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WO2009090997A1 - Curable electromagnetic shielding adhesive film, method for producing the same, use of the same, method for producing electromagnetic shielding article, and electromagnetic shielding article - Google Patents

Curable electromagnetic shielding adhesive film, method for producing the same, use of the same, method for producing electromagnetic shielding article, and electromagnetic shielding article Download PDF

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Publication number
WO2009090997A1
WO2009090997A1 PCT/JP2009/050467 JP2009050467W WO2009090997A1 WO 2009090997 A1 WO2009090997 A1 WO 2009090997A1 JP 2009050467 W JP2009050467 W JP 2009050467W WO 2009090997 A1 WO2009090997 A1 WO 2009090997A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane polyurea
curable
carboxyl group
resin
polyurea resin
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/JP2009/050467
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French (fr)
Japanese (ja)
Inventor
Takahiro Matsuzawa
Hidenobu Kobayashi
Akifumi Kuwabara
Yuji Nishiyama
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
Priority claimed from JP2008114740A external-priority patent/JP2009194353A/en
Priority claimed from JP2008118001A external-priority patent/JP5233392B2/en
Application filed by Toyo Ink Mfg Co Ltd filed Critical Toyo Ink Mfg Co Ltd
Priority to CN2009801022734A priority Critical patent/CN101940080B/en
Publication of WO2009090997A1 publication Critical patent/WO2009090997A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
    • H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
    • 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
    • C08L75/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • 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
    • C09J2475/006—Presence of polyurethane in the substrate

