoxy resin (D) contain the flame retardant (E) and be cured.
  • flame retardants are halogenated flame retardants such as bromine, chlorine, antimony, or halogen-containing ester phosphate, and aluminum hydroxide, magnesium hydroxide, phosphorus compounds, or nitrogen compounds.
  • any known flame retardant can be used, but in view of the recent trend of non-halogen flame in the field of electronic materials, as a flame retardant (E), It is preferable to use a non-halogen flame retardant.
  • phosphorus compound flame retardants or nitrogen compound flame retardants are particularly preferred.
  • the phosphorus compound flame retardant include triallyl 'isopropyl phosphate, tris (3-hydroxypropyl) phosphine oxide, 1,3-phenol-bis (dixylenyl) phosphate, or 2, Phosphate esters such as 2-bis (p-hydroxyphenol) propane 'triclophosphine phosphine oxide polymer (polymerization degree 1-3) phenol condensate, phosphate complex, aromatic condensed phosphate ester, etc.
  • Phosphate esters such as 2-bis (p-hydroxyphenol) propane 'triclophosphine phosphine oxide polymer (polymerization degree 1-3) phenol condensate, phosphate complex, aromatic condensed phosphate ester, etc.
  • Examples thereof include a compound, ammonium polyphosphate, ammonium acid polyphosphate, butyl acid phosphate, butoxetyl acid phosphate, melamine phosphate, and red phosphorus.
  • nitrogen compound-based flame retardant examples include melamine derivatives such as melamine, melamine's cyanurate, melamine, melem, and melon.
  • These flame retardants can be used singly or in combination of two or more.
  • a film-like curable resin composition (III) and a film-like cured resin composition (IV) containing a polyester resin (C) and an epoxy resin (D) can be produced without damaging the film properties. More preferably, it is a mixture of ammonium polyphosphate and a nitrogen-based flame retardant, or a composite thereof.
  • the content of the flame retardant (E) is preferably 5 to 200 parts by weight and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the polyester resin (C). . Content is 5 When the amount is less than parts by weight, it is difficult to flame retardant the film-like curable resin composition ( ⁇ ⁇ ) and the film-like curable resin composition (IV). On the other hand, when the content is more than 200 parts by weight, the film properties necessary as an electromagnetic shielding adhesive film tend to be impaired.
  • the film-like curable resin composition (III) containing the polyester resin (C) and the epoxy resin (D) is resistant to the heat resistance of the film-type cured resin composition (IV).
  • the curable conductive adhesive composition and the resin composition containing the polyester resin (C) and the epoxy resin (D) are each easy to handle.
  • the liquid composition is preferably in the form of a liquid composition, and after coating, it is dried to form a curable conductive adhesive layer (I) and a film-like curable resin composition ( ⁇ ), respectively.
  • the formation of the curable conductive adhesive layer (I) and the formation of the film-like curable resin composition ( ⁇ ) containing the polyester resin (C) and the epoxy resin (D) are usually performed. Can be done using a coating device that is used! Examples of coating apparatuses include a roll knife coater, Tyco 1 ⁇ ' ⁇ ", mouth 1 ⁇ " Noroko 1 ⁇ "Ta' ⁇ ", No 1 ⁇ "Ko 1 ⁇ ” Ta ' ⁇ ", gravure mouth 1 ⁇ Noreco 1 ⁇ Ta ⁇ "Rino 1 ⁇ ” Suuguchi 1 ⁇ "A coater, datebing or blade coater can be used.
  • the drying conditions of the applied coating film the contained solvent is sufficiently volatilized, and the curable conductive adhesive layer (I) and the film-like curable resin composition ( ⁇ ) are cured.
  • the conditions be 80 to 100 ° C for 30 seconds to 5 minutes.
  • the thickness of the curable conductive adhesive layer (I) is preferably 5 to 25 ⁇ m, more preferably 8 to 20 ⁇ m.
  • the thickness of the curable conductive adhesive layer (I) is less than 5 ⁇ m, it is difficult to achieve both electromagnetic shielding properties and adhesion to the adherend. On the other hand, if it exceeds 25 ⁇ , the flexibility of the electromagnetic wave shielding adhesive film may decrease, and satisfactory bending resistance may not be obtained.
  • the thickness of is preferably 3 to 50 ⁇ m, as in the case of a base film made of other materials. 5 to 30 m is more preferable.