Definitions

  • the present invention relates to a curable electromagnetic wave shielding adhesive film that is suitably used for an application of shielding electromagnetic noise generated from an electric circuit by sticking to a flexible printed wiring board or the like that repeatedly undergoes bending, its manufacturing method, and its
  • the present invention relates to a method of use, a method of manufacturing an electromagnetic shielding material, and an electromagnetic shielding material.
  • the flexible printed wiring board has flexibility, so that it meets the demand for higher performance and downsizing of recent office automation equipment, communication equipment, mobile phones, etc. Widely used to incorporate electronic circuits. With such downsizing and high frequency of electronic circuits, countermeasures against unnecessary electromagnetic noise generated therefrom are becoming more and more important.
  • an electromagnetic wave shielding adhesive film that shields electromagnetic noise generated from an electronic circuit has been attached to a flexible printed wiring board.
  • the electromagnetic wave shielding adhesive film itself is required to have thinness and excellent bending resistance so as not to impair the bending resistance of the bonded flexible printed wiring board as a whole. Therefore, as an electromagnetic wave shielding adhesive film, one having a basic structure in which a conductive layer is provided on a thin base film is widely known.
  • the cover film has a conductive adhesive layer on one side of the cover film and, if necessary, a shield layer made of a metal thin film layer, and the adhesive layer and releasability reinforcement on the other side.
  • a reinforcing shield film in which films are sequentially laminated is known (see Patent Document 1).
  • a shield film having a base film made of a conductive adhesive layer and / or a shield layer having a metal thin film and an aromatic polyamide resin is known (see Patent Document 2).
  • 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. (See Patent Document 3).
  • the adhesive layer of the conventional electromagnetic wave shielding adhesive film includes thermoplastic resins such as polystyrene, vinyl acetate, polyester, polyethylene, polypropylene, polyamide, rubber, and acrylic, and phenolic. Epoxy-based, urethane-based, melamine-based, alkyd-based thermosetting resins have been used. However, none of the conventional adhesive layers have both bending resistance and heat resistance, and the resistance to repeated bending is not perfect for use in flexible printed wiring boards.
  • Patent Document 4 discloses an electromagnetic wave shielding adhesive film comprising an adhesive composition containing a polyurethane polyurea resin having a carboxyl group, an epoxy resin having two or more epoxy groups, and a conductive filler. It is disclosed that it is excellent in bending resistance and heat resistance.
  • the electromagnetic wave shielding adhesive film disclosed in Patent Document 4 includes polyphenylene sulfide (hereinafter also abbreviated as PPS), a polyester resin having a carboxyl group, and an epoxy resin having two or more epoxy groups.
  • PPS polyphenylene sulfide
  • the film which hardened the curable film-like composition formed was used as an insulating base film. In the electromagnetic wave shielding adhesive film using such a base film, it is no longer possible to meet more stringent requirements for flex resistance.
  • the present invention is an electromagnetic wave shielding adhesive film that is suitably used for applications such as affixing to a flexible printed wiring board and shielding electromagnetic noise, and after adhering to a flexible printed wiring board, it has sufficient electromagnetic shielding properties.
  • it has heat resistance that can withstand high temperatures during lead-free solder reflow, and has superior bending resistance than conventional ones, and even when exposed to high temperatures and high humidity [specifically, Pressure Cooker Test (Pressure Cracker)
  • PCT Pressure Cooker Test
  • the present invention is such that, when thermocompression bonding to the adherend, the curable conductive adhesive layer is unlikely to protrude from the adhesion region, and also when thermocompression bonding to a circuit board having a step,
  • An object of the present invention is to provide an electromagnetic wave shielding adhesive film having a sufficient concealing property for the conductive polyurethane polyurea adhesive layer.
  • the reason why the concealability is required is to conceal the conductive polyurethane polyurea adhesive layer, which is a colored layer, from above with the polyurethane polyurea insulating layer.
  • the cured polyurethane polyurea insulating layer that covers the conductive polyurethane polyurea adhesive layer after curing needs to be rich in flexibility, but if it is too flexible before curing or during curing, The polyurethane polyurea insulating layer in the curing process extends excessively, and the conductive polyurethane polyurea adhesive layer is exposed or seen through. Therefore, the present invention provides an electromagnetic wave shielding adhesive film that is sufficiently flexible after curing and has excellent bending resistance, but has sufficient concealing property to the conductive polyurethane-polyurea adhesive layer at the stepped portion at the time of sticking. The purpose is to do.
  • the present invention provides a method for inexpensively and stably producing an electromagnetic wave shielding adhesive film having such excellent performance, a method of using the electromagnetic wave shielding adhesive film, and the electromagnetic wave shielding adhesive film.
  • An object of the present invention is to provide a method for producing an electromagnetic wave shielding material, and an electromagnetic wave shielding material obtained from the electromagnetic wave shielding adhesive film.
  • the first invention is A curable electromagnetic shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),
  • the curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • the curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • the present invention relates to a curable electromagnetic wave shielding adhesive film characterized by containing (D).
  • the second invention is A curable electromagnetic shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulating polyurethane polyurea resin composition layer (II).
  • the curable conductive polyurethane polyurea adhesive layer (I) reacts the diol compound (a1) having a carboxyl group, the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and the organic diisocyanate (a3).
  • the polyurethane polyurea resin (A) and the epoxy resin (B) in a total of 100 parts by weight, the conductive filler: 10 to 700 parts by weight, and the aziridine-based curing agent (E) are added to the polyurethane polyurea resin.
  • the curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • the present invention relates to a curable electromagnetic wave shielding adhesive film characterized by containing (D).
  • the third invention is A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight
  • the curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • the curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to
  • the fourth invention is A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight.
  • the curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • the curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • D urethane prepolymer
  • E aziridin-based curing agent
  • the fifth invention is The curable conductive polyurethane polyurea adhesive layer (I) contains 3 to 200 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A), and the curable insulating polyurethane polyurea resin.
  • the present invention relates to an electromagnetic wave shielding adhesive film.
  • the sixth invention is The peelable film 1 is laminated on the surface of the curable insulating polyurethane polyurea resin composition layer (II) that is not in contact with the curable conductive polyurethane polyurea adhesive layer (I).
  • the present invention relates to a curable electromagnetic wave shielding adhesive film of a fifth invention.
  • the seventh invention The peelable film 2 is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) that is not in contact with the curable insulating polyurethane polyurea resin composition layer (II).
  • the present invention relates to a curable electromagnetic wave shielding adhesive film of a fifth invention.
  • the eighth invention is The peelable film 2 is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) that is not in contact with the curable insulating polyurethane polyurea resin composition layer (II), and is curable.
  • a fifth aspect is characterized in that the peelable film 1 is laminated on the surface of the insulating polyurethane polyurea resin composition layer (II) which is not in contact with the curable conductive polyurethane polyurea adhesive layer (I). It relates to the curable electromagnetic wave shielding adhesive film of the invention.
  • the ninth invention Obtained by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1 And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups.
  • a diol compound (c1) having a carboxyl group a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1
  • a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an
  • a curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of conductive filler is formed with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B).
  • the process of The present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film, comprising a step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II).
  • the tenth invention is Obtained by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1 And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups.
  • a diol compound (c1) having a carboxyl group a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1
  • a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c
  • the eleventh invention is Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2
  • a polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, Forming a curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B).
  • the twelfth invention is Obtained by reacting one surface of the peelable film 1 with a diol compound having a carboxyl group (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • a curable insulating polyurethane polyurea resin composition layer (II) and Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2
  • the thirteenth invention is Obtained by reacting one surface of the peelable film 1 with a diol compound having a carboxyl group (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups
  • a curable insulating polyurethane polyurea resin composition layer (II) On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) Obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5), and an epoxy having two or more epoxy groups.
  • Conductive filler 10 to 700 parts by weight with respect to a total of 100 parts by weight of the resin (B), the polyurethane polyurea resin (A) and the epoxy resin (B), and the aziridine-based curing agent (E), Addition of 1 mol of carboxyl group in polyurethane polyurea resin (A) Forming a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing 0.05 to 4 mol of a dinyl group; as well as, A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I), The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.
  • the fourteenth invention is Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • the fifteenth invention Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine
  • Step gel fraction Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference and, A step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II); And a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight.
  • the sixteenth invention is Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine
  • Conductive filler 10 to 700 parts by weight with respect to a total of 100 parts by weight of the resin (B), the polyurethane polyurea resin (A) and the epoxy resin (B), and the aziridine-based curing agent (E), Addition of 1 mol of carboxyl group in polyurethane polyurea resin (A) Forming a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing 0.05 to 4 mol of a dinyl group; as well as,
  • the present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, comprising a step of superposing a peelable film 2 on the curable conductive polyureurethane / polyurea adhesive layer (I).
  • the seventeenth invention Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (F) having a film-forming ability containing an aziridinyl group in a range of 0.05 to 4
  • a gel fraction of 30 from the curable insulating polyurethane polyurea resin composition A step of forming 90% by weight of a curable insulating polyurethane polyurea resin composition layer (II), and a step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II),
  • the present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight.
  • the eighteenth invention Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine
  • a curable insulating polyurethane polyurea having a film-forming ability containing a curable resin (E) in an amount of 0.05 to 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C).
  • a curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is formed.
  • Process and The present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film, comprising a step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II).
  • the nineteenth invention Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine
  • a curable insulating polyurethane polyurea having a film-forming ability containing a curable resin (E) in an amount of 0.05 to 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C).
  • a diol compound (a1) having a carboxyl group a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyan
  • the 20th invention is Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • a curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is formed.
  • a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (E) containing a aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C) and having a film-forming ability.
  • a gel fraction of 30 from a curable insulating polyurethane polyurea resin composition Step of Forming 90 wt% of the curable insulating polyurethane polyurea resin composition layer (II) and, A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II); The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.
  • the twenty-first invention is The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, heated, and cured.
  • An eighth curable electromagnetic wave shield characterized by peeling the peelable film 1 after curing the conductive conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II)
  • the present invention relates to a method for using an adhesive film.
  • the twenty-second invention The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, and the peelable film 1 is attached.
  • An eighth curable electromagnetic wave shielding property characterized by curing after peeling and heating to cure the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II)
  • the present invention relates to a method for using an adhesive film.
  • the twenty-third invention The exposed curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the sixth invention is superimposed on an adherend and heated to adhere the curable conductive polyurethane polyurea adhesive. It is related with the manufacturing method of the electromagnetic wave shielding material characterized by peeling the peelable film 1 after hardening agent layer (I) and curable insulating polyurethane polyurea resin composition layer (II).
  • the twenty-fourth invention is The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the seventh invention is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superimposed on the adherend, heated, and cured.
  • the present invention relates to a method for producing an electromagnetic wave shielding material, comprising curing a conductive conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II).
  • the twenty-fifth invention The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, heated, and cured. It is related with the manufacturing method of the electromagnetic wave shielding material characterized by peeling the peelable film 1 after hardening conductive electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II).
  • the twenty-sixth invention The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, and the peelable film 1 is attached. It is related with the manufacturing method of the electromagnetic wave shielding material characterized by heating after peeling and hardening the said curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II).
  • the 27th invention is The present invention relates to an electromagnetic wave shielding material obtained by the production method according to any of the 23rd to 26th inventions.
  • the curable conductive polyurethane polyurea adhesive layer (I) preferably contains 3 to 200 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A). Even if the conductive adhesive layer (I) having such a composition is thin, the conductive adhesive layer (I) exhibits a sufficient cushioning property at the time of heating and pressure bonding and flows into the insulating film removal portion on the ground circuit. In addition, it has heat resistance enough to withstand lead-free solder reflow by heating and pressure bonding. Furthermore, it has excellent bending resistance, and does not impair the bending resistance of the entire circuit board when pasted on a flexible printed wiring board.
  • the curable electromagnetic wave shielding adhesive film of the present invention has excellent moisture and heat resistance by having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II).
  • bending resistance can be expressed.
  • after being attached to a flexible printed circuit board in addition to sufficient electromagnetic shielding properties, it has heat resistance that can withstand high temperatures during lead-free solder reflow, and is superior in bending resistance to high temperatures and humidity. Even when exposed to the bottom (specifically, even after undergoing a pressure cooker test (hereinafter referred to as PCT)), the conductivity of the conductive polyurethane polyurea adhesive layer (I) does not decrease.
  • PCT pressure cooker test
  • the curable electromagnetic wave shielding adhesive film of the present invention has a curable conductive polyurethane polyurea adhesive layer (I) in a semi-cured state (gel fraction is 30 to 90% by weight).
  • the adhesive does not protrude excessively when thermocompression-bonded to the film, and after curing, a flexible and excellent bending property can be obtained.
  • the curable electromagnetic wave shielding adhesive film of the present invention has a curable insulating polyurethane polyurea resin composition layer (II) in a semi-cured state (gel fraction is 30 to 90% by weight). Excessive elongation during wearing and curing can be suppressed.
  • FIG. 1A is a schematic plan view of a flexible printed wiring board, in which circuits 2A and 2B are formed on a polyimide film 1, and a cover film having a through hole 4 so that a part of the circuit 2A is exposed. 3 are stacked.
  • FIG. 1B is a cross-sectional view taken along the line D-D ′ in FIG.
  • FIG. 1C is a cross-sectional view taken along the line C-C ′ in FIG.
  • FIG. 1 (4) shows a curable electromagnetic wave shielding adhesive property so that parts of the circuits 2A and 2B are exposed on the cover film 3 and the circuit 2B shown in FIGS.
  • FIG. 3 is a schematic plan view of a state in which a film 5 is stacked, pressed and cured.
  • FIG. 1 (5) is a cross-sectional view taken along the line D-D 'of FIG. 1 (4).
  • FIG. 1 (6) is a cross-sectional view taken along the line C-C ′ of FIG. 1 (4).
  • the curable electromagnetic wave shielding adhesive film of the present invention can include four embodiments as a film configuration.
  • the mode (1) of the curable electromagnetic wave shielding adhesive film (hereinafter also referred to as the film mode (1)) includes a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition. It has a layer (II).
  • the curable conductive polyurethane polyurea adhesive layer (I) comprises a polyurethane polyurea resin (A), an epoxy resin (B) having two or more epoxy groups, the polyurethane polyurea resin (A), and the epoxy resin (B And 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight in total.
  • the polyurethane polyurea resin (A) is produced by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with a polyamino compound (a5).
  • the urethane prepolymer (a4) reacts a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). To be generated.
  • the adhesive resin composition containing the polyurethane polyurea resin (A) and the epoxy resin (B) disperses the conductive filler well, exhibits a sufficient adhesive force even when the conductive filler is contained, and further shields against electromagnetic waves. Extrusion of the adhesive layer during thermocompression bonding between the adhesive film and the adherend is small. Therefore, excellent heat resistance and bending resistance that can withstand lead-free solder reflow can be obtained.
  • the polyurethane polyurea resin (A) contained in the curable conductive polyurethaneurea adhesive layer (I) comprises a diol compound having a carboxyl group (a1) and a polyol having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound. It is obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting (a2) and the organic diisocyanate (a3) with a polyamino compound (a5).
  • diol compound (a1) having a carboxyl group examples include dimethylol alkanoic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, or dimethylolpentanoic acid (wherein alkanoic acid has 2 to 8 carbon atoms). And a dihydroxy aromatic carboxylic acid such as dihydroxy succinic acid or dihydroxy benzoic acid (wherein the aromatic carboxylic acid preferably has 7 to 11 carbon atoms). Among them, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable from the viewpoint of reactivity and solubility.
  • the diol compound (a1) having a carboxyl group may be used alone or in combination of two or more.
  • the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound is generally known as a polyol component constituting the polyurethane resin, and is a polyol other than the diol compound (a1) having a carboxyl group.
  • the number average molecular weight (Mn) of the polyol (a2) is appropriately determined in consideration of the heat resistance, adhesive strength, and / or solubility of the resulting polyurethane polyurea resin (A), and preferably 1000 to 5000. It is.
  • Mn is less than 500, the number of urethane bonds in the resulting polyurethane polyurea resin (A) increases too much, and the flexibility of the polymer skeleton tends to decrease and the adhesion to the flexible printed wiring board tends to decrease.
  • Mn exceeds 8000, the number of carboxyl groups derived from the diol compound (a1) in the polyurethane polyurea resin (A) decreases. As a result, since the reaction point with the epoxy resin is reduced, the solder reflow resistance of the obtained conductive cured adhesive layer tends to be lowered.
  • polyether polyols As the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols and the like can be used.
  • polyether polyols 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, Saturated or unsaturated low-molecular diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimer diol, adipic acid, phthalic acid, Reaction with dicarboxylic acids such as 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 their anhydrides Poly
  • polycarbonate polyols include: 1) A reaction product of glycol or bisphenol and a carbonate ester, or 2) a reaction product obtained by reacting glycol or bisphenol with phosgene in the presence of an alkali can be used.
  • the glycol used for the preparation of the reaction product 1) or 2) 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'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octan
  • bisphenol used for preparation of the reaction product of said 1) or 2) for example, bisphenols, such as bisphenol A and bisphenol F, and alkylene oxides, such as ethylene oxide or propylene oxide, are added to these bisphenols. And the like.
  • the carbonic acid ester used for the preparation of the reaction product 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or propylene carbonate.
  • polyols exemplified as the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound may be used alone or in combination of two or more. Further, within the range in which the performance of the resulting polyurethane polyurea resin (A) is not lost, a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and When reacting with the organic diisocyanate (a3), low molecular diols other than the carboxyl group-containing diol compound (that is, diols having a number average molecular weight of less than 500) may be used in combination.
  • low molecular diols examples include various low molecular diols used for the production of polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound.
  • the diol compound (a1) having a carboxyl group and the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound are other than the carboxyl group-containing diol compound.
  • the diol compound (a1) having a carboxyl group is preferably used in a ratio of 0.1 mol to 4.0 mol with respect to 1 mol of the polyol (a2) having a number average molecular weight of 500 to 8000, from 0.2 mol to More preferably, it is used at a ratio of 3.0 moles.
  • the amount of the carboxyl group-containing diol compound (a1) used relative to 1 mol of the polyol (a2) is less than 0.1 mol, the number of carboxyl groups capable of crosslinking with the epoxy resin (B) decreases, and the solder reflow resistance tends to decrease. It is in. On the other hand, when the amount is more than 4.0 mol, the adhesiveness tends to decrease.
  • organic diisocyanate (a3) aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable.
  • aromatic diisocyanate examples include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like.
  • aliphatic diisocyanate examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or lysine diisocyanate.
  • alicyclic diisocyanate examples include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and the like.
  • the urethane prepolymer (a4) having an isocyanate group at the end includes a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). It is obtained by reacting.
  • the conditions for synthesizing the urethane prepolymer (a4) having an isocyanate group at the terminal are not particularly limited except that the isocyanate group becomes excessive, but the equivalent ratio of isocyanate group / hydroxyl group is 1.2 / 1.
  • a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) Is preferably reacted.
  • the reaction temperature is usually from room temperature to 120 ° C., but is preferably from 60 to 100 ° C. from the viewpoint of production time and side reaction control.
  • the polyurethane polyurea resin (A) is obtained by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5).
  • the polyamino compound (a5) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or isophoronediamine, dicyclohexylmethane-4,4′-diamine, 2- (2-aminoethylamino) ethanol, Amines having a hydroxyl group such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, or di-2-hydroxypropylethylenediamine can also be used. Of these, isophoronediamine is preferably used.
  • a reaction terminator When synthesizing the polyurethane polyurea resin (A) by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), a reaction terminator can be used in combination.
  • a reaction terminator dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.
  • the conditions for reacting the urethane prepolymer (a4) having an isocyanate group at the terminal, the polyamino compound (a5) and, if necessary, the reaction terminator are not particularly limited, but the isocyanate group possessed by the urethane prepolymer (a4)
  • the total equivalent ratio of the polyamino compound (a5) and the amino groups in the reaction terminator is preferably in the range of 0.5 to 1.3. When the equivalent ratio is less than 0.5, the solder reflow resistance tends to be insufficient, and when it exceeds 1.3, the polyamino compound (a5) and / or the reaction terminator remain unreacted. , The odor tends to remain.
  • Solvents used in the synthesis of the polyurethane polyurea resin (A) include aromatic solvents such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, isopropanol, and n-butanol, acetone, methyl ethyl ketone, or Examples include ketone solvents such as methyl isobutyl ketone, and ester solvents such as ethyl acetate or butyl acetate. These solvents can be used alone or in combination of two or more.
  • the weight average molecular weight of the resulting polyurethane polyurea resin (A) is preferably in the range of 5000 to 100,000.
  • the polyurethane polyurea resin (A) preferably has an acid value of 3 to 25 mgKOH / g, more preferably 7 to 20 mgKOH / g. Although it can be used outside the above numerical range, it may be difficult to achieve both heat resistance and flexibility.
  • the epoxy resin (B) contained in the curable conductive polyurethane urea adhesive layer (I) is a resin having two or more epoxy groups, and may be liquid or solid.
  • the epoxy resin (B) bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, terpene type epoxy resin, tris (glycidyl) Glycidyl ether type epoxy resin such as oxyphenyl) methane or tetrakis (glycidyloxyphenyl) ethane, Glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane, Tetrabromobisphenol A type epoxy resin, Cresol novolak type epoxy resin, Phenol novolak type Examples thereof include an epoxy resin, an ⁇ -naphthol novolak type epoxy resin, and a brominated phenol
  • epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a tetrakis (glycidyloxyphenyl) ethane type epoxy resin from the viewpoint of high adhesion and heat resistance.
  • the epoxy resin (B) preferably has an epoxy equivalent of 100 to 1500 g / eq, more preferably 150 to 700 g / eq. Although it can be used outside the numerical range, it may be difficult to achieve both heat resistance and flexibility.
  • the blending ratio of the epoxy resin, (B), and polyurethane polyurea resin (A) is 100 parts by weight of the polyurethane polyurea resin (A).
  • the epoxy resin (B) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight.
  • the amount of the epoxy resin (B) is less than 3 parts by weight relative to 100 parts by weight of the polyurethane polyurea resin (A)
  • the solder reflow resistance tends to be lowered.
  • the amount of the epoxy resin (B) is more than 200 parts by weight, the adhesiveness tends to decrease.
  • the curable conductive polyurethane polyurea adhesive layer (I) does not impair the performance such as heat resistance and flex resistance.
  • a phenol resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.
  • the conductive filler contained in the curable conductive polyurethane polyurea adhesive layer imparts conductivity to the adhesive layer, and as the conductive filler, a metal filler, a carbon filler, or a mixture thereof is used. It is done.
  • the metal filler include metal powder such as silver, copper, or nickel, alloy powder such as solder, copper powder plated with silver, or glass fiber or carbon filler plated with metal.
  • a silver filler having a high electrical conductivity is preferable, and a silver filler having a specific surface area of 0.5 to 2.5 m 2 / g that facilitates contact between the fillers is particularly preferable.
  • examples of the shape of the conductive filler include a spherical shape, a flake shape, a dendritic shape, and a fibrous shape.
  • the content of the conductive filler in the curable conductive polyurethane polyurea adhesive layer (I) varies depending on the required degree of electromagnetic shielding effect, but the total weight of the polyurethane polyurea resin (A) and the epoxy resin (B) is 100 weight.
  • the conductive filler is 10 to 700 parts by weight, preferably 50 to 500 parts by weight, based on parts. When content of an electroconductive filler is less than 10 weight part, electroconductive fillers do not fully contact and high electroconductivity is not acquired. Therefore, the electromagnetic wave shielding effect tends to be insufficient.
  • the surface resistance value of the curable conductive polyurethane polyurea adhesive layer does not decrease, the conductivity reaches a saturated state, and the curable conductive polyurethane polyurea
  • the amount of the conductive filler in the adhesive layer becomes excessive, and the adhesion and adhesive force of the curable conductive polyurethane polyurea adhesive layer (I) to the base film are lowered.
  • the adhesive force of the adhesive layer (I) is preferably an adhesive force of 1 N / cm or more with respect to the polyimide film. Although it can be used even if it is less than 1 N / cm, there is a possibility that adhesion to the adherend is insufficient.
  • the curable conductive polyurethane polyurea adhesive layer (I) curing is promoted for the purpose of accelerating the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) or the reaction of the epoxy resin (B) alone.
  • An agent and / or a curing agent can be contained.
  • the curing accelerator for the epoxy resin (B) tertiary amine compounds, phosphine compounds, imidazole compounds and the like can be used, and as the curing agent, dicyandiamide, carboxylic acid hydrazide, acid anhydrides and the like can be used.
  • tertiary amine compounds include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, or 1,5-diazabicyclo (4.3.0) nonene- 5 etc. are mentioned.
  • phosphine compound include triphenylphosphine or tributylphosphine.
  • imidazole compound include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenylimidazole.
  • latent curing accelerators with improved storage stability such as a type in which an imidazole compound and an epoxy resin are reacted to insolubilize in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule can be mentioned.
  • Preferred curing accelerators are preferred.
  • Examples of the carboxylic acid hydrazide as the curing agent include succinic acid hydrazide and adipic acid hydrazide.
  • Examples of the acid anhydride include hexahydrophthalic anhydride, trimellitic anhydride, and the like.
  • the amount used is a total (including the case where only one of the curing accelerator or the curing agent is used), and epoxy.
  • the amount is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin (B).
  • the curable conductive polyurethane polyurea adhesive layer has a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a range that does not deteriorate conductivity, adhesiveness, and / or solder reflow resistance.
  • the curable insulating polyurethane polyurea resin composition layer (II) used in the present invention plays a role of giving mechanical strength to the curable electromagnetic wave shielding adhesive film. That is, it has a function as a substrate or carrier even in an uncured state (before curing), and hits the substrate film in Patent Document 4, for example.
  • the curable insulating polyurethane polyurea resin composition layer (II) contains a polyurethane polyurea resin (C) and an epoxy resin (D) having two or more epoxy groups.
  • the polyurethane polyurea resin (C) is produced by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5).
  • the urethane prepolymer (c4) reacts a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). To be generated.
  • Adhesive resin composition layer (II) containing polyurethane polyurea resin (C) and epoxy resin (D) has less exudation of the adhesive layer during thermocompression bonding and has excellent heat resistance that can withstand lead-free solder reflow In addition, bending resistance can be obtained.
  • the polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) is the same as the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I). Can be mentioned.
  • the epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (B) having two or more epoxy groups.
  • the blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) with respect to 100 parts by weight of the polyurethane polyurea resin (C).
  • the epoxy resin (D) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight.
  • the curable insulating polyurethane polyurea resin composition layer (II) has a phenol content within a range that does not impair the performance such as heat resistance and flex resistance.
  • a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.
  • curing agent can be contained in order to accelerate
  • This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
  • the curable insulating polyurethane polyurea resin composition layer (II) as in the case of the curable conductive polyurethane polyurea adhesive layer (I), a range in which the adhesion and / or solder reflow resistance is not deteriorated.
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) except for the presence or absence of a conductive filler can consist of polyurethane polyurea resin compositions of the same composition, or can consist of polyurethane polyurea resin compositions of different compositions.
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in an uncured (before curing) solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.
  • the embodiment (2) of the curable electromagnetic wave shielding adhesive film in the present invention (hereinafter also referred to as the film embodiment (2)) will be described.
  • the mode (2) of the film has a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine-based curing agent (E) and a curable insulating polyurethane polyurea resin composition layer (II).
  • the adhesive may be excessively protruded from the sticking area when it is heat-bonded to the adherend while maintaining the effect that it is flexible and excellent in bending characteristics after curing and the conductivity is not lowered even after PCT. Shows the additional effect of not.
  • the film mode (2) includes a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulating polyurethane polyurea resin composition layer (II). Is a curable electromagnetic wave shielding adhesive film.
  • the curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight comprises a diol compound having a carboxyl group (a1) and a polyol having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound ( polyurethane polyurea resin (A) obtained by reacting urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting a2) and organic diisocyanate (a3) with polyamino compound (a5), and two 10 to 700 parts by weight of a conductive filler with respect to a total of 100 parts by weight of the epoxy resin (B) having the above epoxy group, the polyurethane polyurea resin (A) and the epoxy resin (B), and an aziridine-based curing Agent (E) is a carboxyl group in the polyurethane polyurea resin (A). Mol, those containing in a range of from 0.05 to 4 moles of an azirid
  • Examples of the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I) include those similar to the polyurethane polyurea resin (A) described in the embodiment (1) of the film. Moreover, about the epoxy resin (B) which has 2 or more epoxy groups, the thing similar to the epoxy resin (B) which has 2 or more epoxy groups demonstrated in the aspect (1) of the film can be mentioned. Further, the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
  • the amount of the epoxy resin (B) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the resin (A).
  • the aziridine-based curing agent (E) used for the curable conductive polyurethane polyurea adhesive layer (I) is preferably a compound having two or more aziridinyl groups. Specifically, trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetramethylolmethane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1 -Aziridinecarboxamide), or N, N′-hexamethylene-1,6-bis (1-aziridinecarboxyamide).
  • the aziridine-based curing agent (E) By using the aziridine-based curing agent (E), by utilizing the high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (A), both are reacted without requiring special aging. It can be in a cured state. That is, by reacting both, the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is set to 30 to 90% by weight, so that the curable conductive adhesive layer protrudes from the sticking region during thermocompression bonding. Can be reduced.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is less than 30% by weight, that is, when most of the polyurethane urea resin (A) remains unreacted, Almost no reduction in overhang can be expected.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, the polyurethane urea resin (A) is mostly composed of the aziridine-based curing agent (E) before the thermocompression bonding step. Since it has already reacted and cured, it becomes difficult to ensure adhesion with the adherend.
  • a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight 0.05 mol of aziridinyl groups per mol of carboxyl groups in the polyurethane polyurea resin (A). It is important to contain the aziridine curing agent (E) in the range of ⁇ 4 mol, preferably in the range of 0.2 to 2 mol, and in the range of 0.4 to 1 mol. More preferred.
  • the aziridinyl group of the aziridine-based curing agent (E) is less than 0.05 mol times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (A), it effectively reduces the protrusion of the adhesive during the thermocompression bonding process.
  • the curable conductive polyurethane polyurea adhesive layer (I) is obtained, the curing / crosslinking of the polyurethane polyurea resin (A) does not proceed.
  • the amount of aziridinyl group is more than 4 moles relative to 1 mole of carboxyl group, the reaction / curing of the polyurethane polyurea resin (A) proceeds excessively.
  • the adhesive layer (I) cannot sufficiently wet the adherend, and the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) cannot be expected, and adhesion to the adherend cannot be ensured.
  • the “gel fraction” as used in the present invention can be determined as follows. A 100-mesh wire mesh is cut into a width of 30 mm and a length of 100 mm, and the weight (W1) of the wire mesh is measured. Subsequently, the peelable film 2 is removed from the curable conductive polyurethane polyurea adhesive layer (I) formed on the peelable film 2, and a curable conductive polyurethane polyurea adhesive layer (I having a width of 10 mm and a length of 80 mm). ) Is wrapped with the above-mentioned wire mesh to make a test piece, and the weight (W2) of the test piece is measured.
  • the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film aspect (2) the curable conductive polyurethane polyurea adhesive layer (I) of the film aspect (1)
  • 1 such as phenol resin, silicone resin, urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, as long as the performance such as heat resistance and flex resistance is not impaired. Seeds or more can be included.
  • curing agent can be contained in order to accelerate
  • the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film aspect (2) includes the curable conductive polyurethane polyurea adhesive layer (I) of the film aspect (1).
  • the curable insulating polyurethane polyurea resin composition layer (II) comprises a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • the polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) is the same as the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I). Can be mentioned.
  • the epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (B) having two or more epoxy groups.
  • the blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) with respect to 100 parts by weight of the polyurethane polyurea resin (C).
  • the epoxy resin (D) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight.
  • the curable insulating polyurethane polyurea resin composition layer (II) has a phenol content within a range that does not impair the performance such as heat resistance and flex resistance.
  • a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.
  • curing agent can be contained in order to accelerate
  • the curable insulating polyurethane polyurea resin composition layer (II) has a silane content within a range that does not deteriorate the adhesion and solder reflow resistance, as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
  • One or more coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. may be added. .
  • the mode (2) of the film has a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine-based curing agent (E) and a curable insulating polyurethane polyurea resin composition layer (II).
  • a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine-based curing agent (E) and a curable insulating polyurethane polyurea resin composition layer (II).
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) include a conductive filler and an aziridine-based curing agent. Except for the presence or absence of (E), it can consist of a polyurethane polyurea resin composition of the same composition, or it can consist of a polyurethane polyurea resin composition of a different composition.
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in an uncured (before curing) solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.
  • the aspect (3) of the curable electromagnetic wave shielding adhesive film (also referred to as the film aspect (3)) will be described. Specifically, it has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II), and the gel fraction as a whole is 30 to 90% by weight.
  • a curable electromagnetic wave shielding adhesive film has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II), and the gel fraction as a whole is 30 to 90% by weight.
  • the curable conductive polyurethane polyurea adhesive layer (I) reacts a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • Examples of the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I) include those similar to the polyurethane polyurea resin (A) described in the film embodiment (1).
  • the epoxy resin (B) having two or more epoxy groups may be the same as the epoxy resin (B) having two or more epoxy groups described in the embodiment (1) of the film.
  • the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
  • the amount of the epoxy resin (B) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polyurea resin (A).
  • curing agent (E) demonstrated in the aspect (2) of the film can be used.
  • the aziridine-based curing agent (E) the high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (A) is utilized, and both are reacted without requiring special aging. It can be made to be semi-cured. That is, by reacting both, the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is set to 30 to 90% by weight, so that the curable conductive adhesive layer protrudes from the adhesion region at the time of thermocompression bonding. Can be reduced.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.
  • the gel fraction layer (I) of the curable conductive polyurethane polyurea adhesive is less than 30% by weight, that is, when most of the polyurethane urea resin (A) remains unreacted, the adhesive protrudes in the thermocompression bonding process. Almost no reduction is expected.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, the polyurethane urea resin (A) is mostly composed of the aziridine-based curing agent (E) before the thermocompression bonding step. Since it has already reacted and cured, it becomes difficult to ensure adhesion with the adherend.
  • a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight 0.05 mol of aziridinyl groups per mol of carboxyl groups in the polyurethane polyurea resin (A). It is important to contain the aziridine curing agent (E) in the range of ⁇ 4 mol, preferably in the range of 0.2 to 2 mol, and in the range of 0.4 to 1 mol. More preferred.
  • the aziridinyl group of the aziridine-based curing agent (E) is less than 0.05 mol times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (A), it effectively reduces the protrusion of the adhesive during the thermocompression bonding process.
  • the curable conductive polyurethane polyurea adhesive layer is obtained, curing and crosslinking of the polyurethane polyurea resin (A) do not proceed.
  • the aziridinyl group is more than 4 moles per mole of carboxyl groups, the reaction and curing of the polyurethane polyurea resin (A) proceeds excessively.
  • the adhesive layer cannot sufficiently wet the adherend, the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) cannot be expected, and the adhesion to the adherend cannot be ensured.
  • the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film embodiment (3) the curable conductive polyurethane polyurea adhesive layer (I) of the film embodiment (1)
  • 1 such as phenol resin, silicone resin, urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, as long as the performance such as heat resistance and flex resistance is not impaired. Seeds or more can be included.
  • curing agent can be contained in order to accelerate
  • the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film aspect (3) includes the curable conductive polyurethane polyurea adhesive layer (I) of the film aspect (1).
  • the curable insulating polyurethane polyurea resin composition layer (II) gives the curable electromagnetic wave shielding adhesive film mechanical strength at the time of sticking and curing. Take a role. That is, it has a function as a substrate or carrier even in an uncured state (before curing), and hits the substrate film in Patent Document 4, for example.
  • the curable insulating polyurethane polyurea resin composition layer (II) comprises a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3).
  • Polyurethane polyurea resin (C) obtained by reacting urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reaction with polyamino compound (c5), and epoxy resin having two or more epoxy groups ( D) and an aziridin-based curing agent (F) having a film-forming ability, containing aziridinyl groups in a range of 0.05 to 4 mol with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C). It is formed from an insulating polyurethane polyurea resin composition.
  • curing agent can be contained in order to accelerate
  • This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
  • the curable insulating polyurethane polyurea resin composition layer (II) as in the case of the curable conductive polyurethane polyurea adhesive layer (I), a range in which the adhesion and / or solder reflow resistance is not deteriorated.
  • the aziridine-based curing agent (F) is based on 1 mol of carboxyl groups in the polyurethane polyurea resin (C).
  • the aziridinyl group is preferably contained in the range of 0.2 to 2 mol, and more preferably in the range of 0.4 to 1 mol.
  • the aziridinyl group of the aziridine-based curing agent (F) is less than 0.05 mol times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C), most of the carboxylic acid in the polyurethane polyurea resin is unreacted.
  • the curable insulating polyurethane polyurea resin composition layer (II) is excessively stretched when heated and pasted to a circuit board, the mechanical strength is lowered, and the curable conductive polyurethane polyurea adhesive at the stepped portion There is a risk of causing a defect such as lack of concealment of the layer (I).
  • the amount of aziridinyl group is more than 4 mol with respect to 1 mol of carboxyl group, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed, and a curable electromagnetic shielding adhesive film is obtained.
  • curable insulating polyurethane polyurea resin composition layer (II) and peelable film 1 Adhesiveness between curable insulating polyurethane polyurea resin composition layer (II) and peelable film 1, and curable insulating polyurethane polyurea resin composition layer (II) and curable conductive polyurethane polyurea adhesive There is a possibility that the adhesion with the layer (I) may be lowered.
  • the polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) may be the same as the polyurethane polyurea resin (A) described in the film embodiment (1).
  • the epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (A) having two or more epoxy groups described in the embodiment (1) of the film.
  • the blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
  • the epoxy resin (D) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight.
  • the curable insulating polyurethane polyurea resin composition layer (II) is phenolic as long as the performance such as heat resistance and flex resistance is not impaired.
  • a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.
  • curing agent can be contained in order to accelerate
  • the curable insulating polyurethane polyurea resin composition layer (II) has a silane content within a range that does not deteriorate the adhesion and solder reflow resistance, as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
  • One or more coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. may be added. .
  • the film mode (3) has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) as constituent layers.
  • the gel fraction of the curable electromagnetic wave shielding adhesive film is 30 to 90% by weight, preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.
  • Such a curable electromagnetic wave shielding adhesive film comprises a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulation having a gel fraction of 30 to 90% by weight.
  • the constituent polyurethane polyurea resin composition layer (II) is preferably a constituent layer, and the gel fraction of each layer is preferably 50 to 85% by weight, more preferably 60 to 80% by weight. .
  • the aziridine-based curing agent (E) is used, and the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is 30 to 90% by weight.
  • the adhesive is not excessively protruded when heat-bonded to the adherend. The effect of can be obtained.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is less than 30% by weight, that is, when most of the polyurethane urea resin (A) is left unreacted, the protrusion of the adhesive in the thermocompression bonding process is reduced.
  • the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, the polyurethane urea resin (A) is mostly composed of the aziridine-based curing agent (E) before the thermocompression bonding step. Since it has already reacted and cured, it becomes difficult to ensure adhesion with the adherend.
  • the aziridine-based curing agent (F) is used, and the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is set to 30 to 90% by weight. Accordingly, excessive elongation of the curable insulating polyurethane polyurea resin composition layer when the curable electromagnetic wave shielding adhesive film is bonded to the circuit board by heating can be suppressed, and the mechanical strength can be maintained. That is, when pasting on a stepped portion of a circuit board, a defect such as lack of concealment of the curable conductive polyurethane polyurea adhesive layer due to excessive elongation of the curable insulating polyurethane polyurea resin composition layer (II) Can be prevented.
  • the curable insulating polyurethane polyurea resin composition layer (II) is formed on the circuit board by heating. Excessive elongation can cause defects such as reduced mechanical strength and lack of concealment of the curable conductive polyurethane polyurea adhesive layer (I).
  • the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) exceeds 90% by weight, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed, In a manufacturing process, there exists a possibility that adhesiveness with a peelable film and a curable conductive polyurethane polyurea adhesive layer (I) may fall.
  • the film mode (3) comprises a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine type curing agent (E) and a curable insulating polyurethane polyurea resin composition containing an aziridine type curing agent (F).
  • a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine type curing agent (E) and a curable insulating polyurethane polyurea resin composition containing an aziridine type curing agent (F).
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) include the presence or absence of a conductive filler and an aziridine type. Except for the content of the curing agent (E), it can be composed of a polyurethane polyurea resin composition having the same composition or a polyurethane polyurea resin composition having a different composition. Further, the content of the aziridine-based curing agent (E) may be the same in the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). It can be different.
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both uncured (before curing) in a solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.
  • a curable electromagnetic wave shield having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight.
  • Adhesive film The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3).
  • Examples of the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I) include those similar to the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
  • the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
  • the epoxy resin (B) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight.
  • the curable conductive polyurethane polyurea adhesive layer (I) has a phenolic resin, a silicone resin, a urea resin, an acrylic resin, and a polyester resin as long as the performance such as heat resistance and flex resistance is not impaired.
  • a resin, a polyamide-based resin, or a polyimide-based resin can be contained.
  • curing agent can be contained in order to accelerate
  • the curable conductive polyurethane polyurea adhesive layer (I) has a silane coupling agent, an antioxidant, a pigment, a dye, a tackifying resin, a plasticizer, and the like within a range not deteriorating the adhesiveness and solder reflow resistance.
  • the curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight will be described. Also in the mode (4) of the film according to the present invention, the curable insulating polyurethane polyurea resin composition layer (II) plays a role of imparting mechanical strength to the curable electromagnetic wave shielding adhesive film upon sticking / curing. Bear. That is, it has a function as a substrate or carrier even in an uncured state (before curing), and hits the substrate film in Patent Document 4, for example.
  • the curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight comprises a diol compound having a carboxyl group (c1) and a polyol having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound.
  • the epoxy resin (D) having at least one epoxy group and the aziridine-based curing agent (E) are added in a range of 0.05 to 4 mol of aziridinyl group with respect to 1 mol of carboxyl group in the polyurethane polyurea resin (C). Containing curable insulating polyurethane polyurea resin having film-forming ability It is formed from a formed product.
  • Examples of the polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) include the same as the polyurethane polyurea resin (A) described in the film embodiment (1). .
  • the epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (A) having two or more epoxy groups.
  • the blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
  • the epoxy resin (D) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight.
  • phenol is used within a range not impairing performance such as heat resistance and flex resistance.
  • a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.
  • curing agent can be contained in order to accelerate
  • the curable insulating polyurethane polyurea resin composition layer (II) has a silane content within a range that does not deteriorate the adhesion and solder reflow resistance, as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
  • One or more coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. may be added. .
  • the aziridine type curing agent (E) will be described.
  • the aziridine-based curing agent (E) by utilizing the high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (C), both are reacted without requiring special aging. Allow to harden. That is, both can be reacted, and the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) can be 30 to 90% by weight. Thereby, excessive elongation of the curable insulating polyurethane polyurea resin composition layer (II) when the electromagnetic wave shielding adhesive film is heated and stuck to the circuit board can be suppressed, and the mechanical strength can be maintained.
  • the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.
  • the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is less than 30% by weight, that is, when most of the polyurethane polyurea resin (C) remains unreacted.
  • the curable insulating polyurethane polyurea resin composition layer (II) is excessively stretched, defects such as a decrease in mechanical strength and exposure of the curable conductive polyurethane polyurea adhesive layer (I) at the stepped portion are caused.
  • the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) exceeds 90% by weight, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed,
  • the adhesion between the curable insulating polyurethane polyurea resin composition layer (II) and the peelable film 1 and the curable insulating polyurethane polyurea resin composition layer (II) And the adhesiveness between the curable conductive polyurethane polyurea adhesive layer (I) are lowered.
  • the aziridinyl group is in an amount of 0.1 with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C). It is important to contain the aziridine curing agent (E) in the range of 05 to 4 mol, preferably in the range of 0.2 to 2 mol, and in the range of 0.4 to 1 mol. Is more preferable.
  • the gel fraction is less than 30%.
  • aziridinyl group of the aziridine type curing agent (E) is less than 0.05 mol with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C)
  • most of the carboxylic acid in the polyurethane polyurea resin is unreacted. Therefore, the gel fraction is less than 30%.
  • there are more than 4 moles of aziridinyl groups with respect to 1 mole of carboxyl groups since aziridinyl groups are excessively present, almost all of the carboxylic acids in the polyurethane polyurea resin (C) are all aziridine-based curing agents (E) and It reacts and the gel fraction exceeds 90%.
  • the mode (4) of the film has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) containing an aziridine-based curing agent (E).
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) include a conductive filler and an aziridine-based curing agent. Except for the presence or absence of (E), it can consist of a polyurethane polyurea resin composition of the same composition, or it can consist of a polyurethane polyurea resin composition of a different composition.
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in an uncured (before curing) solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.
  • a polyurethane polyurea resin (C) and an epoxy resin (D) are formed on one surface of one peelable film (hereinafter referred to as peelable film 1). And drying a curable resin composition containing a curable insulating polyurethane polyurea resin composition layer (II), Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), and a conductive filler is provided on one surface of another peelable film (hereinafter referred to as peelable film 2).
  • curable conductive polyurethane polyurea adhesive layer (I) Coating and drying to form a curable conductive polyurethane polyurea adhesive layer (I), Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.
  • the said curable resin composition is applied and dried to one side of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried.
  • Forming layer (II) On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I).
  • the peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).
  • the said curable conductive resin composition is applied and dried on one surface of the peelable film 2, and curable conductive polyurethane polyurea adhesion
  • attachment is carried out.
  • the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II).
  • the peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).
  • the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea with respect to the embodiment (1) of the curable electromagnetic wave shielding adhesive film of the present invention.
  • a curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.
  • the peelable film used in the present invention a film having a release treatment on one side or both sides, a film having an adhesive applied on one side or both sides, or the like can be used.
  • the release film substrate polyethylene terephthalate, polyethylene naphthalate, polyvinyl fluoride, polyvinylidene fluoride, rigid polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, Plastic sheets such as polycarbonate, polyacrylonitrile, polybutene, soft polyvinyl chloride, polyvinylidene fluoride, polyethylene, polypropylene, polyurethane, ethylene vinyl acetate copolymer, or polyvinyl acetate, glassine paper, fine paper, kraft paper, or coat Examples thereof include papers such as paper, various non-woven fabrics, synthetic paper, metal foil, and
  • a mold release treatment method there is a method in which a mold release agent is applied to one or both sides of a film, or a physical matting treatment is performed.
  • Release agents include hydrocarbon resins such as polyethylene or polypropylene, higher fatty acids or metal salts thereof, higher fatty acid soaps, waxes, animal and vegetable oils, mica, talc, silicone surfactants, silicone oils, silicone resins, fluorine A surface active agent, a fluororesin, or a fluorine-containing silicone resin is used.
  • a method for applying the release agent conventionally known methods such as gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, spray coating method, It can be performed by a bar coating method, a spin coating method, a dip coating method, or the like.
  • a conventionally known coating method such as a gravure coating method, a kiss coating method, a die coating method, The lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, spray coating method, bar coating method, spin coating method, dip coating method, or the like can be used.
  • the peelable film 2 covering the curable conductive polyurethane polyurea adhesive layer (I) is generally peeled before the curable conductive polyurethane polyurea adhesive layer (I) is cured. Therefore, as long as it has releasability from the curable conductive polyurethane polyurea adhesive layer (I) in an uncured state, a film (for example, a polyethylene film or a polyethylene terephthalate film) that has not been subjected to a release treatment can also be used. .
  • a film for example, a polyethylene film or a polyethylene terephthalate film
  • the peelable film 1 that covers the curable insulating polyurethane polyurea resin composition layer (II) generally peels after the curable insulating polyurethane polyurea resin composition layer (II) is cured.
  • a film for example, a polyethylene film or a polyethylene terephthalate film
  • a film that has not been particularly peeled can also be used.
  • the aspect (2) of the curable electromagnetic wave shielding adhesive film will be described.
  • curing agent (E) are contained in one surface of the peelable film 1.
  • FIG. Applying and drying the curable resin composition to form a curable insulating polyurethane polyurea resin composition layer (II), Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), and a conductive filler is applied to one surface of the peelable film 2 and dried to obtain a curable conductive property.
  • Forming a polyurethane polyurea adhesive layer (I) Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.
  • the said curable resin composition is applied and dried on one surface of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried.
  • Forming layer (II) On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I).
  • the peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).
  • the said curable conductive resin composition is applied and dried on one surface of the peelable film 2, and curable conductive polyurethane polyurea adhesion
  • attachment is carried out.
  • the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II).
  • the peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).
  • the drying conditions for obtaining the polyurea resin composition layer (II) and the conditions for superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are selected. be able to.
  • the solvent is sufficiently volatilized, and the polyurethane polyurea resin ( C) is a condition in which the carboxylic acid and the aziridine-based curing agent (E) can react, and it is preferable to heat and dry at 50 ° C. to 150 ° C. for about 10 seconds to 5 minutes, and at 70 ° C. to 120 ° C. for 30 seconds to 3 It is more preferable to heat and dry for about minutes.
  • the curable conductive polyurethane polyurea formed separately from each other in that the cured state of the curable insulating polyurethane polyurea resin composition layer (II) that has been semi-cured by the aziridine-based curing agent (E) can be easily maintained.
  • a method of obtaining a curable electromagnetic wave shielding adhesive film by superimposing the adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) is preferred.
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) have a temperature of 40 ° C. to 120 ° C., a pressure of 0.1 to 5 MPa, and a time. It is preferable to superimpose and integrate them under conditions of about 0.5 seconds to 60 seconds.
  • the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.
  • the aspect (3) of the curable electromagnetic wave shielding adhesive film will be described.
  • curing agent (F) are contained in one surface of the peelable film 1 Coating and drying the curable resin composition to form a curable insulating polyurethane polyurea resin composition layer (II),
  • a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), an aziridine curing agent (E), and a conductive filler is applied to one surface of the peelable film 2.
  • curable conductive polyurethane polyurea adhesive layer (I) Dry to form a curable conductive polyurethane polyurea adhesive layer (I), Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.
  • the said curable resin composition is applied and dried to one side of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried.
  • Forming layer (II) On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I).
  • the peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).
  • the said curable conductive resin composition is applied and dried on one side of the peelable film 2, and curable conductive polyurethane polyurea adhesion
  • attachment is carried out.
  • the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II).
  • the peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) have a curable conductive property such that the gel fraction is 30 to 90% by weight. Drying conditions for obtaining polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II), and curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin The conditions for overlaying the composition layer (II) can be selected. In addition, drying conditions, curing conditions, etc. can be performed on the same conditions as the manufacturing method of the aspect (2) of a curable electromagnetic wave shielding adhesive film.
  • the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.
  • the aspect (4) of a curable electromagnetic wave shielding adhesive film is demonstrated.
  • the curable resin composition containing a polyurethane polyurea resin (C) and an epoxy resin (D) is applied to one surface of the peelable film 1.
  • a curable insulating polyurethane polyurea resin composition layer (II) Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), an aziridine curing agent (E), and a conductive filler is applied to one surface of the peelable film 2.
  • curable conductive polyurethane polyurea adhesive layer (I) Dry to form a curable conductive polyurethane polyurea adhesive layer (I), Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.
  • the said curable resin composition is applied and dried on one surface of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried.
  • Forming layer (II) On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I).
  • the peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).
  • the said curable conductive resin composition is applied and dried on one surface of the peelable film 2, and curable conductive polyurethane polyurea adhesion
  • attachment is carried out.
  • the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II).
  • the peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).
  • the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea adhesive layer (I) can be in a semi-cured state with a gel fraction of 30 to 90% by weight. Selecting the drying conditions for obtaining the resin composition layer (II) and the conditions for superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). Can do. In addition, drying conditions, curing conditions, etc. can be performed on the same conditions as the manufacturing method of the aspect (2) of a curable electromagnetic wave shielding adhesive film.
  • the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.
  • the curable electromagnetic wave shielding adhesive film is a laminate state of peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea resin composition layer (II) / peelable film 1
  • the peelable film 2 is peeled off from the curable electromagnetic wave shielding adhesive film to expose the curable conductive polyurethane polyurea adhesive layer (I).
  • the curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend and heated, whereby the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer ( In II), the polyurethane polyurea resin (A) and the epoxy resin (B), the polyurethane polyurea resin (C) and the epoxy resin (D) are reacted to cure both layers (I) and (II). In the vicinity of the contact interface, there may be a reaction between the polyurethane polyurea resin (A) and the epoxy resin (D), and the polyurethane polyurea resin (C) and the epoxy resin (B).
  • a flexible printed wiring board that is repeatedly bent can be given as a representative example.
  • it can also be applied to rigid printed wiring boards.
  • An electromagnetic shielding material produced by using the above-described curable electromagnetic wave shielding adhesive film as an adherend, for example, using a printed wiring board can be suitably used for an article such as a mobile phone or a digital camera.
  • the weight average molecular weight of the polyurethane polyurea resin described in the Examples, and the number average molecular weight of the polyester resin are the weight average molecular weight and the number average molecular weight in terms of polystyrene determined by GPC measurement, and the conditions for the GPC measurement are as follows: It is as follows.
  • the internal temperature is once cooled to 170 ° C., 92.6 parts of adipic acid, 65.8 parts of isophthalic acid, and 113.6 parts of 1,4-cyclohexanedicarboxylic acid are added, and distilled water is removed from the reaction system under normal pressure.
  • the temperature was raised to 240 ° C. over 3 hours while maintaining the temperature, and further maintained at 240 ° C., and the reaction was continued until the acid value of the product reached 15 mgKOH / g.
  • the apparatus was changed to a vacuum decompression apparatus, 0.06 part of tetrabutyl titanate was added, and the reaction was continued for 6 hours under a reduced pressure of 2 Torr at a temperature of 240 ° C., and then taken out into a polyfluoroethylene resin container. It was. The number average molecular weight of this resin was 18000, and the glass transition temperature was 27 ° C. Subsequently, 100 parts of toluene was added to 100 parts of the obtained polyester resin and dissolved. Next, 5 parts of ethylene glycol bistrimellitate dianhydride was added to each flask and reacted at a temperature of 100 ° C.
  • Example 1 20 parts of epoxy resin (B-1) was added to 333 parts of polyurethane polyurea resin solution (A-1) to obtain an adhesive resin composition.
  • a conductive filler (“AgXF-301” manufactured by Fukuda Metal Foil Powder Industry) was added and stirred and mixed, and the total of polyurethane polyurea resin and epoxy resin (B-1) A curable conductive polyurethane polyurea adhesive containing 150 parts of conductive filler with respect to 100 parts by weight was obtained.
  • 20 parts of epoxy resin (D-1) was added to 333 parts of polyurethane polyurea resin solution (C-1) to obtain insulating resin composition 1.
  • a curable conductive polyurethane polyurea adhesive is applied to the release surface of a film obtained by subjecting one surface of a 75 ⁇ m thick polyethylene terephthalate film as the peelable film 2 to a dry treatment, and the dry film thickness is 8 ⁇ m.
  • the curable conductive polyurethane polyurea adhesive (I) was formed.
  • an insulating resin composition is coated on a release surface of a film obtained by subjecting one side of a 50 ⁇ m-thick polyethylene terephthalate film as the peelable film 1 to dryness, and the dry film thickness is 15 ⁇ m.
  • An insulating resin composition (II) was formed.
  • a shielding adhesive film was prepared.
  • Examples 2 to 13 In the same manner as in Example 1, the polyurethane polyurea resin solution, epoxy resin, and conductive filler of the types and amounts shown in Table 1 and Table 2 were used to curable conductive polyurethane polyurea adhesive, and curable insulating polyurethane. A polyurea resin composition was prepared to produce a curable electromagnetic shielding adhesive film.
  • Example 14 to 28 In the same manner as in Example 1, a curable conductive adhesive and a curable insulating resin using polyurethane polyurea resin solutions, epoxy resins, conductive fillers, and aziridine curing agents of the types and amounts shown in Tables 3 and 4 were used. The composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.
  • Example 29 to 45 In the same manner as in Example 1, a polyurethane polyurea resin solution, an epoxy resin, and a conductive filler of the types and amounts shown in Table 5 and Table 6 were used to curable conductive polyurethane polyurea adhesive, and curable insulating polyurethane. A polyurea resin composition was prepared to produce a curable electromagnetic shielding adhesive film.
  • Example 46 to 61 In the same manner as in Example 1, using the polyurethane polyurea resin solution, epoxy resin, conductive filler, and aziridine-based curing agent of the types and amounts shown in Table 7 and Table 8, curable conductive adhesive and curable insulation The curable resin composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.
  • Example 1 except that a polyphenylene sulfide film (Comparative Example 9) or a polyethylene terephthalate film (Comparative Example 10) was used instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 1. In the same manner as above, an electromagnetic wave shielding film was produced.
  • Example 12 In the same manner as in Example 14, a polyurethane polyurea resin solution, an epoxy resin, a conductive filler, and an aziridine-based curing agent of the types and amounts shown in Tables 11 and 12 are used. A conductive insulating polyurethane polyurea resin composition was prepared to produce an electromagnetic wave shielding adhesive film.
  • Example 29 except that a polyphenylene sulfide film (Comparative Example 34) or a polyethylene terephthalate film (Comparative Example 35) was used instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 29. In the same manner as above, an electromagnetic wave shielding film was produced.
  • Example 46 except that a polyphenylene sulfide film (Comparative Example 47) or a polyethylene terephthalate film (Comparative Example 48) was used instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 46. In the same manner as above, an electromagnetic wave shielding film was produced.
  • a polyimide film having a thickness of 50 ⁇ m (“Kapton 200EN” manufactured by Toray DuPont Co., Ltd.) is pressure-bonded at 150 ° C., 1.0 MPa, and 30 min to form a conductive adhesive layer (I) and a film-like insulating composition.
  • Product (II) was cured. After pressure bonding, for the purpose of measurement reinforcement, the peelable film 1 is removed, and an exposed cured film-like insulating layer is coated with a polyurethane polyurea-based adhesive sheet. And pressure bonding for 30 min. Peeling between the cured conductive adhesive layer and the polyimide film at 23 ° C.
  • a curable electromagnetic shielding adhesive film (or electromagnetic shielding film) having a width of 10 mm and a length of 60 mm is prepared, the peeling film 2 is peeled off, and the exposed curable conductive adhesive layer (I ),
  • (II) was cured. After pressure bonding, the peelable film 1 was removed, and heat treatment was performed in an electric oven at 180 ° C. for 3 minutes and then in an electric oven at 280 ° C. for 90 seconds. The appearance of the sample after the heat treatment was visually observed, and the presence or absence of appearance defects such as foaming, floating, and / or peeling was evaluated. Each test was conducted 5 times, and the evaluation was made by the number of appearance defects.
  • Appearance failure does not occur ⁇ : Appearance failure occurs within 2 times ⁇ : Appearance failure occurs 3 times or more
  • the peelable film 2 is peeled off from the curable electromagnetic shielding adhesive film (or electromagnetic shielding film) having a width of 6 mm and a length of 120 mm, and the exposed curable conductive adhesive layer (I) is removed.
  • a separately prepared flexible printed wiring board (a circuit pattern made of a 12 ⁇ m thick copper foil is formed on a polyimide film having a thickness of 25 ⁇ m, and a cover film having a thickness of 40 ⁇ m with an adhesive is laminated on the circuit pattern.
  • the conductive adhesive layer (I) and the film-like insulating composition (II) were cured by pressure bonding to the cover film surface of the printed wiring board) at 150 ° C., 1 MPa, and 30 min.
  • the peelable film 1 was removed and subjected to an MIT bending tester under conditions of a radius of curvature of 0.38 mm, a load of 500 g, and a speed of 180 times / min, and the bending resistance was evaluated by the number of times until the circuit pattern was disconnected.
  • the evaluation criteria are as follows. ⁇ : 3000 times or more ⁇ : 1500 times or more and less than 3000 times ⁇ : less than 1500 times
  • Circuit board 2A, 2B made of a copper foil with a thickness of 18 ⁇ m and not electrically connected to a flexible printed wiring board (with a thickness of 12.5 ⁇ m formed on the conductive adhesive layer (I).
  • the circuit board 2A is pressure-bonded to the circuit 2A on a circuit board (with a cover film having a through hole having a thickness of 37.5 ⁇ m and a diameter of 1.6 mm) with an adhesive at 150 ° C., 1 MPa, and 30 min.
  • the conductive adhesive layer (I) and the film-like insulating composition (II) were cured (see FIG. 1). After the pressure bonding, the peelable film 1 is removed, and the resistance value between 2A and 2B shown in FIG. 1 (3) is set to PCT (121 ° C., 100% RH) using a four-point probe of “Lorestar GP” manufactured by Mitsubishi Chemical. , And 2 atm).
  • the evaluation criteria are as follows. ⁇ : Less than 500 m ⁇ ⁇ : 500 m ⁇ or more and less than 1000 m ⁇ ⁇ : 1000 m ⁇ or more
  • Ductility test A “small” polyimide film (A) having a thickness of 125 ⁇ m, a width of 20 mm, and a length of 30 mm was placed almost at the center of a “large” polyimide film (B) having a width of 50 mm and a length of 50 mm.
  • a curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) having a width of 50 mm and a length of 60 mm was prepared, the peelable film 2 was peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I), The entire surface of the “large” polyimide film (B) including the whole of the “small” polyimide film (A) is covered and pressure-bonded under conditions of 150 ° C., 1 MPa, and 30 min, and a curable conductive polyurethane polyurea adhesive layer (I ) And the curable insulating polyurethane polyurea resin composition layer (II).
  • the peelable film 1 After crimping, the peelable film 1 is removed, and each side portion of the “small” polyimide film (A) sandwiched between the cured electromagnetic wave shielding film and the “large” polyimide film (B) (depending on the level difference)
  • the projection portion) was observed with the naked eye and with a 50 ⁇ microscope through the insulating layer of the cured electromagnetic wave shielding film, and the degree to which the conductive adhesive layer after the projection portion was cured due to the step was seen through was evaluated.
  • ⁇ The conductive adhesive layer was not seen through both with the naked eye and with a microscope.
  • ⁇ Although the conductive adhesive layer was not seen through with the naked eye, the conductive adhesive layer was seen through with the microscope.
  • X The conductive adhesive layer was seen through both in the naked eye and in the microscope.
  • each curable insulating polyurethane polyurea resin composition described in each example and each comparative example was applied to one surface of a polyimide film having a thickness of 50 ⁇ m (“Kapton 200EN” manufactured by Toray DuPont). Then, it was dried at 100 ° C. for 2 minutes using an electric oven to form a curable insulating polyurethane polyurea composition layer (II) having a dry film thickness of 15 ⁇ m.
  • the curable conductive polyurethane polyurea adhesive layer (I) having a hole and the curable insulating polyurethane polyurea resin composition layer (II) are stacked and subjected to pressure-bonding treatment at 150 ° C., 1.0 MPa, and 30 min. Did.
  • the evaluation criteria are as follows.

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Abstract

Disclosed is a curable electromagnetic shielding adhesive film having a curable conductive polyurethane-polyurea adhesive layer (I) and a curable insulating polyurethane-polyurea resin composition layer (II). The curable conductive polyurethane-polyurea adhesive layer (I) contains a polyurethane-polyurea resin (A) which is obtained by reacting a urethane prepolymer (a4) having an isocyanate group at an end with a polyamino compound (a5), and an epoxy resin (B) having two or more epoxy groups. The urethane prepolymer (a4) is obtained by reacting a carboxyl group-containing diol compound (a1), a polyol (a2) having a number average molecular weight of 500-8,000 which is not a carboxyl group-containing diol compound, and an organic diisocyanate (a3). The curable conductive polyurethane-polyurea adhesive layer (I) also contains 10-700 parts by weight of a conductive filler per 100 parts by weight of the total of the polyurethane-polyurea resin (A) and the epoxy resin (B). The curable insulating polyurethane-polyurea resin composition layer (II) contains a polyurethane-polyurea resin (C) which is obtained by reacting a urethane prepolymer (c4) having an isocyanate group at an end with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. The urethane prepolymer (c4) is obtained by reacting a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500-8,000 which is not a carboxyl group-containing diol compound, and an organic diisocyanate (c3).

Description

硬化性電磁波シールド性接着性フィルム、その製造方法、及びその使用方法、並びに電磁波遮蔽物の製造方法及び電磁波遮蔽物Curable electromagnetic shielding adhesive film, method for producing the same, method for using the same, method for producing electromagnetic shielding and electromagnetic shielding

　本発明は、繰り返し屈曲を受けるフレキシブルプリント配線板などに貼着して、電気回路から発生する電磁ノイズを遮蔽する用途に好適に用いられる硬化性電磁波シールド性接着性フィルム、その製造方法、及びその使用方法、並びに電磁波遮蔽物の製造方法及び電磁波遮蔽物に関する。 The present invention relates to a curable electromagnetic wave shielding adhesive film that is suitably used for an application of shielding electromagnetic noise generated from an electric circuit by sticking to a flexible printed wiring board or the like that repeatedly undergoes bending, its manufacturing method, and its The present invention relates to a method of use, a method of manufacturing an electromagnetic shielding material, and an electromagnetic shielding material.

　フレキシブルプリント配線板は、屈曲性を有することから、近年のＯＡ機器、通信機器、携帯電話などの更なる高性能化、小型化の要請に応えるべく、その狭く複雑な構造からなる筐体内部に電子回路を組み込むために多用されている。そうした電子回路のダウンサイズ化・高周波化に伴い、そこから発生する不要な電磁ノイズに対する対策がますます重要になってきている。そこで、フレキシブルプリント配線板に、電子回路から発生する電磁ノイズを遮蔽する電磁波シールド性接着性フィルムを貼着することが従来よりおこなわれている。
　この電磁波シールド性接着性フィルム自体には、電磁波シールド性に加えて、貼り合わせたフレキシブルプリント配線板全体の耐屈曲性を損なわないよう、薄さと優れた耐屈曲性が要求される。そのため、電磁波シールド性接着性フィルムとしては、厚さの薄い基材フィルム上に導電層を設けてなる基本的構造を有するものが広く知られている。 The flexible printed wiring board has flexibility, so that it meets the demand for higher performance and downsizing of recent office automation equipment, communication equipment, mobile phones, etc. Widely used to incorporate electronic circuits. With such downsizing and high frequency of electronic circuits, countermeasures against unnecessary electromagnetic noise generated therefrom are becoming more and more important. Thus, an electromagnetic wave shielding adhesive film that shields electromagnetic noise generated from an electronic circuit has been attached to a flexible printed wiring board.
In addition to electromagnetic wave shielding properties, the electromagnetic wave shielding adhesive film itself is required to have thinness and excellent bending resistance so as not to impair the bending resistance of the bonded flexible printed wiring board as a whole. Therefore, as an electromagnetic wave shielding adhesive film, one having a basic structure in which a conductive layer is provided on a thin base film is widely known.

　従来の電磁波シールド性接着性フィルムとしては、カバーフィルムの片面に、導電性接着剤層及び必要に応じて金属薄膜層からなるシールド層を有し、他方の面に接着剤層と離型性補強フィルムとが順次積層されてなる補強シールドフィルムが知られている（特許文献１参照）。
　また、導電性接着剤層及び／又は金属薄膜を有するシールド層と芳香族ポリアミド樹脂からなるベースフィルムを有するシールドフィルムが知られている（特許文献２参照）。
　また、セパレートフィルムの片面に樹脂をコーティングしてカバーフィルムを形成し、前記カバーフィルムの表面に金属薄膜層と接着剤層とで構成されるシールド層を設けてなるシールド性接着フィルムが知られている（特許文献３参照）。 As a conventional electromagnetic wave shielding adhesive film, the cover film has a conductive adhesive layer on one side of the cover film and, if necessary, a shield layer made of a metal thin film layer, and the adhesive layer and releasability reinforcement on the other side. A reinforcing shield film in which films are sequentially laminated is known (see Patent Document 1).
Further, a shield film having a base film made of a conductive adhesive layer and / or a shield layer having a metal thin film and an aromatic polyamide resin is known (see Patent Document 2).
Also known is 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. (See Patent Document 3).

　そして、従来の電磁波シールド性接着性フィルムの接着剤層には、ポリスチレン系、酢酸ビニル系、ポリエステル系、ポリエチレン系、ポリプロピレン系、ポリアミド系、ゴム系、アクリル系などの熱可塑性樹脂や、フェノール系、エポキシ系、ウレタン系、メラミン系、アルキッド系などの熱硬化性樹脂が用いられていた。しかし、従来の接着剤層には耐屈曲性及び耐熱性を兼ね備えたものがなく、特にフレキシブルプリント配線板用途に用いるためには、繰り返しの折り曲げに対する耐性が完全でなかった。 The adhesive layer of the conventional electromagnetic wave shielding adhesive film includes thermoplastic resins such as polystyrene, vinyl acetate, polyester, polyethylene, polypropylene, polyamide, rubber, and acrylic, and phenolic. Epoxy-based, urethane-based, melamine-based, alkyd-based thermosetting resins have been used. However, none of the conventional adhesive layers have both bending resistance and heat resistance, and the resistance to repeated bending is not perfect for use in flexible printed wiring boards.

　特許文献４には、カルボキシル基を有するポリウレタンポリウレア樹脂と、２個以上のエポキシ基を有するエポキシ樹脂と、導電性フィラーとを含有する接着剤組成物を用いてなる電磁波シールド性接着性フィルムは、耐屈曲性及び耐熱性に優れる旨、開示されている。
　しかし、特許文献４に開示される電磁波シールド性接着性フィルムは、ポリフェニレンサルファイド（以下、ＰＰＳと略すこともある）や、カルボキシル基を有するポリエステル樹脂と２個以上のエポキシ基を有するエポキシ樹脂とを含有してなる硬化性フィルム状組成物を硬化したフィルムを、絶縁性の基材フィルムとして用いていた。このような基材フィルムを用いた電磁波シールド性接着性フィルムでは、耐屈曲性に対するより厳しい要求に応えられなくなった。更に、電磁波シールド性接着性フィルムを被着体に貼着した後、高温高湿度下に曝すと、導電性が低下してしまうという新たな問題が生じた。
特開２００３－２９８２８５号公報 特開２００４－２７３５７７号公報 特開２００４－９５５６６号公報 ＷＯ２００６－０８８１２７号公報 Patent Document 4 discloses an electromagnetic wave shielding adhesive film comprising an adhesive composition containing a polyurethane polyurea resin having a carboxyl group, an epoxy resin having two or more epoxy groups, and a conductive filler. It is disclosed that it is excellent in bending resistance and heat resistance.
However, the electromagnetic wave shielding adhesive film disclosed in Patent Document 4 includes polyphenylene sulfide (hereinafter also abbreviated as PPS), a polyester resin having a carboxyl group, and an epoxy resin having two or more epoxy groups. The film which hardened the curable film-like composition formed was used as an insulating base film. In the electromagnetic wave shielding adhesive film using such a base film, it is no longer possible to meet more stringent requirements for flex resistance. Furthermore, when the electromagnetic wave shielding adhesive film is attached to the adherend and then exposed to high temperature and high humidity, a new problem has arisen in that the conductivity is lowered.
JP 2003-298285 A JP 2004-273577 A JP 2004-95566 A WO2006-088127

　本発明は、フレキシブルプリント配線板などに貼付して電磁ノイズを遮蔽する用途に好適に用いられる電磁波シールド性接着性フィルムであって、フレキシブルプリント配線板に貼着した後、十分な電磁波シールド性に加えて、鉛フリーハンダリフロー時の高温に耐え得る耐熱性を有し、従来よりも耐屈曲性に優れると共に、高温高湿度下に曝されても〔具体的には、プレッシャークッカーテスト（Pressure Cracker Test：以下、ＰＣＴという）を経ても〕導電性が低下しない、電磁波シールド性接着性フィルムを提供することを目的とする。 The present invention is an electromagnetic wave shielding adhesive film that is suitably used for applications such as affixing to a flexible printed wiring board and shielding electromagnetic noise, and after adhering to a flexible printed wiring board, it has sufficient electromagnetic shielding properties. In addition, it has heat resistance that can withstand high temperatures during lead-free solder reflow, and has superior bending resistance than conventional ones, and even when exposed to high temperatures and high humidity [specifically, Pressure Cooker Test (Pressure Cracker It is an object of the present invention to provide an electromagnetic wave shielding adhesive film in which the conductivity does not decrease even after passing through Test (hereinafter referred to as PCT).

　更に、本発明は、被着体に加熱圧着する際に、貼着領域から硬化性導電性接着剤層がはみ出しにくく、且つ、段差を有する回路基板に加熱圧着する際にも、段差部において、導電性ポリウレタンポリウレア接着層に対して十分な隠蔽性を備えた電磁波シールド性接着性フィルムを提供することを目的とする。ここで、隠蔽性が求められる理由は、有色層である導電性ポリウレタンポリウレア接着層を、その上からポリウレタンポリウレア絶縁層によって隠蔽するためである。すなわち、硬化後において導電性ポリウレタンポリウレア接着層を覆う、硬化後のポリウレタンポリウレア絶縁層は柔軟性に富む必要があるが、硬化前ないし硬化の最中に柔軟性に富みすぎると、段差部において、硬化過程のポリウレタンポリウレア絶縁層が過度に伸長し、導電性ポリウレタンポリウレア接着層が露出してしまうか透けて見えてしまう。そこで、本発明は、硬化後において柔軟性に富み、耐屈曲性に優れながら、貼着時には段差部において、導電性ポリウレタンポリウレア接着層に対する十分な隠蔽性を備えた電磁波シールド性接着性フィルムを提供することを目的とする。 Furthermore, the present invention is such that, when thermocompression bonding to the adherend, the curable conductive adhesive layer is unlikely to protrude from the adhesion region, and also when thermocompression bonding to a circuit board having a step, An object of the present invention is to provide an electromagnetic wave shielding adhesive film having a sufficient concealing property for the conductive polyurethane polyurea adhesive layer. Here, the reason why the concealability is required is to conceal the conductive polyurethane polyurea adhesive layer, which is a colored layer, from above with the polyurethane polyurea insulating layer. That is, the cured polyurethane polyurea insulating layer that covers the conductive polyurethane polyurea adhesive layer after curing needs to be rich in flexibility, but if it is too flexible before curing or during curing, The polyurethane polyurea insulating layer in the curing process extends excessively, and the conductive polyurethane polyurea adhesive layer is exposed or seen through. Therefore, the present invention provides an electromagnetic wave shielding adhesive film that is sufficiently flexible after curing and has excellent bending resistance, but has sufficient concealing property to the conductive polyurethane-polyurea adhesive layer at the stepped portion at the time of sticking. The purpose is to do.

　また、本発明は、このような優れた性能を有する電磁波シールド性接着性フィルムを安価かつ安定的に製造する方法、その電磁波シールド性接着性フィルムを使用する方法、その電磁波シールド性接着性フィルムから電磁波遮蔽物を製造する方法、及びその電磁波シールド性接着性フィルムから得られる電磁波遮蔽物を提供することを目的とする。 In addition, the present invention provides a method for inexpensively and stably producing an electromagnetic wave shielding adhesive film having such excellent performance, a method of using the electromagnetic wave shielding adhesive film, and the electromagnetic wave shielding adhesive film. An object of the present invention is to provide a method for producing an electromagnetic wave shielding material, and an electromagnetic wave shielding material obtained from the electromagnetic wave shielding adhesive film.

　本発明において第一の発明は、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する硬化性電磁波シールド性接着性フィルムであって、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）とを含有し、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部とを含有し、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有することを特徴とする、硬化性電磁波シールド性接着性フィルムに関する。 In the present invention, the first invention is
A curable electromagnetic shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B), containing a conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B),
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups The present invention relates to a curable electromagnetic wave shielding adhesive film characterized by containing (D).

　第二の発明は、
　ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、硬化性電磁波シールド性接着性フィルムであって、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤から形成されてなり、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有することを特徴とする、硬化性電磁波シールド性接着性フィルムに関する。 The second invention is
A curable electromagnetic shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulating polyurethane polyurea resin composition layer (II). There,
The curable conductive polyurethane polyurea adhesive layer (I) reacts the diol compound (a1) having a carboxyl group, the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and the organic diisocyanate (a3). The polyurethane polyurea resin (A) obtained by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with the polyamino compound (a5), and the epoxy resin (B) having two or more epoxy groups ), The polyurethane polyurea resin (A) and the epoxy resin (B) in a total of 100 parts by weight, the conductive filler: 10 to 700 parts by weight, and the aziridine-based curing agent (E) are added to the polyurethane polyurea resin. (A) aziridinyl group for 1 mol of carboxyl group Is formed from the curable conductive polyurethane polyurea adhesive containing 0.05 to 4 moles of the range will be,
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups The present invention relates to a curable electromagnetic wave shielding adhesive film characterized by containing (D).

　第三の発明は、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、ゲル分率が３０～９０重量％である、硬化性電磁波シールド性接着性フィルムであって、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤から形成されてなり、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成されてなる、ことを特徴とする、硬化性電磁波シールド性接着性フィルムに関する。 The third invention is
A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight Because
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B), a conductive filler: 10 to 700 parts by weight, and an aziridine-based curing agent (E) with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B), and the polyurethane polyurea An aziridini with respect to 1 mol of carboxyl groups in the resin (A) It is formed from a curable conductive polyurethane-polyurea adhesives containing in the range of from 0.05 to 4 moles of group,
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (F) having a film-forming ability containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). It is not formed from a curable insulating polyurethane polyurea resin composition. , Characterized in that, it relates to a curable electromagnetic shielding adhesive film.

　第四の発明は、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、硬化性電磁波シールド性接着性フィルムであって、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、導電性フィラーとを含有し、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部とを含有し、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有するフィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成されたことを特徴とする、硬化性電磁波シールド性接着性フィルムに関する。 The fourth invention is
A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight. There,
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B) and a conductive filler, containing a conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B),
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups Curing having film-forming ability containing (D) and an aziridin-based curing agent (E) in a range of 0.05 to 4 mol of aziridinyl group with respect to 1 mol of carboxyl group in the polyurethane polyurea resin (C). Formed from a conductive insulating polyurethane polyurea resin composition Wherein, it relates to a curable electromagnetic shielding adhesive film.

　第五の発明は、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部を含有し、かつ、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、ポリウレタンポリウレア樹脂（Ｃ）１００重量部に対して、エポキシ樹脂（Ｄ）３～２００重量部を含有することを特徴とする第一～第四の発明いずれかの硬化性電磁波シールド性接着性フィルムに関する。 The fifth invention is
The curable conductive polyurethane polyurea adhesive layer (I) contains 3 to 200 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A), and the curable insulating polyurethane polyurea resin. The curing according to any one of the first to fourth inventions, wherein the composition layer (II) contains 3 to 200 parts by weight of the epoxy resin (D) with respect to 100 parts by weight of the polyurethane polyurea resin (C). The present invention relates to an electromagnetic wave shielding adhesive film.

　第六の発明は、
　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が接触していない表面上に、剥離性フィルム１が積層されていることを特徴とする第五の発明の硬化性電磁波シールド性接着性フィルムに関する。 The sixth invention is
The peelable film 1 is laminated on the surface of the curable insulating polyurethane polyurea resin composition layer (II) that is not in contact with the curable conductive polyurethane polyurea adhesive layer (I). The present invention relates to a curable electromagnetic wave shielding adhesive film of a fifth invention.

　第七の発明は、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が接触していない表面上に、剥離性フィルム２が積層されていることを特徴とする第五の発明の硬化性電磁波シールド性接着性フィルムに関する。 The seventh invention
The peelable film 2 is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) that is not in contact with the curable insulating polyurethane polyurea resin composition layer (II). The present invention relates to a curable electromagnetic wave shielding adhesive film of a fifth invention.