  • the electromagnetic wave shielding adhesive film of the present invention is a reinforcing film with or without a slight pressure-sensitive adhesive layer on the surface of the base film on which the curable conductive adhesive layer (I) is not provided. It is preferred to be laminated,
  • the reinforcing film and the slightly pressure-sensitive adhesive layer provided as necessary can be easily peeled off after the electromagnetic wave shielding adhesive film is thermocompression bonded to the adherend. It is important not to contaminate the material film surface.
  • an adhesive layer is further laminated on the base film of the electromagnetic wave shielding adhesive film.
  • a printing process may be performed.
  • the surface of the base film is contaminated, it is not preferable because it causes problems in the lamination of the adhesive layer and the printing process. Therefore, it is important that the surface of the base film after peeling off the reinforcing film or the reinforcing film with a slight pressure-sensitive adhesive layer is not contaminated by the residue derived from the reinforcing film.
  • any known plastic film can be used, but an inexpensive polyester film is preferable.
  • the pressure-sensitive adhesive constituting the fine pressure-sensitive adhesive layer includes a fine particle comprising an acrylic resin, a silicone resin or a rubber resin, and a crosslinking agent. Adhesives can be mentioned.
  • a heat-resistant slightly adhesive for example, an adhesive containing a high molecular weight acrylic resin having a weight average molecular weight of 450,000 to 1,500,000. ,.
  • the slight pressure-sensitive adhesive layer can be formed by using the same coating apparatus as in the case of the curable conductive adhesive layer (I), but not necessarily in the case of the curable conductive adhesive layer (I).
  • the coating method does not have to be the same for the slightly adhesive layer.
  • the curable conductive adhesive layer (I) of the electromagnetic wave shielding adhesive film of the present invention is preferably provided with a protective film for surface protection.
  • a protective film a polyester film, a polyolefin film, paper or the like can be used.
  • the protective film has a re-peelable pressure-sensitive adhesive layer to improve adhesion to the curable conductive adhesive layer (I). You may stick through.
  • the electromagnetic wave shielding adhesive film of the present invention includes, for example, a step of laminating a reinforcing film [1] on one surface of a base film [2] via a slightly adhesive layer [4] as shown in FIG. ,as well as
  • the electromagnetic wave shielding adhesive film of the present invention is more specifically shown, for example, as shown in FIG.
  • It can be produced by a method including a step of superposing a protective film [3] on the curable conductive adhesive layer (I).
  • the electromagnetic wave shielding adhesive film of the present invention is provided with a slightly adhesive layer [4] on one surface of a reinforcing film [1] as shown in FIG. 3, for example.
  • a step of superposing the base material film [2] on [4] is provided with a slightly adhesive layer [4] on one surface of a reinforcing film [1] as shown in FIG. 3, for example.
  • the base film is a film-like curable resin composition (III) containing a polyester resin (C) and an epoxy resin (D).
  • III film-like curable resin composition
  • D epoxy resin
  • a curable resin composition containing a carboxyl group-containing polyester resin (C) and an epoxy resin (D) having two or more epoxy groups is applied on one surface of the reinforcing film [1].
  • It can be produced by a method including a step of superposing a protective film [3] on the curable conductive adhesive layer (I).
  • a curable resin composition containing a carboxyl group-containing polyester resin (C) and an epoxy resin (D) having two or more epoxy groups is applied on one surface of the reinforcing film [1].
  • the film-like curable resin composition ()) layer in which the reinforcing film [1] is laminated on the curable conductive adhesive layer (I) is used as the film-like curable resin composition (III). Layering process so that the curable conductive adhesive layer (I) is in contact with the layer
  • a pressure of 1 to 3 MPa was applied after being applied to the adherend. It is preferably 10 to 50 minutes at ⁇ 170 ° C.
  • the method for producing an electromagnetic wave shielding adhesive film of the present invention is a thin and excellent base film with excellent bending resistance by laminating a protective film on the base film at an early stage of the manufacturing process. Therefore, it is possible to stably supply an electromagnetic wave shielding adhesive film having excellent performance.
  • a curable conductive adhesive layer (I) A curable conductive adhesive layer (I), and
  • the protective film [3] is peeled off from the electromagnetic wave shielding adhesive film containing the layers sequentially laminated, and the exposed curable conductive adhesive layer (I) is laminated and adhered to the surface of the adherend [5].
  • a mode in which the reinforcing film [1] is peeled off together with the slightly adhesive layer [4] after thermocompression bonding and curing the curable conductive adhesive layer (I) to form a conductive cured adhesive layer (II). Can be used.