　第八の発明は、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が接触していない表面上に、剥離性フィルム２が積層されており、かつ、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が接触していない表面上に、剥離性フィルム１が積層されていることを特徴とする第五の発明の硬化性電磁波シールド性接着性フィルムに関する。 The eighth invention is
The peelable film 2 is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) that is not in contact with the curable insulating polyurethane polyurea resin composition layer (II), and is curable. A fifth aspect is characterized in that the peelable film 1 is laminated on the surface of the insulating polyurethane polyurea resin composition layer (II) which is not in contact with the curable conductive polyurethane polyurea adhesive layer (I). It relates to the curable electromagnetic wave shielding adhesive film of the invention.

　第九の発明は、
　剥離性フィルム１の一方の表面上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　剥離性フィルム２の一方の表面上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The ninth invention
Obtained by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1 And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing,
Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2 A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal thereof with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of conductive filler is formed with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B). And the process of
The present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film, comprising a step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II).

　第十の発明は、
　剥離性フィルム１の一方の表面上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The tenth invention is
Obtained by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1 And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing,
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) And a polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5) and an epoxy having two or more epoxy groups. Curable conductive polyurethane polyurea adhesive containing resin (B) and 10 to 700 parts by weight of conductive filler with respect to 100 parts by weight of the total of polyurethane polyurea resin (A) and epoxy resin (B) Forming layer (I); and
A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I),
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第十一の発明は、
　剥離性フィルム２の一方の表面上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The eleventh invention is
Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2 A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, Forming a curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B). The process of
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing (D), and
A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第十二の発明は、
　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　剥離性フィルム２の一方の表面上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The twelfth invention is
Obtained by reacting one surface of the peelable film 1 with a diol compound having a carboxyl group (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). Contains a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups Forming a curable insulating polyurethane polyurea resin composition layer (II), and
Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2 A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, Conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B), and the polyurethane polyurea resin (A) 0.05-4 mol of aziridinyl group per 1 mol of carboxyl group Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in the range and,
A step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第十三の発明は、
　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The thirteenth invention is
Obtained by reacting one surface of the peelable film 1 with a diol compound having a carboxyl group (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). Contains a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups Forming a curable insulating polyurethane polyurea resin composition layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) Obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5), and an epoxy having two or more epoxy groups. Conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the resin (B), the polyurethane polyurea resin (A) and the epoxy resin (B), and the aziridine-based curing agent (E), Addition of 1 mol of carboxyl group in polyurethane polyurea resin (A) Forming a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing 0.05 to 4 mol of a dinyl group; as well as,
A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I),
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第十四の発明は、
剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The fourteenth invention is
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) are added to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) in the polyurethane polyurea resin (A). Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference,
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing (D), and
A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第十五の発明は、
　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程、
　を含む、ゲル分率が３０～９０重量％の硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The fifteenth invention
Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) are added to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) in the polyurethane polyurea resin (A). Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference and,
A step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II);
And a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight.

　第十六の発明は、
　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程を含む、ゲル分率が３０～９０重量％の硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The sixteenth invention is
Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) Obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5), and an epoxy having two or more epoxy groups. Conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the resin (B), the polyurethane polyurea resin (A) and the epoxy resin (B), and the aziridine-based curing agent (E), Addition of 1 mol of carboxyl group in polyurethane polyurea resin (A) Forming a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing 0.05 to 4 mol of a dinyl group; as well as,
The present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, comprising a step of superposing a peelable film 2 on the curable conductive polyureurethane / polyurea adhesive layer (I).

　第十七の発明は、
　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程を含む、ゲル分率が３０～９０重量％の硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The seventeenth invention
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) are added to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) in the polyurethane polyurea resin (A). Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference,
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (F) having a film-forming ability containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). A gel fraction of 30 from the curable insulating polyurethane polyurea resin composition A step of forming 90% by weight of a curable insulating polyurethane polyurea resin composition layer (II), and a step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II), The present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight.

　第十八の発明は、
　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The eighteenth invention
Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing a curable resin (E) in an amount of 0.05 to 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is formed. Process and
The present invention relates to a method for producing a curable electromagnetic wave shielding adhesive film, comprising a step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II).

　第十九の発明は、
　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The nineteenth invention
Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing a curable resin (E) in an amount of 0.05 to 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) And a polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5) and an epoxy having two or more epoxy groups. Curable conductive polyurethane polyurea adhesive containing resin (B) and 10 to 700 parts by weight of conductive filler with respect to 100 parts by weight of the total of polyurethane polyurea resin (A) and epoxy resin (B) Forming layer (I); and
A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I),
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第二十の発明は、
　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法に関する。 The 20th invention is
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is formed. Process,
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (E) containing a aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C) and having a film-forming ability. A gel fraction of 30 from a curable insulating polyurethane polyurea resin composition Step of Forming 90 wt% of the curable insulating polyurethane polyurea resin composition layer (II) and,
A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this.

　第二十一の発明は、
　第八の発明の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた後に、剥離性フィルム１を剥離することを特徴とする第八の硬化性電磁波シールド性接着性フィルムの使用方法に関する。 The twenty-first invention is
The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, heated, and cured. An eighth curable electromagnetic wave shield characterized by peeling the peelable film 1 after curing the conductive conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) The present invention relates to a method for using an adhesive film.

　第二十二の発明は、
　第八の発明の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、剥離性フィルム１を剥離した後に、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させることを特徴とする第八の硬化性電磁波シールド性接着性フィルムの使用方法に関する。 The twenty-second invention
The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, and the peelable film 1 is attached. An eighth curable electromagnetic wave shielding property characterized by curing after peeling and heating to cure the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) The present invention relates to a method for using an adhesive film.

　第二十三の発明は、
　第六の発明の硬化性電磁波シールド性接着性フィルムの、露出している硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた後に、剥離性フィルム１を剥離することを特徴とする電磁波遮蔽物の製造方法に関する。 The twenty-third invention
The exposed curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the sixth invention is superimposed on an adherend and heated to adhere the curable conductive polyurethane polyurea adhesive. It is related with the manufacturing method of the electromagnetic wave shielding material characterized by peeling the peelable film 1 after hardening agent layer (I) and curable insulating polyurethane polyurea resin composition layer (II).

　第二十四の発明は、
第七の発明の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させることを特徴とする電磁波遮蔽物の製造方法に関する。 The twenty-fourth invention is
The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the seventh invention is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superimposed on the adherend, heated, and cured. The present invention relates to a method for producing an electromagnetic wave shielding material, comprising curing a conductive conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II).

　第二十五の発明は、
　第八の発明の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた後に剥離性フィルム１を剥離することを特徴とする電磁波遮蔽物の製造方法に関する。 The twenty-fifth invention
The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, heated, and cured. It is related with the manufacturing method of the electromagnetic wave shielding material characterized by peeling the peelable film 1 after hardening conductive electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II).

　第二十六の発明は、
　第八の発明の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、剥離性フィルム１を剥離した後に、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させることを特徴とする電磁波遮蔽物の製造方法に関する。 The twenty-sixth invention
The peelable film 2 of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, and the peelable film 1 is attached. It is related with the manufacturing method of the electromagnetic wave shielding material characterized by heating after peeling and hardening the said curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II).

　第二十七の発明は、
　第二十三～第二十六の発明いずれか記載の製造方法により得られた電磁波遮蔽物に関する。 The 27th invention is
The present invention relates to an electromagnetic wave shielding material obtained by the production method according to any of the 23rd to 26th inventions.

　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）は、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部を含有することが好ましい。このような組成の導電性接着剤層（Ｉ）は、薄くても加熱・圧着時において十分なクッション性を発揮してグランド回路上の絶縁フィルム除去部分へ流入する。また、加熱・圧着により、鉛フリーハンダリフローにも十分耐え得る耐熱性を有する。更に、優れた耐屈曲性を有し、フレキシブルプリント配線板に貼着した際に、回路基板全体としての耐屈曲性を損なわない。 The curable conductive polyurethane polyurea adhesive layer (I) preferably contains 3 to 200 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A). Even if the conductive adhesive layer (I) having such a composition is thin, the conductive adhesive layer (I) exhibits a sufficient cushioning property at the time of heating and pressure bonding and flows into the insulating film removal portion on the ground circuit. In addition, it has heat resistance enough to withstand lead-free solder reflow by heating and pressure bonding. Furthermore, it has excellent bending resistance, and does not impair the bending resistance of the entire circuit board when pasted on a flexible printed wiring board.

　本発明の硬化性電磁波シールド性接着性フィルムは、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有することにより、優れた耐湿熱性、及び耐屈曲性を発現することができる。特に、フレキシブルプリント配線板に貼着した後、十分な電磁波シールド性に加えて、鉛フリーハンダリフロー時の高温に耐え得る耐熱性を有し、従来よりも耐屈曲性に優れると共に、高温高湿度下に曝されても〔具体的には、プレッシャークッカーテスト（以下、ＰＣＴという）を経ても〕、導電性ポリウレタンポリウレア接着剤層（Ｉ）の導電性が低下しない。 The curable electromagnetic wave shielding adhesive film of the present invention has excellent moisture and heat resistance by having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II). In addition, bending resistance can be expressed. In particular, after being attached to a flexible printed circuit board, in addition to sufficient electromagnetic shielding properties, it has heat resistance that can withstand high temperatures during lead-free solder reflow, and is superior in bending resistance to high temperatures and humidity. Even when exposed to the bottom (specifically, even after undergoing a pressure cooker test (hereinafter referred to as PCT)), the conductivity of the conductive polyurethane polyurea adhesive layer (I) does not decrease.

　また、本発明の硬化性電磁波シールド性接着性フィルムは、半硬化状態（ゲル分率が３０～９０重量％）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を有することにより、被着体に加熱圧着する際に接着剤が過度にはみ出すことがなく、硬化後においては柔軟で優れた屈曲特性を得ることができる。 Further, the curable electromagnetic wave shielding adhesive film of the present invention has a curable conductive polyurethane polyurea adhesive layer (I) in a semi-cured state (gel fraction is 30 to 90% by weight). The adhesive does not protrude excessively when thermocompression-bonded to the film, and after curing, a flexible and excellent bending property can be obtained.

　更にまた、本発明の硬化性電磁波シールド性接着性フィルムは、半硬化状態（ゲル分率が３０～９０重量％）の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を有することにより、貼着・硬化時の過度な伸びを抑制することができる。 Furthermore, the curable electromagnetic wave shielding adhesive film of the present invention has a curable insulating polyurethane polyurea resin composition layer (II) in a semi-cured state (gel fraction is 30 to 90% by weight). Excessive elongation during wearing and curing can be suppressed.

プレッシャークッカーテスト（PressureCracker Test：ＰＣＴ）耐性評価試験方法の説明図である。図１（１）は、フレキシブルプリント配線板の模式的平面図であり、ポリイミドフィルム１上に回路２Ａ，２Ｂが形成され、回路２Ａの一部が露出するように、スルーホール４を有するカバーフィルム３が積層されている。図１（２）は、図１（１）のＤ－Ｄ’における断面図である。図１（３）は、図１（１）のＣ－Ｃ’における断面図である。図１（４）は、図１（１）～図１（３）に示されるカバーフィルム３及び回路２Ｂ上に、回路２Ａ，２Ｂの一部が露出するように、硬化性電磁波シールド性接着性フィルム５を重ね、圧着、硬化した状態の模式的平面図である。図１（５）は、図１（４）のＤ－Ｄ’における断面図である。図１（６）は、図１（４）のＣ－Ｃ’における断面図である。It is explanatory drawing of a pressure cooker test (PressureCracker Test: PCT) tolerance evaluation test method. FIG. 1A is a schematic plan view of a flexible printed wiring board, in which circuits 2A and 2B are formed on a polyimide film 1, and a cover film having a through hole 4 so that a part of the circuit 2A is exposed. 3 are stacked. FIG. 1B is a cross-sectional view taken along the line D-D ′ in FIG. FIG. 1C is a cross-sectional view taken along the line C-C ′ in FIG. FIG. 1 (4) shows a curable electromagnetic wave shielding adhesive property so that parts of the circuits 2A and 2B are exposed on the cover film 3 and the circuit 2B shown in FIGS. 1 (1) to 1 (3). FIG. 3 is a schematic plan view of a state in which a film 5 is stacked, pressed and cured. FIG. 1 (5) is a cross-sectional view taken along the line D-D 'of FIG. 1 (4). FIG. 1 (6) is a cross-sectional view taken along the line C-C ′ of FIG. 1 (4).

符号の説明Explanation of symbols

　１：ポリイミドフィルム
　２：銅箔回路
　３：カバーレイ（接着剤層は図示せず）
　４：スルーホール
　５：硬化性電磁波シールド性接着性フィルムの硬化物
　５ａ：硬化性絶縁性ポリウレタンポリウレア組成物層（II）の硬化層
　５ｂ：硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の硬化層 1: Polyimide film 2: Copper foil circuit 3: Coverlay (adhesive layer not shown)
4: through hole 5: cured product of curable electromagnetic wave shielding adhesive film 5a: cured layer of curable insulating polyurethane polyurea composition layer (II) 5b: cured curable conductive polyurethane polyurea adhesive layer (I) layer

　本発明の硬化性電磁波シールド性接着性フィルムは、フィルム構成として４つの態様を挙げることができる。
　まず硬化性電磁波シールド性接着性フィルムの態様（１）〔以下、フィルムの態様（１）ともいう〕は、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を有するものである。 The curable electromagnetic wave shielding adhesive film of the present invention can include four embodiments as a film configuration.
First, the mode (1) of the curable electromagnetic wave shielding adhesive film (hereinafter also referred to as the film mode (1)) includes a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition. It has a layer (II).

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）は、ポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する。
　前記ポリウレタンポリウレア樹脂（Ａ）は、末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて生成される。
　また、前記ウレタンプレポリマー（ａ４）は、カルボキシル基を有するジオール化合物（ａ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）と、有機ジイソシアネート（ａ３）とを反応させて生成される。 The curable conductive polyurethane polyurea adhesive layer (I) comprises a polyurethane polyurea resin (A), an epoxy resin (B) having two or more epoxy groups, the polyurethane polyurea resin (A), and the epoxy resin (B And 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight in total.
The polyurethane polyurea resin (A) is produced by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with a polyamino compound (a5).
The urethane prepolymer (a4) reacts a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). To be generated.

　ポリウレタンポリウレア樹脂（Ａ）及びエポキシ樹脂（Ｂ）を含有する接着樹脂組成物は、導電性フィラーを良く分散し、導電性フィラーが含まれていても十分な接着力を発揮し、更に、電磁波シールド性接着性フィルムと被着体との熱圧着時に接着剤層のしみ出しが少ない。そのため鉛フリーハンダリフローに耐えることのできる優れた耐熱性及び耐屈曲性を得ることができる。 The adhesive resin composition containing the polyurethane polyurea resin (A) and the epoxy resin (B) disperses the conductive filler well, exhibits a sufficient adhesive force even when the conductive filler is contained, and further shields against electromagnetic waves. Extrusion of the adhesive layer during thermocompression bonding between the adhesive film and the adherend is small. Therefore, excellent heat resistance and bending resistance that can withstand lead-free solder reflow can be obtained.

　硬化性導電性ポリウレタンウレア接着剤層（Ｉ）に含有されるポリウレタンポリウレア樹脂（Ａ）は、カルボキシル基を有するジオール化合物（ａ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）とを反応させて得られる、末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるものである。
　カルボキシル基を有するジオール化合物（ａ１）としては、ジメチロール酢酸、ジメチロールプロピオン酸、ジメチロールブタン酸、又はジメチロールペンタン酸等のジメチロールアルカン酸（ここで、アルカン酸は、炭素原子数２～８であることが好ましい）や、ジヒドロキシコハク酸、又はジヒドロキシ安息香酸等ジヒドロキシ芳香族カルボン酸（ここで、芳香族カルボン酸は、炭素原子数７～１１であることが好ましい）が挙げられる。その中でも特に反応性、溶解性点から、ジメチロールプロピオン酸、ジメチロールブタン酸が好ましい。前記カルボキシル基を有するジオール化合物（ａ１）は、単独で用いても、２種類以上を併用してもよい。 The polyurethane polyurea resin (A) contained in the curable conductive polyurethaneurea adhesive layer (I) comprises a diol compound having a carboxyl group (a1) and a polyol having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound. It is obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting (a2) and the organic diisocyanate (a3) with a polyamino compound (a5).
Examples of the diol compound (a1) having a carboxyl group include dimethylol alkanoic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, or dimethylolpentanoic acid (wherein alkanoic acid has 2 to 8 carbon atoms). And a dihydroxy aromatic carboxylic acid such as dihydroxy succinic acid or dihydroxy benzoic acid (wherein the aromatic carboxylic acid preferably has 7 to 11 carbon atoms). Among them, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable from the viewpoint of reactivity and solubility. The diol compound (a1) having a carboxyl group may be used alone or in combination of two or more.

　カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）は、一般にポリウレタン樹脂を構成するポリオール成分として知られており、カルボキシル基を有するジオール化合物（ａ１）以外のポリオールである。前記ポリオール（ａ２）の数平均分子量（Ｍｎ）は、得られるポリウレタンポリウレア樹脂（Ａ）の耐熱性、接着強度、及び／又は溶解性等を考慮して適宜決定されるが、好ましくは１０００～５０００である。Ｍｎが５００未満であると、得られるポリウレタンポリウレア樹脂（Ａ）中のウレタン結合が多くなり過ぎ、ポリマー骨格の柔軟性が低下してフレキシブルプリント配線板への接着性が低下する傾向があり、また、Ｍｎが８０００を超えると、ジオール化合物（ａ１）由来のカルボキシル基の、ポリウレタンポリウレア樹脂（Ａ）中における数が減少する。その結果、エポキシ樹脂との反応点が減少するため、得られる導電性硬化接着剤層の耐ハンダリフロー性が低下する傾向にある。 The polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound is generally known as a polyol component constituting the polyurethane resin, and is a polyol other than the diol compound (a1) having a carboxyl group. The number average molecular weight (Mn) of the polyol (a2) is appropriately determined in consideration of the heat resistance, adhesive strength, and / or solubility of the resulting polyurethane polyurea resin (A), and preferably 1000 to 5000. It is. When Mn is less than 500, the number of urethane bonds in the resulting polyurethane polyurea resin (A) increases too much, and the flexibility of the polymer skeleton tends to decrease and the adhesion to the flexible printed wiring board tends to decrease. When Mn exceeds 8000, the number of carboxyl groups derived from the diol compound (a1) in the polyurethane polyurea resin (A) decreases. As a result, since the reaction point with the epoxy resin is reduced, the solder reflow resistance of the obtained conductive cured adhesive layer tends to be lowered.

　カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）としては、各種のポリエーテルポリオール類、ポリエステルポリオール類、ポリカーボネートポリオール類、ポリブタジエングリコール類等が使用できる。
　ポリエーテルポリオール類としては、酸化エチレン、酸化プロピレン、又はテトラヒドロフランなどの重合体又は共重合体等が挙げられる。 As the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols and the like can be used.
Examples of polyether polyols include polymers or copolymers such as ethylene oxide, propylene oxide, or tetrahydrofuran.

　ポリエステルポリオール類としては、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３－メチル－１，５－ペンタンジオール、ヘキサンジオール、オクタンジオール、１，４－ブチレンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、もしくはダイマージオール等の飽和又は不飽和の低分子ジオール類と、アジピン酸、フタル酸、イソフタル酸、テレフタル酸、マレイン酸、フマル酸、コハク酸、シュウ酸、マロン酸、グルタル酸、ピメリン酸、スベリン酸、アゼライン酸、もしくはセバシン酸等のジカルボン酸類、又はこれらの無水物類を反応させて得られるポリエステルポリオール類や、ｎ－ブチルグリシジルエーテル、又は２－エチルヘキシルグリシジルエーテル等のアルキルグリシジルエーテル類、バーサティック酸グリシジルエステル等のモノカルボン酸グリシジルエステル類と上記のジカルボン酸類の無水物類とをアルコール類などの水酸基含有化合物の存在下で反応させて得られるポリエステルポリオール類、又は環状エステル化合物を開環重合して得られるポリエステルポリオール類が挙げられる。 Polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, Saturated or unsaturated low-molecular diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimer diol, adipic acid, phthalic acid, Reaction with dicarboxylic acids such as 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 their anhydrides Poly obtained Steal polyols, alkyl glycidyl ethers such as n-butyl glycidyl ether or 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, and anhydrides of the above dicarboxylic acids and alcohols And polyester polyols obtained by reacting in the presence of a hydroxyl group-containing compound such as, or polyester polyols obtained by ring-opening polymerization of a cyclic ester compound.

　ポリカーボネートポリオール類としては、例えば、
１）グリコール又はビスフェノールと炭酸エステルとの反応生成物、あるいは
２）グリコール又はビスフェノールにアルカリの存在下でホスゲンを反応させて得られる反応生成物等が使用できる。
　上記１）又は２）の反応生成物の調製に用いられるグリコールとしては、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、３－メチル－１，５－ペンタンジオール、２－メチル－１，８－オクタンジオール、３，３’－ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，９－ノナンジオール、ネオペンチルグリコール、オクタンジオール、ブチルエチルペンタンジオール、２－エチル－１，３－ヘキサンジオール、シクロヘキサンジオール、３，９－ビス（１，１－ジメチル－２－ヒドロキシエチル、又は２，２，８，１０－テトラオキソスピロ〔５．５〕ウンデカンが挙げられる。 Examples of polycarbonate polyols include:
1) A reaction product of glycol or bisphenol and a carbonate ester, or 2) a reaction product obtained by reacting glycol or bisphenol with phosgene in the presence of an alkali can be used.
Examples of the glycol used for the preparation of the reaction product 1) or 2) 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'-dimethylolheptane, 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-Di Examples include methyl-2-hydroxyethyl or 2,2,8,10-tetraoxospiro [5.5] undecane.

　また、上記１）又は２）の反応生成物の調製に用いられるビスフェノールとしては、例えば、ビスフェノールＡやビスフェノールＦ等のビスフェノール類や、これらのビスフェノール類にエチレンオキサイド又はプロピレンオキサイド等のアルキレンオキサイドを付加させた化合物等が挙げられる。
　また、上記１）の反応生成物の調製に用いられる炭酸エステルとしては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、又はプロピレンカーボネート等が挙げられる。 Moreover, as bisphenol used for preparation of the reaction product of said 1) or 2), for example, bisphenols, such as bisphenol A and bisphenol F, and alkylene oxides, such as ethylene oxide or propylene oxide, are added to these bisphenols. And the like.
Examples of the carbonic acid ester used for the preparation of the reaction product 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or propylene carbonate.

　カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）として例示した各種ポリオールは、単独で用いても、２種類以上併用してもよい。
　更に、得られるポリウレタンポリウレア樹脂（Ａ）の性能が失われない範囲内で、カルボキシル基を有するジオール化合物（ａ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）とを反応させる際に、カルボキシル基含有ジオール化合物以外の低分子ジオール類（すなわち、数平均分子量５００未満のジオール類）を併用してもよい。併用可能な低分子ジオール類としては、例えば、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）の製造に用いられる各種低分子ジオール等が挙げられる。 Various polyols exemplified as the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound may be used alone or in combination of two or more.
Further, within the range in which the performance of the resulting polyurethane polyurea resin (A) is not lost, a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and When reacting with the organic diisocyanate (a3), low molecular diols other than the carboxyl group-containing diol compound (that is, diols having a number average molecular weight of less than 500) may be used in combination. Examples of the low molecular diols that can be used in combination include various low molecular diols used for the production of polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound.

　ウレタンプレポリマー（ａ４）を合成する際に、カルボキシル基を有するジオール化合物（ａ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）とは、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）１モルに対して、カルボキシル基を有するジオール化合物（ａ１）０．１モル～４．０モルとなる比率で用いることが好ましく、０．２モル～３．０モルとなる比率で用いることがより好ましい。ポリオール（ａ２）１モルに対するカルボキシル基含有ジオール化合物（ａ１）の使用量が０．１モルより少ないと、エポキシ樹脂（Ｂ）と架橋可能なカルボキシル基が少なくなり、耐ハンダリフロー性が低下する傾向にある。また、４．０モルより多いと、接着性が低下する傾向にある。 When the urethane prepolymer (a4) is synthesized, the diol compound (a1) having a carboxyl group and the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound are other than the carboxyl group-containing diol compound. The diol compound (a1) having a carboxyl group is preferably used in a ratio of 0.1 mol to 4.0 mol with respect to 1 mol of the polyol (a2) having a number average molecular weight of 500 to 8000, from 0.2 mol to More preferably, it is used at a ratio of 3.0 moles. When the amount of the carboxyl group-containing diol compound (a1) used relative to 1 mol of the polyol (a2) is less than 0.1 mol, the number of carboxyl groups capable of crosslinking with the epoxy resin (B) decreases, and the solder reflow resistance tends to decrease. It is in. On the other hand, when the amount is more than 4.0 mol, the adhesiveness tends to decrease.

　有機ジイソシアネート（ａ３）としては、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族イソシアネート、又はこれらの混合物を使用できるが、特にイソホロンジイソシアネートが好ましい。 As the organic diisocyanate (a3), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable.

　芳香族ジイソシアネートとしては、例えば、１，５－ナフチレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルジメチルメタンジイソシアネート、４，４’－ベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、トリレンジイソシアネート、又はキシリレンジイソシアネート等が挙げられる。 Examples of the aromatic diisocyanate include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like.

　脂肪族ジイシシアネートとしては、例えば、ブタン－１，４－ジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、又はリジンジイソシアネート等が挙げられる。 Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or lysine diisocyanate.

　脂環族ジイソシアネートとしては、例えば、シクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、１，３－ビス（イソシアネートメチル）シクロヘキサン、又はメチルシクロヘキサンジイソシアネート等が挙げられる。 Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and the like.

　末端にイソシアネート基を有するウレタンプレポリマー（ａ４）は、カルボキシル基を有するジオール化合物（ａ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）とを反応させることにより得られる。末端にイソシアネート基を有するウレタンプレポリマー（ａ４）を合成する際の条件は、イソシアネート基が過剰になるようにする他にとくに限定はないが、イソシアネート基／水酸基の当量比が１．２／１～３／１の範囲内になるような割合で、カルボキシル基を有するジオール化合物（ａ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）とを反応させることが好ましい。また、反応温度は通常常温～１２０℃であるが、更に製造時間、副反応の制御の面から６０～１００℃が好ましい。 The urethane prepolymer (a4) having an isocyanate group at the end includes a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). It is obtained by reacting. The conditions for synthesizing the urethane prepolymer (a4) having an isocyanate group at the terminal are not particularly limited except that the isocyanate group becomes excessive, but the equivalent ratio of isocyanate group / hydroxyl group is 1.2 / 1. A diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) Is preferably reacted. The reaction temperature is usually from room temperature to 120 ° C., but is preferably from 60 to 100 ° C. from the viewpoint of production time and side reaction control.

　ポリウレタンポリウレア樹脂（Ａ）は、末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られる。
　ポリアミノ化合物（ａ５）としては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、又はイソホロンジアミン、ジシクロヘキシルメタン－４，４’－ジアミンの他、２－（２－アミノエチルアミノ）エタノール、２－ヒドロキシエチルエチレンジアミン、２－ヒドロキシエチルプロピレンジアミン、ジ－２－ヒドロキシエチルエチレンジアミン、又はジ－２－ヒドロキシプロピルエチレンジアミン等の水酸基を有するアミン類も使用することができる。なかでも、イソホロンジアミンが好適に使用される。 The polyurethane polyurea resin (A) is obtained by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5).
Examples of the polyamino compound (a5) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or isophoronediamine, dicyclohexylmethane-4,4′-diamine, 2- (2-aminoethylamino) ethanol, Amines having a hydroxyl group such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, or di-2-hydroxypropylethylenediamine can also be used. Of these, isophoronediamine is preferably used.

　末端にイソシアネート基を有するウレタンプレポリマー（ａ４）とポリアミノ化合物（ａ５）とを反応させてポリウレタンポリウレア樹脂（Ａ）を合成するときには、分子量を調整する為に反応停止剤を併用することができる。反応停止剤としては、ジ－ｎ－ブチルアミン等のジアルキルアミン類、ジエタノールアミン等のジアルカノールアミン類や、エタノール、イソプロピルアルコール等のアルコール類が使用できる。 When synthesizing the polyurethane polyurea resin (A) by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), a reaction terminator can be used in combination. As the reaction terminator, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

　末端にイソシアネート基を有するウレタンプレポリマー（ａ４）、ポリアミノ化合物（ａ５）及び必要に応じて反応停止剤を反応させる際の条件は、とくに限定はないが、ウレタンプレポリマー（ａ４）が有するイソシアネート基に対する、ポリアミノ化合物（ａ５）及び反応停止剤中のアミノ基の合計の当量比が０．５～１．３の範囲内であることが好ましい。当量比が０．５未満の場合には、耐ハンダリフロー性が不十分になりやすく、１．３より多い場合には、ポリアミノ化合物（ａ５）及び／又は反応停止剤が未反応のまま残存し、臭気が残りやすくなる。 The conditions for reacting the urethane prepolymer (a4) having an isocyanate group at the terminal, the polyamino compound (a5) and, if necessary, the reaction terminator are not particularly limited, but the isocyanate group possessed by the urethane prepolymer (a4) The total equivalent ratio of the polyamino compound (a5) and the amino groups in the reaction terminator is preferably in the range of 0.5 to 1.3. When the equivalent ratio is less than 0.5, the solder reflow resistance tends to be insufficient, and when it exceeds 1.3, the polyamino compound (a5) and / or the reaction terminator remain unreacted. , The odor tends to remain.

　ポリウレタンポリウレア樹脂（Ａ）を合成する際に用いられる溶剤としては、ベンゼン、トルエン、キシレン等の芳香族系溶剤、メタノール、エタノール、イソプロパノール、又はｎ－ブタノール等のアルコール系溶剤、アセトン、メチルエチルケトン、又はメチルイソブチルケトン等のケトン系溶剤、酢酸エチル、又は酢酸ブチル等のエステル系溶剤が挙げられる。これらの溶剤は、１種を単独で、又は２種以上を混合して用いることができる。
　得られるポリウレタンポリウレア樹脂（Ａ）の重量平均分子量は、５０００～１０００００の範囲にあることが好ましい。重量平均分子量が５０００に満たない場合には、耐ハンダリフロー性が劣る傾向にあり、１０００００を超える場合には、接着性が低下する傾向にある。また、ポリウレタンポリウレア樹脂（Ａ）は、酸価が３～２５ｍｇＫＯＨ／ｇであることが好ましく、７～２０ｍｇＫＯＨ／ｇがより好ましい。なお前記数値範囲以外でも使用できるが、耐熱性と屈曲性の両立が困難になる可能性がある。 Solvents used in the synthesis of the polyurethane polyurea resin (A) include aromatic solvents such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, isopropanol, and n-butanol, acetone, methyl ethyl ketone, or Examples include ketone solvents such as methyl isobutyl ketone, and ester solvents such as ethyl acetate or butyl acetate. These solvents can be used alone or in combination of two or more.
The weight average molecular weight of the resulting polyurethane polyurea resin (A) is preferably in the range of 5000 to 100,000. When the weight average molecular weight is less than 5,000, the solder reflow resistance tends to be inferior, and when it exceeds 100,000, the adhesion tends to be lowered. The polyurethane polyurea resin (A) preferably has an acid value of 3 to 25 mgKOH / g, more preferably 7 to 20 mgKOH / g. Although it can be used outside the above numerical range, it may be difficult to achieve both heat resistance and flexibility.

　また、硬化性導電性ポリウレタンウレア接着剤層（Ｉ）に含有されるエポキシ樹脂（Ｂ）は、２個以上のエポキシ基を有する樹脂であり、液状であっても固形状であってもよい。
　エポキシ樹脂（Ｂ）としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、スピロ環型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テルペン型エポキシ樹脂、トリス（グリシジルオキシフェニル）メタン、又はテトラキス（グリシジルオキシフェニル）エタンなどのグリシジルエーテル型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタンなどのグリシジルアミン型エポキシ樹脂、テトラブロムビスフェノールＡ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、α－ナフトールノボラック型エポキシ樹脂、又は臭素化フェノールノボラック型エポキシ樹脂等が挙げられる。これらのエポキシ樹脂は、１種を単独で、又は２種以上を組み合わせて用いることができる。これらのうち高接着性、耐熱性の点から、ビスフェノールＡ型エポキシ樹脂やクレゾールノボラック型エポキシ樹脂、又はテトラキス（グリシジルオキシフェニル）エタン型エポキシ樹脂を用いることが好ましい。エポキシ樹脂（Ｂ）は、エポキシ当量が１００～１５００ｇ／ｅｑであることが好ましく、１５０～７００ｇ／ｅｑであることがより好ましい。前記数値範囲以外でも使用できるが、耐熱性と屈曲性の両立が困難になる可能性がある。 The epoxy resin (B) contained in the curable conductive polyurethane urea adhesive layer (I) is a resin having two or more epoxy groups, and may be liquid or solid.
As the epoxy resin (B), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, terpene type epoxy resin, tris (glycidyl) Glycidyl ether type epoxy resin such as oxyphenyl) methane or tetrakis (glycidyloxyphenyl) ethane, Glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane, Tetrabromobisphenol A type epoxy resin, Cresol novolak type epoxy resin, Phenol novolak type Examples thereof include an epoxy resin, an α-naphthol novolak type epoxy resin, and a brominated phenol novolak type epoxy resin. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a tetrakis (glycidyloxyphenyl) ethane type epoxy resin from the viewpoint of high adhesion and heat resistance. The epoxy resin (B) preferably has an epoxy equivalent of 100 to 1500 g / eq, more preferably 150 to 700 g / eq. Although it can be used outside the numerical range, it may be difficult to achieve both heat resistance and flexibility.

　本発明で用いられる硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）において、エポキシ樹脂と（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率は、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。ポリウレタンポリウレア樹脂（Ａ）１００重量部に対してエポキシ樹脂（Ｂ）が３重量部より少ないと、耐ハンダリフロー性が低くなる傾向がある。一方、エポキシ樹脂（Ｂ）が２００重量部より多いと、接着性が低下する傾向がある
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 In the curable conductive polyurethane polyurea adhesive layer (I) used in the present invention, the blending ratio of the epoxy resin, (B), and polyurethane polyurea resin (A) is 100 parts by weight of the polyurethane polyurea resin (A). The epoxy resin (B) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight. When the amount of the epoxy resin (B) is less than 3 parts by weight relative to 100 parts by weight of the polyurethane polyurea resin (A), the solder reflow resistance tends to be lowered. On the other hand, when the amount of the epoxy resin (B) is more than 200 parts by weight, the adhesiveness tends to decrease. The curable conductive polyurethane polyurea adhesive layer (I) does not impair the performance such as heat resistance and flex resistance. Within a range, one or more of a phenol resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.

　また、硬化性導電性ポリウレタンポリウレア接着剤層に含有される導電性フィラーは、接着剤層に導電性を付与するものであり、導電性フィラーとしては、金属フィラー、カーボンフィラー又はそれらの混合物が用いられる。
　金属フィラーとしては、銀、銅、又はニッケル等の金属粉、ハンダ等の合金粉、銀メッキされた銅粉、又は金属メッキされたガラス繊維やカーボンフィラーなどが挙げられる。なかでも、導電率の高い銀フィラーが好ましく、特にフィラー同士の接触を得やすい比表面積０．５～２．５ｍ２／ｇである銀フィラーが好ましい。
　また、導電性フィラーの形状としては、球状、フレーク状、樹枝状、又は繊維状などが挙げられる。 Moreover, the conductive filler contained in the curable conductive polyurethane polyurea adhesive layer imparts conductivity to the adhesive layer, and as the conductive filler, a metal filler, a carbon filler, or a mixture thereof is used. It is done.
Examples of the metal filler include metal powder such as silver, copper, or nickel, alloy powder such as solder, copper powder plated with silver, or glass fiber or carbon filler plated with metal. Among them, a silver filler having a high electrical conductivity is preferable, and a silver filler having a specific surface area of 0.5 to 2.5 m 2 / g that facilitates contact between the fillers is particularly preferable.
In addition, examples of the shape of the conductive filler include a spherical shape, a flake shape, a dendritic shape, and a fibrous shape.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）における導電性フィラーの含有量は、必要とする電磁波シールド効果の度合いによって異なるが、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）との合計１００重量部に対して、導電性フィラーは１０～７００重量部であり、５０～５００重量部であることが好ましい。導電性フィラーの含有量が１０重量部を下回ると、導電性フィラー同士が十分に接触せず、高い導電性が得られない。そのため電磁波シールド効果が不十分となりやすい。また、導電性フィラーの含有量が７００重量部を超えても、硬化性導電性ポリウレタンポリウレア接着剤層の表面抵抗値は下がらなくなり、電導率が飽和状態に達する上に、硬化性導電性ポリウレタンポリウレア接着剤層中の導電性フィラーの量が過多となり、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の基材フィルムへの密着性や接着力が低下する。接着剤層（Ｉ）の接着力は、ポリイミドフィルムに対して接着力１Ｎ／ｃｍ以上であることが好ましい。１Ｎ／ｃｍ未満でも使用できるが、被着体との密着が不足する可能性がある。 The content of the conductive filler in the curable conductive polyurethane polyurea adhesive layer (I) varies depending on the required degree of electromagnetic shielding effect, but the total weight of the polyurethane polyurea resin (A) and the epoxy resin (B) is 100 weight. The conductive filler is 10 to 700 parts by weight, preferably 50 to 500 parts by weight, based on parts. When content of an electroconductive filler is less than 10 weight part, electroconductive fillers do not fully contact and high electroconductivity is not acquired. Therefore, the electromagnetic wave shielding effect tends to be insufficient. In addition, even when the content of the conductive filler exceeds 700 parts by weight, the surface resistance value of the curable conductive polyurethane polyurea adhesive layer does not decrease, the conductivity reaches a saturated state, and the curable conductive polyurethane polyurea The amount of the conductive filler in the adhesive layer becomes excessive, and the adhesion and adhesive force of the curable conductive polyurethane polyurea adhesive layer (I) to the base film are lowered. The adhesive force of the adhesive layer (I) is preferably an adhesive force of 1 N / cm or more with respect to the polyimide film. Although it can be used even if it is less than 1 N / cm, there is a possibility that adhesion to the adherend is insufficient.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）との反応や、エポキシ樹脂（Ｂ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる。エポキシ樹脂（Ｂ）の硬化促進剤としては、３級アミン化合物、ホスフィン化合物、イミダゾール化合物等が使用でき、硬化剤としては、ジシアンジアミド、カルボン酸ヒドラジド、又は酸無水物等が使用できる。 In the curable conductive polyurethane polyurea adhesive layer (I), curing is promoted for the purpose of accelerating the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) or the reaction of the epoxy resin (B) alone. An agent and / or a curing agent can be contained. As the curing accelerator for the epoxy resin (B), tertiary amine compounds, phosphine compounds, imidazole compounds and the like can be used, and as the curing agent, dicyandiamide, carboxylic acid hydrazide, acid anhydrides and the like can be used.

　硬化促進剤のうち、３級アミン化合物としては、トリエチルアミン、ベンジルジメチルアミン、１，８－ジアザビシクロ（５．４．０）ウンデセン－７、又は１，５－ジアザビシクロ（４．３．０）ノネン－５等が挙げられる。また、ホスフィン化合物としては、トリフェニルホスフィン、又はトリブチルホスフィン等が挙げられる。また、イミダゾール化合物としては、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニル－４－メチルイミダゾール、２，４－ジメチルイミダゾール、又は２－フェニルイミダゾール等のイミダゾール化合物が挙げられ、更にはイミダゾール化合物とエポキシ樹脂を反応させて溶剤に不溶化したタイプ、又はイミダゾール化合物をマイクロカプセルに封入したタイプ等の保存安定性を改良した潜在性硬化促進剤が挙げられるが、これらの中でも、潜在性硬化促進剤が好ましい。 Of the curing accelerators, tertiary amine compounds include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, or 1,5-diazabicyclo (4.3.0) nonene- 5 etc. are mentioned. Examples of the phosphine compound include triphenylphosphine or tributylphosphine. Examples of the imidazole compound include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenylimidazole. Furthermore, latent curing accelerators with improved storage stability such as a type in which an imidazole compound and an epoxy resin are reacted to insolubilize in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule can be mentioned. Preferred curing accelerators are preferred.

　硬化剤としてのカルボン酸ヒドラジドとしては、コハク酸ヒドラジド、又はアジピン酸ヒドラジド等が挙げられる。また、酸無水物としては、無水ヘキサヒドロフタル酸、又は無水トリメリット酸等が挙げられる。 Examples of the carboxylic acid hydrazide as the curing agent include succinic acid hydrazide and adipic acid hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride, trimellitic anhydride, and the like.

　これらの硬化促進剤又は硬化剤としては、それぞれ２種類以上を併用してもよく、その使用量は合計で（硬化促進剤又は硬化剤のどちらか一方のみを使用する場合も含まれる）、エポキシ樹脂（Ｂ）１００重量部に対して０．１～３０重量部の範囲であることが好ましい。 As these curing accelerators or curing agents, two or more kinds may be used in combination, and the amount used is a total (including the case where only one of the curing accelerator or the curing agent is used), and epoxy. The amount is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin (B).

　また、硬化性導電性ポリウレタンポリウレア接着剤層には、導電性、接着性、及び／又は耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 In addition, the curable conductive polyurethane polyurea adhesive layer has a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a range that does not deteriorate conductivity, adhesiveness, and / or solder reflow resistance. You may add 1 or more types, such as a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

　続いて、本発明で用いる硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）について説明する。硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、硬化性電磁波シールド性接着性フィルムに機械的強度を与える役割を担う。即ち、未硬化状態（硬化前）でも基材ないし担体としての機能を有し、例えば、特許文献４における基材フィルムに当たる。 Subsequently, the curable insulating polyurethane polyurea resin composition layer (II) used in the present invention will be described. The curable insulating polyurethane polyurea resin composition layer (II) plays a role of giving mechanical strength to the curable electromagnetic wave shielding adhesive film. That is, it has a function as a substrate or carrier even in an uncured state (before curing), and hits the substrate film in Patent Document 4, for example.

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、ポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する。
　前記ポリウレタンポリウレア樹脂（Ｃ）は、末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて生成される。
　また、前記ウレタンプレポリマー（ｃ４）は、カルボキシル基を有するジオール化合物（ｃ１）と、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）と、有機ジイソシアネート（ｃ３）とを反応させて生成される。 The curable insulating polyurethane polyurea resin composition layer (II) contains a polyurethane polyurea resin (C) and an epoxy resin (D) having two or more epoxy groups.
The polyurethane polyurea resin (C) is produced by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5).
The urethane prepolymer (c4) reacts a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). To be generated.

　ポリウレタンポリウレア樹脂（Ｃ）及びエポキシ樹脂（Ｄ）を含有する接着樹脂組成物層（II）は、熱圧着時の接着剤層のしみ出しが少なく、鉛フリーハンダリフローに耐え得る、優れた耐熱性及び耐屈曲性を得ることができる。 Adhesive resin composition layer (II) containing polyurethane polyurea resin (C) and epoxy resin (D) has less exudation of the adhesive layer during thermocompression bonding and has excellent heat resistance that can withstand lead-free solder reflow In addition, bending resistance can be obtained.

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）に含有されるポリウレタンポリウレア樹脂（Ｃ）としては、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）に含有されるポリウレタンポリウレア樹脂（Ａ）と同様のものを挙げることができる。
　２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）についても、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と同様のものを挙げることができる。
　エポキシ樹脂（Ｄ）とポリウレタンポリウレア樹脂（Ｃ）との配合比率も、エポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ｃ）１００重量部に対して、エポキシ樹脂（Ｄ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。 The polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) is the same as the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I). Can be mentioned.
The epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (B) having two or more epoxy groups.
The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) with respect to 100 parts by weight of the polyurethane polyurea resin (C). The epoxy resin (D) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight.

　更に、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 Further, like the curable conductive polyurethane polyurea adhesive layer (I), the curable insulating polyurethane polyurea resin composition layer (II) has a phenol content within a range that does not impair the performance such as heat resistance and flex resistance. One or more of a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.

　また、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）との反応や、エポキシ樹脂（Ｄ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。
　また、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様に、接着性、及び／又は耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (C) and an epoxy resin (D), and reaction of an epoxy resin (D) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
Further, in the curable insulating polyurethane polyurea resin composition layer (II), as in the case of the curable conductive polyurethane polyurea adhesive layer (I), a range in which the adhesion and / or solder reflow resistance is not deteriorated. Add one or more of silane coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. May be.

　本発明によるフィルムの態様（１）において、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、導電性フィラーの有無を除き、同一組成のポリウレタンポリウレア樹脂組成物からなることも、あるいは異なる組成のポリウレタンポリウレア樹脂組成物からなることもできる。また、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、いずれも未硬化（硬化前）の固化されたドライ状態であり、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のみからなる場合でも全体としてフィルム状となるので、特に支持体又は担体を必要としないが、後述するように、剥離性シートに貼着した状態で保存することもできる。 In the aspect (1) of the film according to the present invention, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) except for the presence or absence of a conductive filler, It can consist of polyurethane polyurea resin compositions of the same composition, or can consist of polyurethane polyurea resin compositions of different compositions. The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in an uncured (before curing) solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.

　次に、本発明における硬化性電磁波シールド性接着性フィルムの態様（２）〔以下、フィルムの態様（２）ともいう〕について説明する。 Next, the embodiment (2) of the curable electromagnetic wave shielding adhesive film in the present invention (hereinafter also referred to as the film embodiment (2)) will be described.

　フィルムの態様（２）は、アジリジン系硬化剤（Ｅ）を含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有することにより、硬化後において柔軟で屈曲特性に優れ、ＰＣＴを経ても導電性が低下しないという効果を維持したまま、更に、被着体に加熱圧着する際に接着剤が貼着領域から過度にはみ出すことがないという追加の効果を示す。 The mode (2) of the film has a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine-based curing agent (E) and a curable insulating polyurethane polyurea resin composition layer (II). In addition, the adhesive may be excessively protruded from the sticking area when it is heat-bonded to the adherend while maintaining the effect that it is flexible and excellent in bending characteristics after curing and the conductivity is not lowered even after PCT. Shows the additional effect of not.

　フィルムの態様（２）は、具体的には、ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する硬化性電磁波シールド性接着性フィルムである。
　ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）は、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーと、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有するものである。 Specifically, the film mode (2) includes a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulating polyurethane polyurea resin composition layer (II). Is a curable electromagnetic wave shielding adhesive film.
The curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight comprises a diol compound having a carboxyl group (a1) and a polyol having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound ( polyurethane polyurea resin (A) obtained by reacting urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting a2) and organic diisocyanate (a3) with polyamino compound (a5), and two 10 to 700 parts by weight of a conductive filler with respect to a total of 100 parts by weight of the epoxy resin (B) having the above epoxy group, the polyurethane polyurea resin (A) and the epoxy resin (B), and an aziridine-based curing Agent (E) is a carboxyl group in the polyurethane polyurea resin (A). Mol, those containing in a range of from 0.05 to 4 moles of an aziridinyl group.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）に含有されるポリウレタンポリウレア樹脂（Ａ）としては、フィルムの態様（１）で説明したポリウレタンポリウレア樹脂（Ａ）と同様のものを挙げることができる。
　また、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）についても、フィルムの態様（１）で説明した２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と同様のものを挙げることができる。
　またエポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率も、フィルムの態様（１）で説明したエポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。 Examples of the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I) include those similar to the polyurethane polyurea resin (A) described in the embodiment (1) of the film.
Moreover, about the epoxy resin (B) which has 2 or more epoxy groups, the thing similar to the epoxy resin (B) which has 2 or more epoxy groups demonstrated in the aspect (1) of the film can be mentioned.
Further, the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film. The amount of the epoxy resin (B) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the resin (A).

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）に用いられるアジリジン系硬化剤（Ｅ）としては、アジリジニル基を２つ以上有する化合物であることが好ましい。具体的には、トリメチロールプロパン－トリ－β－アジリジニルプロピオネート、テトラメチロールメタン－トリ－β－アジリジニルプロピオネート、Ｎ，Ｎ’－ジフェニルメタン－４，４’－ビス（１－アジリジンカルボキシアミド）、又はＮ，Ｎ’－ヘキサメチレン－１，６－ビス（１－アジリジンカルボキシアミド）等が挙げられる。 The aziridine-based curing agent (E) used for the curable conductive polyurethane polyurea adhesive layer (I) is preferably a compound having two or more aziridinyl groups. Specifically, trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1 -Aziridinecarboxamide), or N, N′-hexamethylene-1,6-bis (1-aziridinecarboxyamide).

　アジリジン系硬化剤（Ｅ）を使用することにより、アジリジニル基とポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基との高い反応性を利用して、特別なエージングを必要とせず、両者を反応させ、半硬化状態にさせることができる。つまり、両者を反応させ、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率を３０～９０重量％とすることによって、加熱圧着時に貼着領域から硬化性導電性接着剤層がはみ出すのを低減することができる。硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率は、５０～８５重量％であることが好ましく、６０～８０重量％であることがより好ましい。 By using the aziridine-based curing agent (E), by utilizing the high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (A), both are reacted without requiring special aging. It can be in a cured state. That is, by reacting both, the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is set to 30 to 90% by weight, so that the curable conductive adhesive layer protrudes from the sticking region during thermocompression bonding. Can be reduced. The gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率が３０重量％未満の場合、即ち、ポリウレタンウレア樹脂（Ａ）の大半が未反応で残っている場合、加熱圧着工程における接着剤のはみ出しの低減をほとんど期待できない。一方、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率が９０重量％を超える場合、加熱圧着工程に至る前にポリウレタンウレア樹脂（Ａ）の大半がアジリジン系硬化剤（Ｅ）と既に反応・硬化してしまうので、被着体との接着性を確保しにくくなる。 When the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is less than 30% by weight, that is, when most of the polyurethane urea resin (A) remains unreacted, Almost no reduction in overhang can be expected. On the other hand, when the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, the polyurethane urea resin (A) is mostly composed of the aziridine-based curing agent (E) before the thermocompression bonding step. Since it has already reacted and cured, it becomes difficult to ensure adhesion with the adherend.

　ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を得るためには、ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対して、アジリジニル基が０．０５～４モルの範囲でアジリジン系硬化剤（Ｅ）を含有することが重要であり、０．２～２モルの範囲で含有することが好ましく、０．４～１モルの範囲で含有することがより好ましい。
　ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対して、アジリジン系硬化剤（Ｅ）のアジリジニル基が０．０５モル倍未満の場合、加熱圧着工程時の接着剤のはみ出しを効果的に低減するほどには、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を得る際に、ポリウレタンポリウレア樹脂（Ａ）の硬化・架橋が進行しない。他方、カルボキシル基１モルに対して、アジリジニル基が４モルより多いと、ポリウレタンポリウレア樹脂（Ａ）の反応・硬化が過度に進行してしまうので、加熱圧着工程の際に硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が被着体を十分に濡らすことができず、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）との反応も期待できず、被着体に対する接着性が確保できない。 In order to obtain a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight, 0.05 mol of aziridinyl groups per mol of carboxyl groups in the polyurethane polyurea resin (A). It is important to contain the aziridine curing agent (E) in the range of ˜4 mol, preferably in the range of 0.2 to 2 mol, and in the range of 0.4 to 1 mol. More preferred.
When the aziridinyl group of the aziridine-based curing agent (E) is less than 0.05 mol times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (A), it effectively reduces the protrusion of the adhesive during the thermocompression bonding process. Thus, when the curable conductive polyurethane polyurea adhesive layer (I) is obtained, the curing / crosslinking of the polyurethane polyurea resin (A) does not proceed. On the other hand, if the amount of aziridinyl group is more than 4 moles relative to 1 mole of carboxyl group, the reaction / curing of the polyurethane polyurea resin (A) proceeds excessively. The adhesive layer (I) cannot sufficiently wet the adherend, and the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) cannot be expected, and adhesion to the adherend cannot be ensured.

　なお、本発明でいう「ゲル分率」とは以下のようにして求めることができる。
　１００メッシュの金網を幅３０ｍｍ、長さ１００ｍｍに裁断し、その金網の重量（Ｗ１）を測定する。続いて、剥離性フィルム２上に形成した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）から剥離性フィルム２を除去し、幅１０ｍｍ、長さ８０ｍｍの硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を前述の金網で包み、試験片とし、その試験片の重量（Ｗ２）を測定する。作製した試験片をメチルエチルケトン（以下、ＭＥＫという）中に浸漬させ室温で１時間振とうした後、試験片をＭＥＫから取り出し、１５０℃で１０分間乾燥した後、乾燥後の試験片の重量（Ｗ３）を測定する。下記計算式［Ｉ］を用いて、溶解せずに金網に残った接着剤の重量（Ｗ）をゲル分率として算出する。
Ｗ＝〔（Ｗ３－Ｗ１）／（Ｗ２－Ｗ１）〕×１００　［％］　　［Ｉ］ The “gel fraction” as used in the present invention can be determined as follows.
A 100-mesh wire mesh is cut into a width of 30 mm and a length of 100 mm, and the weight (W1) of the wire mesh is measured. Subsequently, the peelable film 2 is removed from the curable conductive polyurethane polyurea adhesive layer (I) formed on the peelable film 2, and a curable conductive polyurethane polyurea adhesive layer (I having a width of 10 mm and a length of 80 mm). ) Is wrapped with the above-mentioned wire mesh to make a test piece, and the weight (W2) of the test piece is measured. The prepared test piece was immersed in methyl ethyl ketone (hereinafter referred to as MEK) and shaken at room temperature for 1 hour. Then, the test piece was taken out of the MEK and dried at 150 ° C. for 10 minutes, and then the weight of the test piece after drying (W3 ). Using the following calculation formula [I], the weight (W) of the adhesive remaining on the wire mesh without being dissolved is calculated as a gel fraction.
W = [(W3-W1) / (W2-W1)] × 100 [%] [I]

　フィルムの態様（２）の硬化性電磁波シールド性接着性フィルムの硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、フィルムの態様（１）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 In the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film aspect (2), the curable conductive polyurethane polyurea adhesive layer (I) of the film aspect (1) In the same manner as in the above, 1 such as phenol resin, silicone resin, urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, as long as the performance such as heat resistance and flex resistance is not impaired. Seeds or more can be included.