  • the protective film [3] is peeled off from the electromagnetic wave shielding adhesive film containing the layers sequentially laminated, and the exposed curable conductive adhesive layer (I) is laminated and adhered to the surface of the adherend [5].
  • the film-like curable resin composition (III) layer and the curable conductive adhesive layer (I) are cured by thermocompression bonding, and the film-like curable resin composition (IV) layer and the conductive film are respectively cured.
  • the reinforcing film [1] can be used in a mode of peeling off.
  • an adherend to which the electromagnetic wave shielding adhesive film according to the present invention can be attached for example, a flexible printed wiring board that is repeatedly bent can be given as a representative example.
  • adherends include a rigid printed wiring board.
  • Mn the number average molecular weight obtained from adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol
  • 390 parts, dimethylolbutanoic acid 16 parts, 158 parts of isophorone diisocyanate and 40 parts of toluene were charged and reacted at 90 ° C. for 3 hours under a nitrogen atmosphere.
  • 300 parts of toluene was added to obtain a urethane polymer solution having an isocyanate group at the terminal.
  • Diol obtained from adipic acid and 3-methyl-1,5-pentanediol (Mn 10 02) 352 parts, dimethylol in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube
  • a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube Thirty-two parts of butanoic acid, 176 parts of isophorone diisocyanate, and 40 parts of toluene were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere.
  • 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal.
  • 981) 432 parts, isophorone diisocyanate 13 7 parts, and toluene 40 parts were charged and reacted at 90 ° C for 3 hours in a nitrogen atmosphere.
  • 300 parts of toluene was added to the resulting product to obtain a urethane prepolymer solution having an isocyanate group at the terminal.
  • the number average molecular weight of the obtained polyester resin was 18000, and the glass transition temperature was 27 ° C.
  • the acid value of the resin of the resin solution (C-1) was 14 mg KOHZg, the number average molecular weight was 24000, and the glass transition temperature was 29 ° C.
  • the acid value of the resin in the resin solution (C-2) was 30 mg KOHZg, the number average molecular weight was 22000, and the glass transition temperature was 28 ° C.
  • the acid value of the resin in the resin solution (C-3) was 41 mg KOHZg, the number average molecular weight was 20000, and the glass transition temperature was 27 ° C.
  • the number average molecular weight of the obtained polyester resin was 19000, and the glass transition temperature was 45 ° C.
  • the acid value of the resin of the resin solution (C-4) was 1 lmgKOHZg, the number average molecular weight was 19000, and the glass transition temperature was 47 ° C.
  • the acid value of the resin of the resin solution (C-5) was 25 mg KOHZg, the number average molecular weight was 19000, and the glass transition temperature was 46 ° C.
  • the acid value of the resin of the resin solution (C-6) was 68 mgKOHZg, the number average molecular weight was 18000, and the glass transition temperature was 45 ° C. [0100] Synthesis Example 7
  • the resulting curable conductive adhesive composition was applied to a thickness of 13 ⁇ m (dry film thickness) using a comma coater and dried to prepare an electromagnetic wave shielding adhesive film.
  • 166 parts of flaky silver powder (“AgXF-301" manufactured by Fukuda Metal Foil Powder Industry) was added and mixed by stirring to obtain a curable conductive adhesive composition. It was.
  • a 13 ⁇ m thickness (dry film thickness) of the curable conductive adhesive composition obtained previously is applied to the base film (polyphenylene sulfide film) surface of the obtained laminate using a comma coater. It was coated and dried to produce an electromagnetic wave shielding adhesive film.
  • Various curable conductive adhesives can be obtained by repeating the operations described in Example 1, except that the types and amounts of polyurethane polyurethane resin solution, epoxy resin and flaky silver powder shown in Table 1 and Table 2 are used.
  • An agent composition was prepared to produce an electromagnetic wave shielding adhesive film.
  • Polyester resin solution (C-1) 250 parts by weight Tetrakis (glycidyloxyphenyl) ethane type epoxy resin (Epicoat 1031 made by Japan Epoxy Resin, Epoxy equivalent 190gZeq) 10 parts by weight Acid ammonium flame retardant (Clariantja) “Exolit AP422” manufactured by Bread)
  • a 50 ⁇ m thick polyethylene terephthalate film with a 50 ⁇ m-thick resin composition added to one surface as a reinforcing film.