　また、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）との反応や、エポキシ樹脂（Ｂ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、フィルムの態様（１）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (A) and an epoxy resin (B), and reaction of an epoxy resin (B) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I) of the film mode (1).

　また、フィルムの態様（２）の硬化性電磁波シールド性接着性フィルムの硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、フィルムの態様（１）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、接着性、及び／又は耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 In addition, the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film aspect (2) includes the curable conductive polyurethane polyurea adhesive layer (I) of the film aspect (1). Similar to I), silane coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, as long as adhesion and / or solder reflow resistance are not deteriorated. You may add 1 type or more, such as a leveling regulator, a filler, or a flame retardant.

　一方、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成される。 On the other hand, the curable insulating polyurethane polyurea resin composition layer (II) comprises a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). ) Obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy having two or more epoxy groups. It is formed from a curable insulating polyurethane polyurea resin composition having a film-forming ability, containing the resin (D).

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）に含有されるポリウレタンポリウレア樹脂（Ｃ）としては、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）に含有されるポリウレタンポリウレア樹脂（Ａ）と同様のものを挙げることができる。
　２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）についても、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と同様のものを挙げることができる。
　エポキシ樹脂（Ｄ）とポリウレタンポリウレア樹脂（Ｃ）との配合比率も、エポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ｃ）１００重量部に対して、エポキシ樹脂（Ｄ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。 The polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) is the same as the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I). Can be mentioned.
The epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (B) having two or more epoxy groups.
The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) with respect to 100 parts by weight of the polyurethane polyurea resin (C). The epoxy resin (D) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight.

　更に、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 Further, like the curable conductive polyurethane polyurea adhesive layer (I), the curable insulating polyurethane polyurea resin composition layer (II) has a phenol content within a range that does not impair the performance such as heat resistance and flex resistance. One or more of a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.

　また、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）との反応や、エポキシ樹脂（Ｄ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。
　また、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様に、接着性、耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (C) and an epoxy resin (D), and reaction of an epoxy resin (D) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
Further, the curable insulating polyurethane polyurea resin composition layer (II) has a silane content within a range that does not deteriorate the adhesion and solder reflow resistance, as in the case of the curable conductive polyurethane polyurea adhesive layer (I). One or more coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. may be added. .

　フィルムの態様（２）は、アジリジン系硬化剤（Ｅ）を含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有することにより、硬化後において柔軟で屈曲特性に優れ、ＰＣＴを経ても導電性が低下しないという効果を維持したまま、更に、被着体に加熱圧着する際に接着剤が過度にはみ出すことがないという追加の効果を示す。 The mode (2) of the film has a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine-based curing agent (E) and a curable insulating polyurethane polyurea resin composition layer (II). In addition, while maintaining the effect of being flexible and excellent in bending properties after curing, and not being deteriorated in conductivity even after PCT, the adhesive is not excessively protruded when heat-bonded to the adherend. Show the effect.

　本発明によるフィルムの態様（２）において、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、導電性フィラー及びアジリジン系硬化剤（Ｅ）の有無を除き、同一組成のポリウレタンポリウレア樹脂組成物からなることも、あるいは異なる組成のポリウレタンポリウレア樹脂組成物からなることもできる。また、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、いずれも未硬化（硬化前）の固化されたドライ状態であり、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のみからなる場合でも全体としてフィルム状となるので、特に支持体又は担体を必要としないが、後述するように、剥離性シートに貼着した状態で保存することもできる。 In the embodiment (2) of the film according to the present invention, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) include a conductive filler and an aziridine-based curing agent. Except for the presence or absence of (E), it can consist of a polyurethane polyurea resin composition of the same composition, or it can consist of a polyurethane polyurea resin composition of a different composition. The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in an uncured (before curing) solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.

　次に硬化性電磁波シールド性接着性フィルムの態様（３）〔フィルムの態様（３）ともいう〕について説明する。
　具体的には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有し、全体としてのゲル分率が３０～９０重量％である、硬化性電磁波シールド性接着性フィルムである。 Next, the aspect (3) of the curable electromagnetic wave shielding adhesive film (also referred to as the film aspect (3)) will be described.
Specifically, it has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II), and the gel fraction as a whole is 30 to 90% by weight. A curable electromagnetic wave shielding adhesive film.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）は、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーと、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有するものである。 The curable conductive polyurethane polyurea adhesive layer (I) reacts a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). The polyurethane polyurea resin (A) obtained by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with the polyamino compound (a5), and the epoxy resin (B) having two or more epoxy groups ), 10 to 700 parts by weight of conductive filler and aziridine curing agent (E) with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B), and the polyurethane polyurea resin (A) aziridinyl per 1 mol of carboxyl groups The are those containing in a range of from 0.05 to 4 moles.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）に含有されるポリウレタンポリウレア樹脂（Ａ）としては、フィルムの態様（１）で説明したポリウレタンポリウレア樹脂（Ａ）と同様のものが挙げられる。
　また、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）についても、フィルムの態様（１）で説明した２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と同様のものが挙げられる。
　また、エポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率も、フィルムの態様（１）で説明したエポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。 Examples of the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I) include those similar to the polyurethane polyurea resin (A) described in the film embodiment (1).
The epoxy resin (B) having two or more epoxy groups may be the same as the epoxy resin (B) having two or more epoxy groups described in the embodiment (1) of the film.
Also, the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film. The amount of the epoxy resin (B) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polyurea resin (A).

　アジリジン系硬化剤（Ｅ）については、フィルムの態様（２）で説明したアジリジン系硬化剤（Ｅ）と同様のものを用いることできる。
　また、アジリジン系硬化剤（Ｅ）を使用することにより、アジリジニル基とポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基との高い反応性を利用して、特別なエージングを必要とせず、両者を反応させ、半硬化状態にさせることができる。つまり、両者を反応させ、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率を３０～９０重量％とすることによって、加熱圧着時に貼着領域から硬化性導電性接着剤層がはみ出すのを低減することができる。硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率は、５０～８５重量％であることが好ましく、６０～８０重量％であることがより好ましい。
　硬化性導電性ポリウレタンポリウレア接着剤のゲル分率層（Ｉ）が３０重量％未満の場合、即ちポリウレタンウレア樹脂（Ａ）の大半が未反応で残っている場合、加熱圧着工程における接着剤のはみ出しの低減をほとんど期待できない。一方、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率が９０重量％を超える場合、加熱圧着工程に至る前にポリウレタンウレア樹脂（Ａ）の大半がアジリジン系硬化剤（Ｅ）と既に反応・硬化してしまうので、被着体との接着性を確保しにくくなる。 About the aziridine type hardening | curing agent (E), the thing similar to the aziridine type hardening | curing agent (E) demonstrated in the aspect (2) of the film can be used.
In addition, by using the aziridine-based curing agent (E), the high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (A) is utilized, and both are reacted without requiring special aging. It can be made to be semi-cured. That is, by reacting both, the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is set to 30 to 90% by weight, so that the curable conductive adhesive layer protrudes from the adhesion region at the time of thermocompression bonding. Can be reduced. The gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.
When the gel fraction layer (I) of the curable conductive polyurethane polyurea adhesive is less than 30% by weight, that is, when most of the polyurethane urea resin (A) remains unreacted, the adhesive protrudes in the thermocompression bonding process. Almost no reduction is expected. On the other hand, when the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, the polyurethane urea resin (A) is mostly composed of the aziridine-based curing agent (E) before the thermocompression bonding step. Since it has already reacted and cured, it becomes difficult to ensure adhesion with the adherend.

　ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を得るためには、ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対して、アジリジニル基が０．０５～４モルの範囲でアジリジン系硬化剤（Ｅ）を含有することが重要であり、０．２～２モルの範囲で含有することが好ましく、０．４～１モルの範囲で含有することがより好ましい。
　ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対して、アジリジン系硬化剤（Ｅ）のアジリジニル基が０．０５モル倍未満の場合、加熱圧着工程時の接着剤のはみ出しを効果的に低減するほどには、硬化性導電性ポリウレタンポリウレア接着剤層を得る際に、ポリウレタンポリウレア樹脂（Ａ）の硬化・架橋が進行しない。他方、カルボキシル基１モルに対して、アジリジニル基が４モルより多いと、ポリウレタンポリウレア樹脂（Ａ）の反応・硬化が過度に進行してしまうので、加熱圧着工程の際に硬化性導電性ポリウレタンポリウレア接着剤層が被着体を十分に濡らすことができず、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）との反応も期待できず、被着体に対する接着性が確保できない。 In order to obtain a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight, 0.05 mol of aziridinyl groups per mol of carboxyl groups in the polyurethane polyurea resin (A). It is important to contain the aziridine curing agent (E) in the range of ˜4 mol, preferably in the range of 0.2 to 2 mol, and in the range of 0.4 to 1 mol. More preferred.
When the aziridinyl group of the aziridine-based curing agent (E) is less than 0.05 mol times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (A), it effectively reduces the protrusion of the adhesive during the thermocompression bonding process. Thus, when the curable conductive polyurethane polyurea adhesive layer is obtained, curing and crosslinking of the polyurethane polyurea resin (A) do not proceed. On the other hand, if the aziridinyl group is more than 4 moles per mole of carboxyl groups, the reaction and curing of the polyurethane polyurea resin (A) proceeds excessively. The adhesive layer cannot sufficiently wet the adherend, the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) cannot be expected, and the adhesion to the adherend cannot be ensured.

　フィルムの態様（３）の硬化性電磁波シールド性接着性フィルムの硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、フィルムの態様（１）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 In the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film embodiment (3), the curable conductive polyurethane polyurea adhesive layer (I) of the film embodiment (1) In the same manner as in the above, 1 such as phenol resin, silicone resin, urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, as long as the performance such as heat resistance and flex resistance is not impaired. Seeds or more can be included.

　また、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）との反応や、エポキシ樹脂（Ｂ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、フィルムの態様（１）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (A) and an epoxy resin (B), and reaction of an epoxy resin (B) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I) of the film mode (1).

　また、フィルムの態様（３）の硬化性電磁波シールド性接着性フィルムの硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、フィルムの態様（１）の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、接着性、及び／又は耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Further, the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the film aspect (3) includes the curable conductive polyurethane polyurea adhesive layer (I) of the film aspect (1). Similar to I), silane coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, as long as adhesion and / or solder reflow resistance are not deteriorated. You may add 1 type or more, such as a leveling regulator, a filler, or a flame retardant.

　一方、本発明によるフィルムの態様（３）においても、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、硬化性電磁波シールド性接着性フィルムに、貼着・硬化時における機械的強度を与える役割を担う。即ち、未硬化状態（硬化前）でも基材ないし担体としての機能を有し、例えば、特許文献４における基材フィルムに当たる。
　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とアジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成される。 On the other hand, also in the mode (3) of the film according to the present invention, the curable insulating polyurethane polyurea resin composition layer (II) gives the curable electromagnetic wave shielding adhesive film mechanical strength at the time of sticking and curing. Take a role. That is, it has a function as a substrate or carrier even in an uncured state (before curing), and hits the substrate film in Patent Document 4, for example.
The curable insulating polyurethane polyurea resin composition layer (II) comprises a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reaction with polyamino compound (c5), and epoxy resin having two or more epoxy groups ( D) and an aziridin-based curing agent (F) having a film-forming ability, containing aziridinyl groups in a range of 0.05 to 4 mol with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C). It is formed from an insulating polyurethane polyurea resin composition.

　また、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）との反応や、エポキシ樹脂（Ｄ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。
　また、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様に、接着性、及び／又は耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (C) and an epoxy resin (D), and reaction of an epoxy resin (D) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
Further, in the curable insulating polyurethane polyurea resin composition layer (II), as in the case of the curable conductive polyurethane polyurea adhesive layer (I), a range in which the adhesion and / or solder reflow resistance is not deteriorated. Add one or more of silane coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. May be.

　本発明によるフィルムの態様（３）の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）において、アジリジン系硬化剤（Ｆ）は、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．２～２モルの範囲で含有することが好ましく、０．４～１モルの範囲で含有することがより好ましい。
　ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対して、アジリジン系硬化剤（Ｆ）のアジリジニル基が０．０５モル倍未満の場合、ポリウレタンポリウレア樹脂中のカルボン酸の多くが未反応で存在するため、回路基板に加熱貼付する際に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が過度に伸びることによって、機械的強度の低下、及び段差部における硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の隠蔽性欠如といった不良を発生させる恐れがある。他方、カルボキシル基１モルに対して、アジリジニル基が４モルより多いと、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の流動性が過度に抑制され、硬化性電磁波シールド性接着性フィルムを製造する際、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）と剥離性フィルム１との密着性、及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）と硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）との密着性が低下する恐れがある。 In the curable insulating polyurethane polyurea resin composition layer (II) of the embodiment (3) of the film according to the present invention, the aziridine-based curing agent (F) is based on 1 mol of carboxyl groups in the polyurethane polyurea resin (C). The aziridinyl group is preferably contained in the range of 0.2 to 2 mol, and more preferably in the range of 0.4 to 1 mol.
When the aziridinyl group of the aziridine-based curing agent (F) is less than 0.05 mol times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C), most of the carboxylic acid in the polyurethane polyurea resin is unreacted. Therefore, when the curable insulating polyurethane polyurea resin composition layer (II) is excessively stretched when heated and pasted to a circuit board, the mechanical strength is lowered, and the curable conductive polyurethane polyurea adhesive at the stepped portion There is a risk of causing a defect such as lack of concealment of the layer (I). On the other hand, when the amount of aziridinyl group is more than 4 mol with respect to 1 mol of carboxyl group, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed, and a curable electromagnetic shielding adhesive film is obtained. Adhesiveness between curable insulating polyurethane polyurea resin composition layer (II) and peelable film 1, and curable insulating polyurethane polyurea resin composition layer (II) and curable conductive polyurethane polyurea adhesive There is a possibility that the adhesion with the layer (I) may be lowered.

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）に含有されるポリウレタンポリウレア樹脂（Ｃ）としては、フィルムの態様（１）で説明したポリウレタンポリウレア樹脂（Ａ）と同様のものを用いることができる。
　２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）についても、フィルムの態様（１）で説明した２個以上のエポキシ基を有するエポキシ樹脂（Ａ）と同様のものを挙げることができる。
　エポキシ樹脂（Ｄ）とポリウレタンポリウレア樹脂（Ｃ）との配合比率も、フィルムの態様（１）で説明したエポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ｃ）１００重量部に対して、エポキシ樹脂（Ｄ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。 The polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) may be the same as the polyurethane polyurea resin (A) described in the film embodiment (1). .
The epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (A) having two or more epoxy groups described in the embodiment (1) of the film.
The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film. (C) The epoxy resin (D) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight.

　更に硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 Further, as with the curable conductive polyurethane polyurea adhesive layer (I), the curable insulating polyurethane polyurea resin composition layer (II) is phenolic as long as the performance such as heat resistance and flex resistance is not impaired. One or more of a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.

　また、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）との反応や、エポキシ樹脂（Ｄ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。
　また、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様に、接着性、耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (C) and an epoxy resin (D), and reaction of an epoxy resin (D) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
Further, the curable insulating polyurethane polyurea resin composition layer (II) has a silane content within a range that does not deteriorate the adhesion and solder reflow resistance, as in the case of the curable conductive polyurethane polyurea adhesive layer (I). One or more coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. may be added. .

　フィルムの態様（３）は、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを構成層として有する。硬化性電磁波シールド性接着性フィルムのゲル分率は３０～９０重量％であり、５０～８５重量％であることが好ましく、６０～８０重量％であることがより好ましい。
　このような硬化性電磁波シールド性接着性フィルムは、ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを構成層とすることが好ましく、各層のゲル分率は、それぞれ５０～８５重量％であることが好ましく、６０～８０重量％であることがより好ましい。 The film mode (3) has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) as constituent layers. The gel fraction of the curable electromagnetic wave shielding adhesive film is 30 to 90% by weight, preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.
Such a curable electromagnetic wave shielding adhesive film comprises a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulation having a gel fraction of 30 to 90% by weight. The constituent polyurethane polyurea resin composition layer (II) is preferably a constituent layer, and the gel fraction of each layer is preferably 50 to 85% by weight, more preferably 60 to 80% by weight. .

　すなわち、本発明によるフィルムの態様（３）においては、アジリジン系硬化剤（Ｅ）を使用し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率を３０～９０重量％とすることによって、硬化後において柔軟で屈曲特性に優れ、ＰＣＴを経ても導電性が低下しないという効果を維持したまま、更に、被着体に加熱圧着する際に接着剤が過度にはみ出すことがないという追加の効果を得ることができる。硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率が３０重量％未満、即ちポリウレタンウレア樹脂（Ａ）の大半が未反応で残っている場合、加熱圧着工程における接着剤のはみ出しの低減をほとんど期待できない。一方、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率が９０重量％を超える場合、加熱圧着工程に至る前にポリウレタンウレア樹脂（Ａ）の大半がアジリジン系硬化剤（Ｅ）と既に反応・硬化してしまっているので、被着体との接着性を確保しにくくなる。 That is, in the embodiment (3) of the film according to the present invention, the aziridine-based curing agent (E) is used, and the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is 30 to 90% by weight. In addition, while maintaining the effect of being flexible and excellent in bending properties after curing, and not being deteriorated in conductivity even after PCT, the adhesive is not excessively protruded when heat-bonded to the adherend. The effect of can be obtained. When the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is less than 30% by weight, that is, when most of the polyurethane urea resin (A) is left unreacted, the protrusion of the adhesive in the thermocompression bonding process is reduced. I can hardly expect. On the other hand, when the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, the polyurethane urea resin (A) is mostly composed of the aziridine-based curing agent (E) before the thermocompression bonding step. Since it has already reacted and cured, it becomes difficult to ensure adhesion with the adherend.

　また、本発明によるフィルムの態様（３）においては、アジリジン系硬化剤（Ｆ）を使用し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率を３０～９０重量％とすることによって、硬化性電磁波シールド性接着性フィルムを回路基板に加熱貼付する際の、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層の過度の伸びを抑制し、機械的強度を保持することができる。即ち、回路基板の段差部分などに貼着する際、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の過度の伸びによる硬化性導電性ポリウレタンポリウレア接着剤層の隠蔽性の欠如のような不良を防ぐことができる。
　ゲル分率が３０重量％未満、即ちポリウレタンウレア樹脂（Ｃ）の大半が未反応で残っている場合、回路基板に加熱貼付する際に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が過度に伸びることによって、機械的強度の低下、及び硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の隠蔽性の欠如のような不良を発生させる恐れがある。一方、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率が９０重量％を超える場合、該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の流動性が過度に抑制され、製造工程において、剥離性フィルム、及び硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）との密着性が低下する恐れがある。 In the film mode (3) according to the present invention, the aziridine-based curing agent (F) is used, and the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is set to 30 to 90% by weight. Accordingly, excessive elongation of the curable insulating polyurethane polyurea resin composition layer when the curable electromagnetic wave shielding adhesive film is bonded to the circuit board by heating can be suppressed, and the mechanical strength can be maintained. That is, when pasting on a stepped portion of a circuit board, a defect such as lack of concealment of the curable conductive polyurethane polyurea adhesive layer due to excessive elongation of the curable insulating polyurethane polyurea resin composition layer (II) Can be prevented.
When the gel fraction is less than 30% by weight, that is, when most of the polyurethaneurea resin (C) remains unreacted, the curable insulating polyurethane polyurea resin composition layer (II) is formed on the circuit board by heating. Excessive elongation can cause defects such as reduced mechanical strength and lack of concealment of the curable conductive polyurethane polyurea adhesive layer (I). On the other hand, when the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) exceeds 90% by weight, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed, In a manufacturing process, there exists a possibility that adhesiveness with a peelable film and a curable conductive polyurethane polyurea adhesive layer (I) may fall.

　フィルムの態様（３）は、アジリジン系硬化剤（Ｅ）を含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、アジリジン系硬化剤（Ｆ）を含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有することにより、硬化後においては柔軟で屈曲特性に優れており、更にＰＣＴを経ても導電性が低下しないという効果を維持したまま、被着体に加熱圧着する際に接着剤が過度にはみ出すことがなく、加熱圧着する際に段差のコーナー部において、導電性ポリウレタンポリウレア接着層が露出しないような耐延性を発揮することができる。 The film mode (3) comprises a curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine type curing agent (E) and a curable insulating polyurethane polyurea resin composition containing an aziridine type curing agent (F). By having the physical layer (II), after being cured, it is flexible and excellent in bending properties, and further, when it is thermocompression bonded to the adherend while maintaining the effect that the conductivity does not decrease even after passing through PCT. The adhesive does not protrude excessively and can exhibit ductility so that the conductive polyurethane-polyurea adhesive layer is not exposed at the corners of the steps when heat-pressing.

　本発明によるフィルムの態様（３）において、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、導電性フィラーの有無とアジリジン系硬化剤（Ｅ）の含有量を除き、同一組成のポリウレタンポリウレア樹脂組成物からなることも、あるいは異なる組成のポリウレタンポリウレア樹脂組成物からなることもできる。また、アジリジン系硬化剤（Ｅ）の含有量も、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とにおいて、同一であることも異なることもできる。更に、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、いずれも未硬化（硬化前）の固化されたドライ状態であり、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のみからなる場合でも全体としてフィルム状となるので、特に支持体又は担体を必要としないが、後述するように、剥離性シートに貼着した状態で保存することもできる。 In the embodiment (3) of the film according to the present invention, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) include the presence or absence of a conductive filler and an aziridine type. Except for the content of the curing agent (E), it can be composed of a polyurethane polyurea resin composition having the same composition or a polyurethane polyurea resin composition having a different composition. Further, the content of the aziridine-based curing agent (E) may be the same in the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). It can be different. Furthermore, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both uncured (before curing) in a solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.

　次に、本発明における硬化性電磁波シールド性接着性フィルムの態様（４）〔以下、フィルムの態様（４）ともいう〕について説明する。具体的には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、硬化性電磁波シールド性接着性フィルムである。
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、導電性フィラーとを含有し、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部とを含有する。
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）に含有されるポリウレタンポリウレア樹脂（Ａ）としては、フィルムの態様（１）で説明したポリウレタンポリウレア樹脂（Ａ）と同様のものを挙げることができる。 Next, the aspect (4) of the curable electromagnetic wave shielding adhesive film in the present invention (hereinafter also referred to as the film aspect (4)) will be described. Specifically, a curable electromagnetic wave shield having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight. Adhesive film.
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B) and a conductive filler, containing 10 to 700 parts by weight of conductive filler with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B).
Examples of the polyurethane polyurea resin (A) contained in the curable conductive polyurethane polyurea adhesive layer (I) include those similar to the polyurethane polyurea resin (A) described in the embodiment (1) of the film.

　また、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）についても、フィルムの態様（１）で説明した２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と同様のものを挙げることができる。
　エポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率も、フィルムの態様（１）で説明したエポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。 Moreover, about the epoxy resin (B) which has 2 or more epoxy groups, the thing similar to the epoxy resin (B) which has 2 or more epoxy groups demonstrated in the aspect (1) of the film can be mentioned.
The blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film. (A) The epoxy resin (B) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight.

　更に、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 Further, the curable conductive polyurethane polyurea adhesive layer (I) has a phenolic resin, a silicone resin, a urea resin, an acrylic resin, and a polyester resin as long as the performance such as heat resistance and flex resistance is not impaired. One or more of a resin, a polyamide-based resin, or a polyimide-based resin can be contained.

　また、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）との反応や、エポキシ樹脂（Ｄ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。
　また、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）には、接着性、耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (C) and an epoxy resin (D), and reaction of an epoxy resin (D) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
Further, the curable conductive polyurethane polyurea adhesive layer (I) has a silane coupling agent, an antioxidant, a pigment, a dye, a tackifying resin, a plasticizer, and the like within a range not deteriorating the adhesiveness and solder reflow resistance. You may add 1 or more types, such as a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

　続いて、ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）について説明する。
　本発明によるフィルムの態様（４）においても、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、硬化性電磁波シールド性接着性フィルムに、貼着・硬化時における機械的強度を与える役割を担う。即ち、未硬化状態（硬化前）でも基材ないし担体としての機能を有し、例えば、特許文献４における基材フィルムに当たる。
　ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）は、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とアジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成される。 Next, the curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight will be described.
Also in the mode (4) of the film according to the present invention, the curable insulating polyurethane polyurea resin composition layer (II) plays a role of imparting mechanical strength to the curable electromagnetic wave shielding adhesive film upon sticking / curing. Bear. That is, it has a function as a substrate or carrier even in an uncured state (before curing), and hits the substrate film in Patent Document 4, for example.
The curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight comprises a diol compound having a carboxyl group (c1) and a polyol having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound. A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting (c2) and the organic diisocyanate (c3) with a polyamino compound (c5); The epoxy resin (D) having at least one epoxy group and the aziridine-based curing agent (E) are added in a range of 0.05 to 4 mol of aziridinyl group with respect to 1 mol of carboxyl group in the polyurethane polyurea resin (C). Containing curable insulating polyurethane polyurea resin having film-forming ability It is formed from a formed product.

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）に含有されるポリウレタンポリウレア樹脂（Ｃ）としては、フィルムの態様（１）で説明したポリウレタンポリウレア樹脂（Ａ）と同様のものを挙げることができる。
　２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）についても、２個以上のエポキシ基を有するエポキシ樹脂（Ａ）と同様のものを挙げることができる。
　エポキシ樹脂（Ｄ）とポリウレタンポリウレア樹脂（Ｃ）との配合比率も、フィルムの態様（１）で説明したエポキシ樹脂（Ｂ）とポリウレタンポリウレア樹脂（Ａ）との配合比率と同様に、ポリウレタンポリウレア樹脂（Ｃ）１００重量部に対して、エポキシ樹脂（Ｄ）３～２００重量部であることが好ましく、５～１００重量部であることがより好ましい。
　更に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と同様に、耐熱性や耐屈曲性等の性能を損なわない範囲で、フェノール系樹脂、シリコーン系樹脂、ユリア系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、又はポリイミド系樹脂などの１種又はそれ以上を含有させることができる。 Examples of the polyurethane polyurea resin (C) contained in the curable insulating polyurethane polyurea resin composition layer (II) include the same as the polyurethane polyurea resin (A) described in the film embodiment (1). .
The epoxy resin (D) having two or more epoxy groups can be the same as the epoxy resin (A) having two or more epoxy groups.
The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is the same as the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the embodiment (1) of the film. (C) The epoxy resin (D) is preferably 3 to 200 parts by weight and more preferably 5 to 100 parts by weight with respect to 100 parts by weight.
Further, in the curable insulating polyurethane polyurea resin composition layer (II), as in the case of the curable conductive polyurethane polyurea adhesive layer (I), phenol is used within a range not impairing performance such as heat resistance and flex resistance. One or more of a resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, or a polyimide resin can be contained.

　また、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）との反応や、エポキシ樹脂（Ｄ）の単独での反応を促進させる目的で、硬化促進剤、及び／又は硬化剤を含有させることができる点についても、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様である。
　また、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）には、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の場合と同様に、接着性、耐ハンダリフロー性を劣化させない範囲で、シランカップリング剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、又は難燃剤等の１種又はそれ以上を添加してもよい。 Moreover, a hardening accelerator and / or a hardening | curing agent can be contained in order to accelerate | stimulate reaction of polyurethane polyurea resin (C) and an epoxy resin (D), and reaction of an epoxy resin (D) independently. This is also the same as in the case of the curable conductive polyurethane polyurea adhesive layer (I).
Further, the curable insulating polyurethane polyurea resin composition layer (II) has a silane content within a range that does not deteriorate the adhesion and solder reflow resistance, as in the case of the curable conductive polyurethane polyurea adhesive layer (I). One or more coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, fillers, flame retardants, etc. may be added. .

　アジリジン系硬化剤（Ｅ）について説明する。アジリジン系硬化剤（Ｅ）を使用することにより、アジリジニル基とポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基との高い反応性を利用して、特別なエージングを必要とせず、両者を反応させ、半硬化状態にさせる。つまり、両者を反応させ、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率を３０～９０重量％とすることができる。それにより電磁波シールド性接着性フィルムを回路基板に加熱貼付する際の、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の過度の伸びを抑制し、機械的強度を保持することができる。また更に、回路基板の段差部分などにおける硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の過度の伸びによる硬化性導電性ポリウレタンポリウレア接着剤層の隠蔽性欠如といった不良を防ぐことができる。
　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率は、５０～８５重量％であることが好ましく、６０～８０重量％であることがより好ましい。 The aziridine type curing agent (E) will be described. By using the aziridine-based curing agent (E), by utilizing the high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (C), both are reacted without requiring special aging. Allow to harden. That is, both can be reacted, and the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) can be 30 to 90% by weight. Thereby, excessive elongation of the curable insulating polyurethane polyurea resin composition layer (II) when the electromagnetic wave shielding adhesive film is heated and stuck to the circuit board can be suppressed, and the mechanical strength can be maintained. Furthermore, it is possible to prevent defects such as lack of concealment of the curable conductive polyurethane polyurea adhesive layer due to excessive elongation of the curable insulating polyurethane polyurea resin composition layer (II) at the step portion of the circuit board.
The gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is preferably 50 to 85% by weight, and more preferably 60 to 80% by weight.

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率が３０重量％未満、即ちポリウレタンポリウレア樹脂（Ｃ）の大半が未反応で残っている場合、回路基板に加熱貼付する際に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が過度に伸びることによって、機械的強度の低下、及び段差部における硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の露出といった不良を発生させる。一方、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率が９０重量％を超える場合、該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の流動性が過度に抑制され、硬化性電磁波シールド性接着性フィルムを製造する際、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）と剥離性フィルム１との密着性、及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）と硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）との密着性が低下する。 When the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is less than 30% by weight, that is, when most of the polyurethane polyurea resin (C) remains unreacted, When the curable insulating polyurethane polyurea resin composition layer (II) is excessively stretched, defects such as a decrease in mechanical strength and exposure of the curable conductive polyurethane polyurea adhesive layer (I) at the stepped portion are caused. On the other hand, when the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) exceeds 90% by weight, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed, When producing a curable electromagnetic wave shielding adhesive film, the adhesion between the curable insulating polyurethane polyurea resin composition layer (II) and the peelable film 1 and the curable insulating polyurethane polyurea resin composition layer (II) And the adhesiveness between the curable conductive polyurethane polyurea adhesive layer (I) are lowered.

　ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を得るためには、ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対して、アジリジニル基が０．０５～４モルの範囲でアジリジン系硬化剤（Ｅ）を含有することが重要であり、０．２～２モルの範囲で含有することが好ましく、０．４～１モルの範囲で含有することがより好ましい。
　ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対して、アジリジン系硬化剤（Ｅ）のアジリジニル基が０．０５モル未満の場合、ポリウレタンポリウレア樹脂中のカルボン酸の多くが未反応で存在するためゲル分率が３０％未満となる。他方、カルボキシル基１モルに対して、アジリジニル基が４モルより多いと、アジリジニル基が過度に存在するため、ポリウレタンポリウレア樹脂（Ｃ）中のカルボン酸が殆ど全て、アジリジン系硬化剤（Ｅ）と反応し、ゲル分率が９０％を超えてしまう。 In order to obtain a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight, the aziridinyl group is in an amount of 0.1 with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C). It is important to contain the aziridine curing agent (E) in the range of 05 to 4 mol, preferably in the range of 0.2 to 2 mol, and in the range of 0.4 to 1 mol. Is more preferable.
When the aziridinyl group of the aziridine type curing agent (E) is less than 0.05 mol with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C), most of the carboxylic acid in the polyurethane polyurea resin is unreacted. Therefore, the gel fraction is less than 30%. On the other hand, when there are more than 4 moles of aziridinyl groups with respect to 1 mole of carboxyl groups, since aziridinyl groups are excessively present, almost all of the carboxylic acids in the polyurethane polyurea resin (C) are all aziridine-based curing agents (E) and It reacts and the gel fraction exceeds 90%.

　フィルムの態様（４）は、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、アジリジン系硬化剤（Ｅ）を含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有することにより、硬化後において柔軟で屈曲特性に優れ、ＰＣＴを経ても導電性が低下しないという効果を維持したまま、更に、更に、被着体に加熱圧着する際に接着剤が過度にはみ出すことがないという追加の効果を示す。 The mode (4) of the film has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) containing an aziridine-based curing agent (E). In addition, while maintaining the effect of being flexible and excellent in bending properties after curing and not lowering the conductivity even after PCT, the adhesive is not excessively protruded when thermally bonded to the adherend. Show additional effects.

　本発明によるフィルムの態様（４）において、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、導電性フィラー及びアジリジン系硬化剤（Ｅ）の有無を除き、同一組成のポリウレタンポリウレア樹脂組成物からなることも、あるいは異なる組成のポリウレタンポリウレア樹脂組成物からなることもできる。また、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、いずれも未硬化（硬化前）の固化されたドライ状態であり、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のみからなる場合でも全体としてフィルム状となるので、特に支持体又は担体を必要としないが、後述するように、剥離性シートに貼着した状態で保存することもできる。 In the aspect (4) of the film according to the present invention, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) include a conductive filler and an aziridine-based curing agent. Except for the presence or absence of (E), it can consist of a polyurethane polyurea resin composition of the same composition, or it can consist of a polyurethane polyurea resin composition of a different composition. The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in an uncured (before curing) solidified dry state, Even when the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) alone are formed into a film as a whole, no support or carrier is required. However, as will be described later, it can be stored in a state of being attached to a peelable sheet.

　次に、本発明の硬化性電磁波シールド性接着性フィルムの態様（１）～（４）の製造方法の具体的態様について説明する。
　まず、フィルムの態様（１）の第１の製造方法によれば、一の剥離性フィルム（以下、剥離性フィルム１という）の一方の面に、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）とを含有する硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　別途、他の剥離性フィルム（以下、剥離性フィルム２という）の一方の面に、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）と導電性フィラーとを含有する硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　次いで、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる。 Next, specific embodiments of the production method of the embodiments (1) to (4) of the curable electromagnetic wave shielding adhesive film of the present invention will be described.
First, according to the 1st manufacturing method of the aspect (1) of a film, a polyurethane polyurea resin (C) and an epoxy resin (D) are formed on one surface of one peelable film (hereinafter referred to as peelable film 1). And drying a curable resin composition containing a curable insulating polyurethane polyurea resin composition layer (II),
Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), and a conductive filler is provided on one surface of another peelable film (hereinafter referred to as peelable film 2). Coating and drying to form a curable conductive polyurethane polyurea adhesive layer (I),
Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.

　あるいは、フィルムの態様（１）の第２の製造方法によれば、剥離性フィルム１の一方の面に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる。 Or according to the 2nd manufacturing method of the aspect (1) of a film, the said curable resin composition is applied and dried to one side of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried. Forming layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I). The peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).

　あるいは、フィルムの態様（１）の第３の製造方法によれば、剥離性フィルム２の一方の面に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる。 Or according to the 3rd manufacturing method of the aspect (1) of a film, the said curable conductive resin composition is applied and dried on one surface of the peelable film 2, and curable conductive polyurethane polyurea adhesion | attachment is carried out. Forming the agent layer (I),
On the curable conductive polyurethane polyurea adhesive layer (I), the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II). The peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).

　例示したような製造方法により、本発明の硬化性電磁波シールド性接着性フィルムの態様（１）について、剥離性フィルム２／硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）／硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）／剥離性フィルム１／という積層状態の硬化性電磁波シールド性接着性フィルムを得ることができる。 By the production method as illustrated, the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea with respect to the embodiment (1) of the curable electromagnetic wave shielding adhesive film of the present invention. A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.

　次に、本発明にて使用する剥離性フィルムについて説明する。
　剥離性フィルム１及び剥離性フィルム２は、片面あるいは両面に離型処理をしたフィルムや、片面あるいは両面に粘着剤を塗布したフィルムなどを使用することができる。
　離型フィルムの基材としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリフッ化ビニル、ポリフッ化ビニリデン、硬質ポリ塩化ビニル、ポリ塩化ビニリデン、ナイロン、ポリイミド、ポリスチレン、ポリビニルアルコール、エチレン・ビニルアルコール共重合体、ポリカーボネート、ポリアクリロニトリル、ポリブテン、軟質ポリ塩化ビニル、ポリフッ化ビニリデン、ポリエチレン、ポリプロピレン、ポリウレタン、エチレン酢酸ビニル共重合体、又はポリ酢酸ビニル等のプラスチックシート等、グラシン紙、上質紙、クラフト紙、又はコート紙等の紙類、各種の不織布、合成紙、又は金属箔や、これらを組み合わせた複合フィルムなどが挙げられる。 Next, the peelable film used in the present invention will be described.
As the peelable film 1 and the peelable film 2, a film having a release treatment on one side or both sides, a film having an adhesive applied on one side or both sides, or the like can be used.
As the release film substrate, polyethylene terephthalate, polyethylene naphthalate, polyvinyl fluoride, polyvinylidene fluoride, rigid polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, Plastic sheets such as polycarbonate, polyacrylonitrile, polybutene, soft polyvinyl chloride, polyvinylidene fluoride, polyethylene, polypropylene, polyurethane, ethylene vinyl acetate copolymer, or polyvinyl acetate, glassine paper, fine paper, kraft paper, or coat Examples thereof include papers such as paper, various non-woven fabrics, synthetic paper, metal foil, and composite films combining these.

　離型処理方法としては、離型剤をフィルムの片面あるいは両面に塗布したり、物理的にマット化処理する方法がある。
　離型剤としては、ポリエチレン、又はポリプロピレン等の炭化水素系樹脂、高級脂肪酸又はその金属塩、高級脂肪酸石鹸、ワックス、動植物油脂、マイカ、タルク、シリコーン系界面活性剤、シリコーンオイル、シリコーン樹脂、フッ素系界面活性剤、フッ素樹脂、又はフッ素含有シリコーン樹脂などが用いられる。
　離型剤の塗布方法としては、従来公知の方式、例えば、グラビアコート方式、キスコート方式、ダイコート方式、リップコート方式、コンマコート方式、ブレードコート方式、ロールコート方式、ナイフコート方式、スプレーコート方式、バーコート方式、スピンコート方式、又はディップコート方式等により行うことができる。 As a mold release treatment method, there is a method in which a mold release agent is applied to one or both sides of a film, or a physical matting treatment is performed.
Release agents include hydrocarbon resins such as polyethylene or polypropylene, higher fatty acids or metal salts thereof, higher fatty acid soaps, waxes, animal and vegetable oils, mica, talc, silicone surfactants, silicone oils, silicone resins, fluorine A surface active agent, a fluororesin, or a fluorine-containing silicone resin is used.
As a method for applying the release agent, conventionally known methods such as gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, spray coating method, It can be performed by a bar coating method, a spin coating method, a dip coating method, or the like.

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を設ける方法としては、従来公知の塗布方法、例えば、グラビアコート方式、キスコート方式、ダイコート方式、リップコート方式、コンマコート方式、ブレードコート方式、ロールコート方式、ナイフコート方式、スプレーコート方式、バーコート方式、スピンコート方式、又はディップコート方式等により行うことができる。 As a method of providing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II), a conventionally known coating method such as a gravure coating method, a kiss coating method, a die coating method, The lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, spray coating method, bar coating method, spin coating method, dip coating method, or the like can be used.

　なお、後述するように、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被覆する剥離性フィルム２は、一般的に、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の硬化前に剥離するので、未硬化状態の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）との剥離性を有する限り、特に剥離処理を行っていないフィルム（例えば、ポリエチレンフィルムやポリエチレンテレフタレートフィルム）を使用することもできる。また、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を被覆する剥離性フィルム１は、一般的に、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化した後に剥離するので、硬化後のポリウレタンポリウレア層との剥離性を有する限り、特に剥離処理を行っていないフィルム（例えば、ポリエチレンフィルムやポリエチレンテレフタレートフィルム）を使用することもできる。 As will be described later, the peelable film 2 covering the curable conductive polyurethane polyurea adhesive layer (I) is generally peeled before the curable conductive polyurethane polyurea adhesive layer (I) is cured. Therefore, as long as it has releasability from the curable conductive polyurethane polyurea adhesive layer (I) in an uncured state, a film (for example, a polyethylene film or a polyethylene terephthalate film) that has not been subjected to a release treatment can also be used. . In addition, the peelable film 1 that covers the curable insulating polyurethane polyurea resin composition layer (II) generally peels after the curable insulating polyurethane polyurea resin composition layer (II) is cured. As long as it has peelability from the subsequent polyurethane polyurea layer, a film (for example, a polyethylene film or a polyethylene terephthalate film) that has not been particularly peeled can also be used.

　次に、硬化性電磁波シールド性接着性フィルムの態様（２）について説明する。
　フィルムの態様（２）の第１の製造方法によれば、剥離性フィルム１の一方の面に、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）とアジリジン系硬化剤（Ｅ）とを含有する硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　別途、剥離性フィルム２の一方の面に、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）と導電性フィラーとを含有する硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　次いで、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる。 Next, the aspect (2) of the curable electromagnetic wave shielding adhesive film will be described.
According to the 1st manufacturing method of the aspect (2) of a film, the polyurethane polyurea resin (C), the epoxy resin (D), and the aziridine type hardening | curing agent (E) are contained in one surface of the peelable film 1. FIG. Applying and drying the curable resin composition to form a curable insulating polyurethane polyurea resin composition layer (II),
Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), and a conductive filler is applied to one surface of the peelable film 2 and dried to obtain a curable conductive property. Forming a polyurethane polyurea adhesive layer (I),
Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.

　あるいは、フィルムの態様（２）の第２の製造方法によれば、剥離性フィルム１の一方の面に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる。 Or according to the 2nd manufacturing method of the aspect (2) of a film, the said curable resin composition is applied and dried on one surface of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried. Forming layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I). The peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).

　あるいは、フィルムの態様（２）の第３の製造方法によれば、剥離性フィルム２の一方の面に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる。 Or according to the 3rd manufacturing method of the aspect (2) of a film, the said curable conductive resin composition is applied and dried on one surface of the peelable film 2, and curable conductive polyurethane polyurea adhesion | attachment is carried out. Forming the agent layer (I),
On the curable conductive polyurethane polyurea adhesive layer (I), the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II). The peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).

　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率が３０～９０重量％の半硬化状態となるように、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）や硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を得る際の乾燥条件、及び硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる条件を選択することができる。
　例えば、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）や硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を得る際の乾燥条件としては、溶剤が十分に揮発し、且つ、ポリウレタンポリウレア樹脂（Ｃ）のカルボン酸とアジリジン系硬化剤（Ｅ）が反応可能な条件であり、５０℃～１５０℃で１０秒～５分程度加熱乾燥することが好ましく、７０℃～１２０℃で３０秒～３分程度加熱乾燥することがより好ましい。
　また、アジリジン系硬化剤（Ｅ）により半硬化状態にした硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の硬化状態を維持し易いという点で、それぞれ別個に形成した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせて硬化性電磁波シールド性接着性フィルムを得る方法が好ましい。この場合、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とは、温度が４０℃～１２０℃、圧力が０．１～５ＭＰa、時間が０．５秒～６０秒間程度の条件で重ね合わせて一体化することが好ましい。 The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane so that the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is in a semi-cured state of 30 to 90% by weight. The drying conditions for obtaining the polyurea resin composition layer (II) and the conditions for superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are selected. be able to.
For example, as drying conditions for obtaining the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II), the solvent is sufficiently volatilized, and the polyurethane polyurea resin ( C) is a condition in which the carboxylic acid and the aziridine-based curing agent (E) can react, and it is preferable to heat and dry at 50 ° C. to 150 ° C. for about 10 seconds to 5 minutes, and at 70 ° C. to 120 ° C. for 30 seconds to 3 It is more preferable to heat and dry for about minutes.
Moreover, the curable conductive polyurethane polyurea formed separately from each other in that the cured state of the curable insulating polyurethane polyurea resin composition layer (II) that has been semi-cured by the aziridine-based curing agent (E) can be easily maintained. A method of obtaining a curable electromagnetic wave shielding adhesive film by superimposing the adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) is preferred. In this case, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) have a temperature of 40 ° C. to 120 ° C., a pressure of 0.1 to 5 MPa, and a time. It is preferable to superimpose and integrate them under conditions of about 0.5 seconds to 60 seconds.

　例示したような製造方法により、本発明の硬化性電磁波シールド性接着性フィルムの態様（２）について、剥離性フィルム２／硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）／硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）／剥離性フィルム１／という積層状態の硬化性電磁波シールド性接着性フィルムを得ることができる。 According to the production method as exemplified, for the embodiment (2) of the curable electromagnetic wave shielding adhesive film of the present invention, the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.

　次に硬化性電磁波シールド性接着性フィルムの態様（３）について説明する。
　フィルムの態様（３）の第１の製造方法によれば、例えば、剥離性フィルム１の一方の面に、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）とアジリジン系硬化剤（Ｆ）を含有する硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　別途、剥離性フィルム２の一方の面に、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）とアジリジン系硬化剤（Ｅ）と導電性フィラーとを含有する硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　次いで、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる。 Next, the aspect (3) of the curable electromagnetic wave shielding adhesive film will be described.
According to the 1st manufacturing method of the aspect (3) of a film, for example, the polyurethane polyurea resin (C), the epoxy resin (D), and the aziridine type hardening | curing agent (F) are contained in one surface of the peelable film 1 Coating and drying the curable resin composition to form a curable insulating polyurethane polyurea resin composition layer (II),
Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), an aziridine curing agent (E), and a conductive filler is applied to one surface of the peelable film 2. Dry to form a curable conductive polyurethane polyurea adhesive layer (I),
Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.

　あるいは、フィルムの態様（３）の第２の製造方法によれば、剥離性フィルム１の一方の面に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる。 Or according to the 2nd manufacturing method of the aspect (3) of a film, the said curable resin composition is applied and dried to one side of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried. Forming layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I). The peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).

　あるいは、フィルムの態様（３）の第３の製造方法によれば、剥離性フィルム２の一方の面に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる。 Or according to the 3rd manufacturing method of the aspect (3) of a film, the said curable conductive resin composition is applied and dried on one side of the peelable film 2, and curable conductive polyurethane polyurea adhesion | attachment is carried out. Forming the agent layer (I),
On the curable conductive polyurethane polyurea adhesive layer (I), the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II). The peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）、及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）のゲル分率が３０～９０重量％の半硬化状態となるように、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）や硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を得る際の乾燥条件、及び硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる条件を選択することができる。なお乾燥条件や硬化条件等は、硬化性電磁波シールド性接着性フィルムの態様（２）の製造方法と同様の条件で行うことができる。 The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) have a curable conductive property such that the gel fraction is 30 to 90% by weight. Drying conditions for obtaining polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II), and curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin The conditions for overlaying the composition layer (II) can be selected. In addition, drying conditions, curing conditions, etc. can be performed on the same conditions as the manufacturing method of the aspect (2) of a curable electromagnetic wave shielding adhesive film.

　例示したような製造方法により、本発明の硬化性電磁波シールド性接着性フィルムの態様（３）について、剥離性フィルム２／硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）／硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）／剥離性フィルム１／という積層状態の硬化性電磁波シールド性接着性フィルムを得ることができる。 According to the production method as exemplified, for the mode (3) of the curable electromagnetic wave shielding adhesive film of the present invention, the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.

　次に硬化性電磁波シールド性接着性フィルムの態様（４）について説明する。
　フィルムの態様（４）の第１の製造方法によれば、例えば、剥離性フィルム１の一方の面に、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）を含有する硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　別途、剥離性フィルム２の一方の面に、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）とアジリジン系硬化剤（Ｅ）と導電性フィラーとを含有する硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　次いで、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる。 Next, the aspect (4) of a curable electromagnetic wave shielding adhesive film is demonstrated.
According to the 1st manufacturing method of the aspect (4) of a film, for example, the curable resin composition containing a polyurethane polyurea resin (C) and an epoxy resin (D) is applied to one surface of the peelable film 1. And drying to form a curable insulating polyurethane polyurea resin composition layer (II),
Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), an aziridine curing agent (E), and a conductive filler is applied to one surface of the peelable film 2. Dry to form a curable conductive polyurethane polyurea adhesive layer (I),
Next, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are overlaid.

　あるいは、フィルムの態様（４）の第２の製造方法によれば、剥離性フィルム１の一方の面に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、
　該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる。 Or according to the 2nd manufacturing method of the aspect (4) of a film, the said curable resin composition is applied and dried on one surface of the peelable film 1, and a curable insulating polyurethane polyurea resin composition is dried. Forming layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), the curable conductive resin composition is applied and dried to form a curable conductive polyurethane polyurea adhesive layer (I). The peelable film 2 is superposed on the conductive conductive polyurethane polyurea adhesive layer (I).

　あるいは、フィルムの態様（４）の第３の製造方法によれば、剥離性フィルム２の一方の面に、前記硬化性導電性樹脂組成物を塗工・乾燥し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、
　該硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、前記硬化性樹脂組成物を塗工・乾燥し、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成し、該硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる。 Or according to the 3rd manufacturing method of the aspect (4) of a film, the said curable conductive resin composition is applied and dried on one surface of the peelable film 2, and curable conductive polyurethane polyurea adhesion | attachment is carried out. Forming the agent layer (I),
On the curable conductive polyurethane polyurea adhesive layer (I), the curable resin composition is applied and dried to form a curable insulating polyurethane polyurea resin composition layer (II). The peelable film 1 is superposed on the porous polyurethane polyurea resin composition layer (II).

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）のゲル分率が３０～９０重量％の半硬化状態となるように、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）や硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を得る際の乾燥条件、及び硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる条件を選択することができる。なお乾燥条件や硬化条件等は、硬化性電磁波シールド性接着性フィルムの態様（２）の製造方法と同様の条件で行うことができる。 The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea adhesive layer (I) can be in a semi-cured state with a gel fraction of 30 to 90% by weight. Selecting the drying conditions for obtaining the resin composition layer (II) and the conditions for superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). Can do. In addition, drying conditions, curing conditions, etc. can be performed on the same conditions as the manufacturing method of the aspect (2) of a curable electromagnetic wave shielding adhesive film.

　例示したような製造方法により、本発明の硬化性電磁波シールド性接着性フィルムの態様（４）について、剥離性フィルム２／硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）／硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）／剥離性フィルム１／という積層状態の硬化性電磁波シールド性接着性フィルムを得ることができる。 According to the production method as exemplified, for the mode (4) of the curable electromagnetic wave shielding adhesive film of the present invention, the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea A curable electromagnetic wave shielding adhesive film in a laminated state of resin composition layer (II) / peelable film 1 / can be obtained.

　更に、本発明の硬化性電磁波シールド性接着性フィルムの使い方の具体的態様を説明する。
　硬化性電磁波シールド性接着性フィルムは、剥離性フィルム２／硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）／硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）／剥離性フィルム１／という積層状態をとることが好ましいが、前記硬化性電磁波シールド性接着性フィルムから、剥離性フィルム２を剥がし、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を露出させる。その硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱することにより、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）中の、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｂ）、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｄ）を反応させ、両層（Ｉ）（II）を硬化させる。接触界面近傍において、ポリウレタンポリウレア樹脂（Ａ）とエポキシ樹脂（Ｄ）、ポリウレタンポリウレア樹脂（Ｃ）とエポキシ樹脂（Ｂ）の反応も生じる場合もある。そして、両層（Ｉ）（II）の硬化後に、剥離性フィルム１を剥がすことによって、被着体を電磁波から遮蔽することが可能となる。
　なお、硬化性電磁波シールド性接着性フィルムを被着体へ重ね合わせた後、剥離性フィルム１を剥がしてから、前記両層（Ｉ）（II）を加熱し、硬化する使用態様も好ましい。 Furthermore, the specific aspect of the usage of the curable electromagnetic wave shielding adhesive film of this invention is demonstrated.
The curable electromagnetic wave shielding adhesive film is a laminate state of peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea resin composition layer (II) / peelable film 1 However, the peelable film 2 is peeled off from the curable electromagnetic wave shielding adhesive film to expose the curable conductive polyurethane polyurea adhesive layer (I). The curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend and heated, whereby the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer ( In II), the polyurethane polyurea resin (A) and the epoxy resin (B), the polyurethane polyurea resin (C) and the epoxy resin (D) are reacted to cure both layers (I) and (II). In the vicinity of the contact interface, there may be a reaction between the polyurethane polyurea resin (A) and the epoxy resin (D), and the polyurethane polyurea resin (C) and the epoxy resin (B). And it becomes possible to shield a to-be-adhered body from electromagnetic waves by peeling the peelable film 1 after hardening of both layers (I) (II).
In addition, after superimposing a curable electromagnetic wave shielding adhesive film on a to-be-adhered body, after peeling off the peelable film 1, the use mode which heats and cures both said layers (I) (II) is also preferable.

　本発明の硬化性電磁波シールド性接着性フィルムを貼着することのできる被着体としては、例えば、繰り返し屈曲を受けるフレキシブルプリント配線板を代表例として挙げることができる。もちろん、リジッドプリント配線板にも適用できる。 As an adherend to which the curable electromagnetic wave shielding adhesive film of the present invention can be attached, for example, a flexible printed wiring board that is repeatedly bent can be given as a representative example. Of course, it can also be applied to rigid printed wiring boards.

上述した硬化性電磁波シールド性接着性フィルムを、被着体として、例えばプリント配線板を用いて製造した電磁波遮蔽物は、例えば携帯電話や、デジタルカメラ等といった物品に好適に用いることができる。 An electromagnetic shielding material produced by using the above-described curable electromagnetic wave shielding adhesive film as an adherend, for example, using a printed wiring board can be suitably used for an article such as a mobile phone or a digital camera.