  • the surface is coated with a comma coater to a thickness of 20 m (dry film thickness), dried to form a film-like curable resin composition layer, and a reinforcing film and a film-like curable resin composition.
  • a laminate with the product was obtained.
  • Polyester resin solution (C-2) 250 parts by weight, tetrakis (glycidyloxyphenyl) ethane type epoxy resin (Epicoat 1031 made by Japan Epoxy Resin, epoxy equivalent 190gZeq) 20 parts by weight, and polyphosphorus
  • acid ammonium flame retardant (“Exolit AP423J” manufactured by Clariant Japan) was obtained to obtain a solution of the curable resin composition.
  • An electromagnetic shielding adhesive film was prepared.
  • Polyester resin solution (C-3) 250 parts by weight, tetrakis (glycidyloxyphenyl) ethane type epoxy resin (Epicoat 1031 made by Japan Epoxy Resin, epoxy equivalent 190gZeq) 15 parts by weight, and polyphosphorus
  • CBC “C-30” acid ammonium flame retardant
  • Polyester resin solution (C-4) 250 parts by weight Tetrakis (glycidyloxyphenyl) ethane type epoxy resin (Epicoat 1031 made by Japan Epoxy Resin, Epoxy equivalent 190gZeq) 10 parts by weight As described in Example 12, except that 70 parts by weight of an acid ammonium flame retardant (CBC “C-60”) was added to obtain a solution of the curable resin composition. By repeating the operation described above, an electromagnetic wave shielding adhesive film was produced.
  • CBC “C-60” acid ammonium flame retardant
  • An electromagnetic wave shielding adhesive film was prepared by repeating the procedure described in Example 12 except that the oil composition solution was obtained.
  • An electromagnetic wave shielding adhesive film was prepared by repeating the operations described in Example 12 except that the solution of the conductive rosin composition was obtained.
  • a curable conductive adhesive composition can be obtained by repeating the procedure described in Example 1 except that the types and amounts of polyurethane polyurethane resin solution, epoxy resin and flaky silver powder shown in Table 3 are used. And an electromagnetic wave shielding adhesive film was prepared.
  • Carboxyl group-containing tolylbudagen rubber (Zeon Nippon “Nipol 1072J”, combined acrylonitrile content 27.0%, mu-one viscosity 48) 100 parts, bisphenol A type epoxy Mix 200 parts of “Epicoat 828”, 14 parts of finely pulverized dicyandiamide (“Epicure DICY7” manufactured by Japan Epoxy Resin) and 2 parts of imidazole curing accelerator (“Amicure PN-40” manufactured by Ajinomoto Fine Techno) An adhesive resin composition was prepared by dissolving in toluene to a content of 30%.
  • Example 1 By using the obtained curable conductive adhesive composition, the operation described in Example 1 was repeated to produce an electromagnetic wave shielding adhesive film.
  • An electromagnetic wave shielding adhesive film was prepared by repeating the operation described in Example 12 except that 250 parts by weight of the polyester resin solution (C-6) was used.
  • An electromagnetic wave shielding adhesive film was prepared by repeating the operation described in Example 12 except that 250 parts by weight of the polyester resin solution (C-7) was used.
  • DICY Fine powder dicyandiamide (Japan Epoxy Resin “Epicure DICY7J”)
  • PN-40 Imidazole curing accelerator (Ajinomoto Fine Techno “PN-40”)
  • AgXF-301 Flake silver powder ("AgxF-301" manufactured by Fukuda Metal Foil Powder Industry)
  • An electromagnetic wave shielding adhesive film with a width of 1 Omm and a length of 70 mm is prepared.
  • a polyimide film with a thickness of 50 m (“Kapton 200EN” manufactured by Toray 'DuPont ”) is applied to the curable conductive adhesive surface at 150 ° C. 1.
  • Crimpable conductive adhesive with OMPa and 30min conditions The curable film-like resin composition layer as a layer and a base material that was used as needed!
  • the reinforcing film or the reinforcing film with a slight pressure-sensitive adhesive layer was removed, and a T peel peel test was conducted at 23 ° C and a relative humidity of 50% at a bow tensioning speed of 50 mmZmin.
  • the adhesive force between the conductive cured adhesive layer and the polyimide film was measured, and the center value was defined as the polyimide film adhesive strength (NZcm).
  • An electromagnetic wave shielding adhesive film with a width of 10 mm and a length of 60 mm is prepared, and a 50 ⁇ m thick polyimide film (“Kapton 200EN” manufactured by Toray DuPont) is applied to the curable conductive adhesive layer at 150 ° C.
  • the conductive adhesive layer and the curable film-like resin composition layer as a base material used as needed were cured by pressure bonding under conditions of lMPa and 30 min.
  • the reinforcing film or the reinforcing film with a slight pressure-sensitive adhesive layer was removed, and heat treatment was performed in a 180 ° C electric oven for 3 minutes and then in a 280 ° C electric oven for 90 seconds. The appearance of the sample after the heat treatment was visually observed to evaluate the presence or absence of appearance defects such as foaming, floating, and peeling.
  • the sample after heat treatment that is, the sample of the electromagnetic wave shielding adhesive film [6] and polyimide film [7] after heat treatment, is placed on the surface of a horizontal base [8], Measure the length L in Fig. 8, and increase the curl rate from the following formula (1).
  • the evaluation criteria are as shown below.
  • Curling rate is 5% or more and less than 20%
  • a flexible printed wiring board with a separate curable conductive adhesive layer of an electromagnetic wave shielding adhesive film with a width of 6 mm and a length of 120 mm (a circuit pattern with a 12 m thick copper foil force is formed on a 25 m thick polyimide film)
  • pressure is applied to the bar film surface at 150 ° C lMPa and 30 min on the circuit pattern with a 40 m thick cover film with adhesive and laminated on the circuit pattern.
  • a curable conductive adhesive layer and a curable film-like resin composition layer as a base material used as needed / cured were cured.
  • the evaluation criteria are as follows.
  • ⁇ 500 times or more and less than 1000 times
  • An electromagnetic wave shielding adhesive film with a width of 50 mm and a length of 80 mm, and its curability A heat-resistant polyester film that has been peeled off is laminated to the conductive adhesive layer and pressed under the conditions of 150 ° C, lMPa, and 30 minutes, and used as a curable conductive adhesive layer and as required.
  • the curable film-like resin composition layer as the base material was cured. After pressure bonding, the heat-resistant polyester film that had been peeled off was removed to expose the conductive cured adhesive layer.
  • the surface resistivity of the conductive cured adhesive layer was measured using a four-point probe of “Loresta GP” manufactured by Mitsubishi Chemical.
  • the evaluation criteria are as follows.
  • the electromagnetic wave shielding adhesive film according to the present invention is a flexible film that is repeatedly bent. It can be suitably used for applications such as sticking to a printed wiring board or the like to shield electromagnetic noise generated by an electric circuit cover.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne un film adhésif de protection contre les ondes électromagnétiques qui comprend un film de base et une couche adhésive conductrice durcissable (I), où la couche adhésive conductrice durcissable (I) comprend : une résine de polyuréthane-polyurée (A) préparée en faisant réagir un composé polyamino (e) avec un prépolymère d'uréthane (d) ayant un groupe isocyanate à une extrémité et obtenu en faisant réagir un composé diol carboxylé (a), un polyol (b) qui possède une masse moléculaire moyenne en nombre de 500 à 8000 et qui n’est pas un composé diol carboxylé, et un diisocyanate organique (c) ; une résine époxy (B) ayant deux groupes époxy ou plus ; et une charge conductrice.
PCT/JP2006/302825 2005-02-18 2006-02-17 Film adhésif de protection contre les ondes électromagnétiques, procédé de fabrication de celui-ci et procédé de protection d’une partie adhérée contre les ondes électromagnétiques Ceased WO2006088127A1 (fr)

Priority Applications (2)

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JP2007503742A JP4114706B2 (ja) 2005-02-18 2006-02-17 電磁波シールド性接着フィルム及びその製造方法、並びに被着体の電磁波遮蔽方法
KR1020077021259A KR100874302B1 (ko) 2005-02-18 2006-02-17 전자파 차폐성 접착필름, 그 제조방법 및 피착체의 전자파차폐방법

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JP (1) JP4114706B2 (fr)
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JPWO2014010524A1 (ja) * 2012-07-11 2016-06-23 タツタ電線株式会社 硬化性導電性接着剤組成物、電磁波シールドフィルム、導電性接着フィルム、接着方法及び回路基板
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JP2017115152A (ja) * 2017-01-18 2017-06-29 藤森工業株式会社 導電性接着剤層、及びｆｐｃ用電磁波シールド材
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KR100874302B1 (ko) 2008-12-18
CN100584180C (zh) 2010-01-20
JP4114706B2 (ja) 2008-07-09
TWI360386B (en) 2012-03-11

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