　次に、実施例を示して本発明を更に詳細に説明するが、本発明はこれらによって限定されるものではない。実施例及び比較例において、「部」及び「％」とあるのは、「重量部」及び「重量％」をそれぞれ意味するものとする。
　なお、実施例中に記載したポリウレタンポリウレア樹脂の重量平均分子量、及びポリエステル樹脂の数平均分子量は、ＧＰＣ測定で求めたポリスチレン換算の重量平均分子量、及び数平均分子量であり、ＧＰＣ測定の条件は、以下のとおりである。
　装置：Ｓｈｏｄｅｘ　ＧＰＣ　Ｓｙｓｔｅｍ－２１（昭和電工製）
　カラム：Ｓｈｏｄｅｘ　ＫＦ－８０２、ＫＦ－８０３Ｌ、ＫＦ－８０５Ｌ
　　　　　（昭和電工製）の合計３本を連結して使用。
　溶媒：テトラヒドロフラン
　流速：１．０ｍＬ／ｍｉｎ
　温度：４０℃
　試料濃度：０．３重量％
　試料注入量：１００μＬ Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these. In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
In addition, the weight average molecular weight of the polyurethane polyurea resin described in the Examples, and the number average molecular weight of the polyester resin are the weight average molecular weight and the number average molecular weight in terms of polystyrene determined by GPC measurement, and the conditions for the GPC measurement are as follows: It is as follows.
Equipment: Shodex GPC System-21 (manufactured by Showa Denko)
Column: Shodex KF-802, KF-803L, KF-805L
A total of 3 (made by Showa Denko) are connected and used.
Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min
Temperature: 40 ° C
Sample concentration: 0.3% by weight
Sample injection volume: 100 μL

［ポリウレタンポリウレア樹脂（Ａ）、（Ｃ）の合成］
［合成例１］
　攪拌機、温度計、還流冷却器、滴下装置、及び窒素導入管を備えた反応容器に、アジピン酸とテレフタル酸及び３－メチル－１，５－ペンタンジオールから得られる数平均分子量（以下、「Ｍｎ」という）＝１００６であるジオール４１４部、ジメチロールブタン酸８部、イソホロンジイソシアネート１４５部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン２７部、ジ－ｎ－ブチルアミン３部、２－プロパノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１６部を添加し、７０℃で３時間反応させ、重量平均分子量（以下、「Ｍｗ」という）＝５４，０００、酸価５ｍｇＫＯＨ／ｇであるポリウレタンポリウレア樹脂の溶液を得た。これに、トルエン１４４部、２－プロパノール７２部を加えて、不揮発分３０％であるポリウレタンポリウレア樹脂溶液（Ａ－１）〔又は（Ｃ－１）〕を得た。 [Synthesis of Polyurethane Polyurea Resins (A) and (C)]
[Synthesis Example 1]
A number average molecular weight obtained from adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol (hereinafter “Mn”) Diol) of 1006) = 1006, 8 parts of dimethylolbutanoic acid, 145 parts of isophorone diisocyanate, and 40 parts of toluene were allowed to react at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 816 parts of the resulting urethane prepolymer solution was added to a mixture of 27 parts of isophoronediamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene. By reacting for a time, a solution of a polyurethane polyurea resin having a weight average molecular weight (hereinafter referred to as “Mw”) = 54,000 and an acid value of 5 mgKOH / g was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane polyurea resin solution (A-1) [or (C-1)] having a nonvolatile content of 30%.

［合成例２］
　攪拌機、温度計、還流冷却器、滴下装置、及び窒素導入管を備えた反応容器に、アジピン酸と３－メチル－１，５－ペンタンジオール及び１，６－ヘキサンカーボネートジオールとから得られるＭｎ＝９８１であるジオール３９０部、ジメチロールブタン酸１６部、イソホロンジイソシアネート１５８部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン２９部、ジ－ｎ－ブチルアミン３部、２－プロパノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１４部を添加し、７０℃で３時間反応させ、Ｍｗ＝４３，０００、酸価１０ｍｇＫＯＨ／ｇであるポリウレタンポリウレア樹脂の溶液を得た。これに、トルエン１４４部、２－プロパノール７２部を加えて、不揮発分３０％であるポリウレタンポリウレア樹脂溶液（Ａ－２）〔又は（Ｃ－２）〕を得た。 [Synthesis Example 2]
Mn obtained from adipic acid, 3-methyl-1,5-pentanediol, and 1,6-hexane carbonate diol was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. A diol (390 parts), dimethylol butanoic acid (16 parts), isophorone diisocyanate (158 parts) and toluene (40 parts) were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 814 parts of the resulting urethane prepolymer solution was added to a mixture of 29 parts of isophorone diamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene. By reacting for a period of time, a polyurethane polyurea resin solution having Mw = 43,000 and an acid value of 10 mgKOH / g was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane polyurea resin solution (A-2) [or (C-2)] having a nonvolatile content of 30%.

［合成例３］
　攪拌機、温度計、還流冷却器、滴下装置、及び窒素導入管を備えた反応容器に、アジピン酸と３－メチル－１，５－ペンタンジオールとから得られるＭｎ＝１００２であるジオール３５２部、ジメチロールブタン酸３２部、イソホロンジイソシアネート１７６部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン３２部、ジ－ｎ－ブチルアミン４部、２－プロパノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１０部を添加し、７０℃で３時間反応させ、Ｍｗ＝３５，０００、酸価２１ｍｇＫＯＨ／ｇであるポリウレタンポリウレア樹脂の溶液を得た。これに、トルエン１４４部、２－プロパノール７２部を加えて、不揮発分３０％であるポリウレタンポリウレア樹脂溶液（Ａ－３）〔又は（Ｃ－３）〕を得た。 [Synthesis Example 3]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 352 parts of a diol having Mn = 1002 obtained from adipic acid and 3-methyl-1,5-pentanediol, 32 parts of methylol 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. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 810 parts of the resulting urethane prepolymer solution was added to a mixture of 32 parts of isophorone diamine, 4 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene. By reacting for a period of time, a polyurethane polyurea resin solution having Mw = 35,000 and an acid value of 21 mgKOH / g was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane polyurea resin solution (A-3) [or (C-3)] having a nonvolatile content of 30%.

［合成例４］
　攪拌機、温度計、還流冷却器、滴下装置、及び窒素導入管を備えた反応容器に、アジピン酸と３－メチル－１，５－ペンタンジオール及び１，６－ヘキサンカーボネートジオールとから得られるＭｎ＝９８１であるジオール４３２部、イソホロンジイソシアネート１３７部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン２５部、ジ－ｎ－ブチルアミン３部、２－プロパノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１８部を添加し、７０℃で３時間反応させ、Ｍｗ＝４８，０００、酸価０ｍｇＫＯＨ／ｇであるポリウレタンポリウレア樹脂の溶液を得た。これに、トルエン１４４部、２－プロパノール７２部を加えて、不揮発分３０％であるポリウレタンポリウレア樹脂溶液（Ａ－４）〔又は（Ｃ－４）〕を得た。 [Synthesis Example 4]
Mn obtained from adipic acid, 3-methyl-1,5-pentanediol and 1,6-hexane carbonate diol was added to a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube. A diol of 432 of 981, 137 parts of isophorone diisocyanate, and 40 parts of toluene were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, to a mixture of 25 parts of isophoronediamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, 818 parts of the resulting urethane prepolymer solution was added, By reacting for a time, a polyurethane polyurea resin solution having Mw = 48,000 and an acid value of 0 mgKOH / g was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane polyurea resin solution (A-4) [or (C-4)] having a nonvolatile content of 30%.

［ポリエステル樹脂（Ｐ－１）の合成］
［合成例５］
　撹拌機、温度計、窒素ガス導入管及び還流脱水装置を備えたフラスコに、テレフタル酸ジメチル１８４．４部、ネオペンチルグリコール９４．８部、エチレングリコール９４．２部、２－メチル－１，３－プロパンジオール５４．７部及び酢酸亜鉛０．０３５部を仕込んだ。原料を加熱溶融して撹拌できるようになったら撹拌を開始して、留出するメタノールを常圧下で反応系外に除きながら１７０℃から２２０℃まで３時間かけて徐々に昇温し、２２０℃で１時間保持した。内温を一旦１７０℃まで冷却し、アジピン酸９２．６部、イソフタル酸６５．８部、及び１，４－シクロヘキサンジカルボン酸１１３．６部を加え、留出する水を常圧下で反応系外に除きながら２４０℃まで３時間かけて昇温し、更に２４０℃で保持して、生成物の酸価が１５ｍｇＫＯＨ／ｇになるまで反応を続けた。
　次に、装置を真空減圧装置に替えて、テトラブチルチタネート０．０６部を加え、２４０℃の温度で２トールの減圧下で６時間反応を続けた後、ポリフッ化エチレン樹脂製の容器に取り出した。
　この樹脂の数平均分子量は１８０００、ガラス転移温度は２７℃であった。
　続いて、得られたポリエステル樹脂１００部に対して、トルエン１００部を加えて溶解した。次いでそれぞれのフラスコにエチレングリコールビストリメリテート二無水物を５部添加し、１００℃の温度で５時間反応させ、Ｍｗ＝２４，０００、酸価１４ｍｇＫＯＨ／ｇであるポリエステル樹脂の溶液を得た。これにトルエンを加え希釈して、不揮発分が３０％である、カルボキシル基を有するポリエステル樹脂の溶液（Ｐ－１）を得た。 [Synthesis of polyester resin (P-1)]
[Synthesis Example 5]
In a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and reflux dehydrator, dimethyl terephthalate 184.4 parts, neopentyl glycol 94.8 parts, ethylene glycol 94.2 parts, 2-methyl-1,3 -Charge 54.7 parts of propanediol and 0.035 parts of zinc acetate. When the raw material can be heated and melted and stirred, stirring is started and the temperature is gradually raised from 170 ° C. to 220 ° C. over 3 hours while removing the distilled methanol outside the reaction system at normal pressure. Held for 1 hour. The internal temperature is once cooled to 170 ° C., 92.6 parts of adipic acid, 65.8 parts of isophthalic acid, and 113.6 parts of 1,4-cyclohexanedicarboxylic acid are added, and distilled water is removed from the reaction system under normal pressure. The temperature was raised to 240 ° C. over 3 hours while maintaining the temperature, and further maintained at 240 ° C., and the reaction was continued until the acid value of the product reached 15 mgKOH / g.
Next, the apparatus was changed to a vacuum decompression apparatus, 0.06 part of tetrabutyl titanate was added, and the reaction was continued for 6 hours under a reduced pressure of 2 Torr at a temperature of 240 ° C., and then taken out into a polyfluoroethylene resin container. It was.
The number average molecular weight of this resin was 18000, and the glass transition temperature was 27 ° C.
Subsequently, 100 parts of toluene was added to 100 parts of the obtained polyester resin and dissolved. Next, 5 parts of ethylene glycol bistrimellitate dianhydride was added to each flask and reacted at a temperature of 100 ° C. for 5 hours to obtain a polyester resin solution having Mw = 24,000 and an acid value of 14 mgKOH / g. Toluene was added thereto for dilution to obtain a solution (P-1) of a carboxyl group-containing polyester resin having a nonvolatile content of 30%.

［実施例１］
　ポリウレタンポリウレア樹脂溶液（Ａ－１）３３３部に対して、エポキシ樹脂（Ｂ－１）２０部を加えて接着樹脂組成物を得た。この接着樹脂組成物３５３部に対して、導電性フィラー（福田金属箔粉工業製「ＡｇＸＦ－３０１」）１８０部を加えて攪拌混合し、ポリウレタンポリウレア樹脂とエポキシ樹脂（Ｂ－１）との合計１００重量部に対して、導電性フィラー１５０部を含有する、硬化性導電性ポリウレタンポリウレア接着剤を得た。
　別途ポリウレタンポリウレア樹脂溶液（Ｃ－１）３３３部に対して、エポキシ樹脂（Ｄ－１）２０部を加えて絶縁性樹脂組成物１を得た。
　次いで、剥離性フィルム２として厚さ７５μｍのポリエチレンテレフタレートフィルムの片面に剥離処理を施したフィルムの剥離処理面上に、硬化性導電性ポリウレタンポリウレア接着剤を塗工、乾燥し、乾燥膜厚が８μｍの硬化性導電性ポリウレタンポリウレア接着剤（Ｉ）を形成した。
　別途、剥離性フィルム１として厚さ５０μｍのポリエチレンテレフタレートフィルムの片面に剥離処理を施したフィルムの剥離処理面上に、絶縁性樹脂組成物を塗工、乾燥し、乾燥膜厚が１５μｍの硬化性絶縁性樹脂組成物（II）を形成した。
　剥離性フィルム２に設けた硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）面と剥離性フィルム１に設けた硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）面とを貼り合わせて硬化性電磁波シールド性接着性フィルムを作製した。 [Example 1]
20 parts of epoxy resin (B-1) was added to 333 parts of polyurethane polyurea resin solution (A-1) to obtain an adhesive resin composition. To 353 parts of this adhesive resin composition, 180 parts of a conductive filler (“AgXF-301” manufactured by Fukuda Metal Foil Powder Industry) was added and stirred and mixed, and the total of polyurethane polyurea resin and epoxy resin (B-1) A curable conductive polyurethane polyurea adhesive containing 150 parts of conductive filler with respect to 100 parts by weight was obtained.
Separately, 20 parts of epoxy resin (D-1) was added to 333 parts of polyurethane polyurea resin solution (C-1) to obtain insulating resin composition 1.
Next, a curable conductive polyurethane polyurea adhesive is applied to the release surface of a film obtained by subjecting one surface of a 75 μm thick polyethylene terephthalate film as the peelable film 2 to a dry treatment, and the dry film thickness is 8 μm. The curable conductive polyurethane polyurea adhesive (I) was formed.
Separately, an insulating resin composition is coated on a release surface of a film obtained by subjecting one side of a 50 μm-thick polyethylene terephthalate film as the peelable film 1 to dryness, and the dry film thickness is 15 μm. An insulating resin composition (II) was formed.
A curable electromagnetic wave obtained by laminating the curable conductive polyurethane polyurea adhesive layer (I) surface provided on the peelable film 2 and the curable insulating polyurethane polyurea resin composition layer (II) surface provided on the peelable film 1 A shielding adhesive film was prepared.

［実施例２～１３］
　実施例１と同様にして、表１及び表２に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、及び導電性フィラーを用いて硬化性導電性ポリウレタンポリウレア接着剤、及びに硬化性絶縁性ポリウレタンポリウレア樹脂組成物を調製し、硬化性電磁波シールド性接着性フィルムを作製した。 [Examples 2 to 13]
In the same manner as in Example 1, the polyurethane polyurea resin solution, epoxy resin, and conductive filler of the types and amounts shown in Table 1 and Table 2 were used to curable conductive polyurethane polyurea adhesive, and curable insulating polyurethane. A polyurea resin composition was prepared to produce a curable electromagnetic shielding adhesive film.

［実施例１４～２８］
　実施例１と同様にして、表３及び表４に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、導電性フィラー、アジリジン系硬化剤を用いて硬化性導電性接着剤及び硬化性絶縁性樹脂組成物を調製し、硬化性電磁波シールド性接着性フィルムを作製した。 [Examples 14 to 28]
In the same manner as in Example 1, a curable conductive adhesive and a curable insulating resin using polyurethane polyurea resin solutions, epoxy resins, conductive fillers, and aziridine curing agents of the types and amounts shown in Tables 3 and 4 were used. The composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.

［実施例２９～４５］
　実施例１と同様にして、表５及び表６に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、及び導電性フィラーを用いて硬化性導電性ポリウレタンポリウレア接着剤、及びに硬化性絶縁性ポリウレタンポリウレア樹脂組成物を調製し、硬化性電磁波シールド性接着性フィルムを作製した。 [Examples 29 to 45]
In the same manner as in Example 1, a polyurethane polyurea resin solution, an epoxy resin, and a conductive filler of the types and amounts shown in Table 5 and Table 6 were used to curable conductive polyurethane polyurea adhesive, and curable insulating polyurethane. A polyurea resin composition was prepared to produce a curable electromagnetic shielding adhesive film.

［実施例４６～６１］
　実施例１と同様にして、表７及び表８に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、導電性フィラー、及びアジリジン系硬化剤を用いて、硬化性導電性接着剤及び硬化性絶縁性樹脂組成物を調製し、硬化性電磁波シールド性接着性フィルムを作製した。 [Examples 46 to 61]
In the same manner as in Example 1, using the polyurethane polyurea resin solution, epoxy resin, conductive filler, and aziridine-based curing agent of the types and amounts shown in Table 7 and Table 8, curable conductive adhesive and curable insulation The curable resin composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.

［比較例１～７、及び１１］
　実施例１と同様にして、表９及び表１０に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、及び導電性フィラーを用いて硬化性導電性ポリウレタンポリウレア接着剤、及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物を調製し、電磁波シールド性接着性フィルムを作製した。 [Comparative Examples 1 to 7 and 11]
In the same manner as in Example 1, a curable conductive polyurethane polyurea adhesive and a curable insulating polyurethane polyurea using the polyurethane polyurea resin solution, epoxy resin, and conductive filler of the types and amounts shown in Table 9 and Table 10 were used. A resin composition was prepared to produce an electromagnetic wave shielding adhesive film.

［比較例８］
　ポリウレタンポリウレア樹脂溶液（Ｃ－１）３３３部の代わりに、合成例５で得たカルボキシル基を有するポリエステル樹脂の溶液（Ｐ－１）３３３部を用いて、剥離性フィルム１の剥離処理面上に、１５μｍの厚みの硬化性絶縁性樹脂組成物層（II）を設けた以外は実施例１と同様にして、電磁波シールド性接着性フィルムを作製した。 [Comparative Example 8]
In place of 333 parts of the polyurethane polyurea resin solution (C-1), 333 parts of the polyester resin solution (P-1) having a carboxyl group obtained in Synthesis Example 5 was used on the release-treated surface of the release film 1. An electromagnetic wave shielding adhesive film was produced in the same manner as in Example 1 except that the curable insulating resin composition layer (II) having a thickness of 15 μm was provided.

［比較例９～１０］
　実施例１で用いた硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の代わりに、ポリフェニレンサルファイドフィルム（比較例９）、又はポリエチレンテレフタレートフィルム（比較例１０）を用いた以外は、実施例１と同様にして電磁波シールドフィルムを作製した。 [Comparative Examples 9 to 10]
Example 1 except that a polyphenylene sulfide film (Comparative Example 9) or a polyethylene terephthalate film (Comparative Example 10) was used instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 1. In the same manner as above, an electromagnetic wave shielding film was produced.

［比較例１２～２０］
　実施例１４と同様にして、表１１及び表１２に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、導電性フィラー、及びアジリジン系硬化剤を用いて硬化性導電性ポリウレタンポリウレア接着剤、及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物を調製し、電磁波シールド性接着性フィルムを作製した。 [Comparative Examples 12 to 20]
In the same manner as in Example 14, a polyurethane polyurea resin solution, an epoxy resin, a conductive filler, and an aziridine-based curing agent of the types and amounts shown in Tables 11 and 12 are used. A conductive insulating polyurethane polyurea resin composition was prepared to produce an electromagnetic wave shielding adhesive film.

［比較例２１］
　ポリウレタンポリウレア樹脂溶液（Ｃ－１）３３３部の代わりに、合成例５で得たカルボキシル基を有するポリエステル樹脂の溶液（Ｐ－１）３３３部を用いて、剥離性フィルム１の剥離処理面上に、１５μｍの厚みの硬化性絶縁性樹脂組成物層（II）を設けた以外は実施例１４と同様にして、電磁波シールド性接着性フィルムを作製した。 [Comparative Example 21]
In place of 333 parts of the polyurethane polyurea resin solution (C-1), 333 parts of the polyester resin solution (P-1) having a carboxyl group obtained in Synthesis Example 5 was used on the release-treated surface of the release film 1. An electromagnetic wave shielding adhesive film was produced in the same manner as in Example 14 except that a curable insulating resin composition layer (II) having a thickness of 15 μm was provided.

［比較例２２～２３］
　実施例１４で用いたフィルム状硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の代わりに、ポリフェニレンサルファイドフィルム（比較例２２）、又はポリエチレンテレフタレートフィルム（比較例２３）を用いた以外は、実施例１４と同様にして電磁波シールドフィルムを作製した。 [Comparative Examples 22 to 23]
Implementation was carried out except that a polyphenylene sulfide film (Comparative Example 22) or a polyethylene terephthalate film (Comparative Example 23) was used instead of the film-like curable insulating polyurethane polyurea resin composition layer (II) used in Example 14. An electromagnetic wave shielding film was produced in the same manner as in Example 14.

［比較例２４～３１］
　実施例２９と同様にして、表１３及び表１４に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、及び導電性フィラーを用いて導電性接着剤を調製し、電磁波シールド性接着性フィルムを作製した。 [Comparative Examples 24-31]
In the same manner as in Example 29, a conductive adhesive was prepared using the polyurethane polyurea resin solution, epoxy resin, and conductive filler of the types and amounts shown in Table 13 and Table 14, and an electromagnetic wave shielding adhesive film was produced. did.

［比較例３２～３３］
　ポリウレタンポリウレア樹脂溶液（Ｃ－１）３３３部の代わりに、合成例５で得たカルボキシル基を有するポリエステル樹脂の溶液（Ｐ－１）３３３部を用い、比較例３２ではアジリジン系硬化剤を用いずに、比較例３３ではアジリジン系硬化剤を用い、剥離性フィルム１の剥離処理面上に、１５μｍの厚みの硬化性絶縁性樹脂組成物層（II）を設けた以外は実施例２９と同様にして、電磁波シールド性接着性フィルムを作製した。 [Comparative Examples 32-33]
Instead of 333 parts of the polyurethane polyurea resin solution (C-1), 333 parts of the polyester resin solution (P-1) having a carboxyl group obtained in Synthesis Example 5 was used. In Comparative Example 32, no aziridine curing agent was used. In Comparative Example 33, an aziridine-based curing agent was used, and the same procedure as in Example 29 was performed except that a curable insulating resin composition layer (II) having a thickness of 15 μm was provided on the release-treated surface of the peelable film 1. Thus, an electromagnetic wave shielding adhesive film was produced.

［比較例３４～３５］
　実施例２９で用いた硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の代わりに、ポリフェニレンサルファイドフィルム（比較例３４）、又はポリエチレンテレフタレートフィルム（比較例３５）を用いた以外は、実施例２９と同様にして電磁波シールドフィルムを作製した。 [Comparative Examples 34 to 35]
Example 29 except that a polyphenylene sulfide film (Comparative Example 34) or a polyethylene terephthalate film (Comparative Example 35) was used instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 29. In the same manner as above, an electromagnetic wave shielding film was produced.

［比較例３６～４４］
　実施例４６と同様にして、表１５及び表１６に示す種類及び量のポリウレタンポリウレア樹脂溶液、エポキシ樹脂、導電性フィラー、及びアジリジン系硬化剤を用いて、硬化性導電性接着剤及び硬化性絶縁性樹脂組成物を調製し、硬化性電磁波シールド性接着性フィルムを作製した。 [Comparative Examples 36 to 44]
In the same manner as in Example 46, using the polyurethane polyurea resin solution, epoxy resin, conductive filler, and aziridine-based curing agent of the types and amounts shown in Table 15 and Table 16, curable conductive adhesive and curable insulation The curable resin composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.

［比較例４５～４６］
　ポリウレタンポリウレア樹脂溶液（Ｃ－１）３３３部の代わりに、合成例５で得たカルボキシル基を有するポリエステル樹脂の溶液（Ｐ－１）３３３部を用い、比較例４５ではアジリジン系硬化剤を用いずに、比較例４６ではアジリジン系硬化剤を用い、剥離性フィルム１の剥離処理面上に、１５μｍの厚みの硬化性絶縁性樹脂組成物層（II）を設けた以外は実施例４６と同様にして、電磁波シールド性接着性フィルムを作製した。 [Comparative Examples 45 to 46]
Instead of 333 parts of the polyurethane polyurea resin solution (C-1), 333 parts of the polyester resin solution (P-1) having a carboxyl group obtained in Synthesis Example 5 was used. In Comparative Example 45, no aziridine curing agent was used. Further, in Comparative Example 46, an aziridine-based curing agent was used, and the same procedure as in Example 46 was performed except that a curable insulating resin composition layer (II) having a thickness of 15 μm was provided on the release-treated surface of the peelable film 1. Thus, an electromagnetic wave shielding adhesive film was produced.

［比較例４７～４８］
　実施例４６で用いた硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の代わりに、ポリフェニレンサルファイドフィルム（比較例４７）、又はポリエチレンテレフタレートフィルム（比較例４８）を用いた以外は、実施例４６と同様にして電磁波シールドフィルムを作製した。 [Comparative Examples 47 to 48]
Example 46 except that a polyphenylene sulfide film (Comparative Example 47) or a polyethylene terephthalate film (Comparative Example 48) was used instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 46. In the same manner as above, an electromagnetic wave shielding film was produced.

　各実施例及び各比較例で得られた剥離性フィルム付き硬化性電磁波シールド性接着性フィルム（又は電磁波シールドフィルム）について、ポリイミドフィルム接着性、耐熱性、耐屈曲性、及びプレッシャークッカー（以下ＰＣＴ）耐性を以下の方法で評価した。結果を表１～表１６に示す。
（１）ポリイミドフィルム接着性の評価
　幅１０ｍｍ、長さ７０ｍｍの硬化性電磁波シールド性接着性フィルム（又は電磁波シールドフィルム）を用意し、剥離性フィルム２を剥がし、露出した硬化性導電性接着剤層に、厚さが５０μｍのポリイミドフィルム（東レ・デュポン社製「カプトン２００ＥＮ」）を１５０℃、１．０ＭＰａ、及び３０ｍｉｎの条件で圧着し、導電性接着剤層（Ｉ）及びフィルム状絶縁性組成物（II）を硬化させた。
　圧着後、測定用の補強のために、剥離性フィルム１を除去し、露出した硬化したフィルム状絶縁層に、ポリウレタンポリウレア系の接着シートを用い、前記ポリイミドフィルム担持体を、１５０℃、１ＭＰａ、及び３０ｍｉｎの条件で圧着した。
　２３℃相対湿度５０％の雰囲気下、引っ張り速度５０ｍｍ／ｍｉｎ、及び剥離角度９０°で、硬化した導電性接着剤層とポリイミドフィルムとの間を剥離し、剥離力の中心値をポリイミドフィルム接着強度（Ｎ／ｃｍ）とした。
　なお、比較例１１及び１２の場合は、測定用の補強はしなかった。 About the curable electromagnetic shielding adhesive film (or electromagnetic shielding film) with a peelable film obtained in each Example and each Comparative Example, polyimide film adhesiveness, heat resistance, bending resistance, and pressure cooker (hereinafter PCT) Resistance was evaluated by the following method. The results are shown in Tables 1 to 16.
(1) Evaluation of polyimide film adhesiveness A curable electromagnetic shielding adhesive film (or electromagnetic shielding film) having a width of 10 mm and a length of 70 mm is prepared, the peeling film 2 is peeled off, and the exposed curable conductive adhesive layer is exposed. A polyimide film having a thickness of 50 μm (“Kapton 200EN” manufactured by Toray DuPont Co., Ltd.) is pressure-bonded at 150 ° C., 1.0 MPa, and 30 min to form a conductive adhesive layer (I) and a film-like insulating composition. Product (II) was cured.
After pressure bonding, for the purpose of measurement reinforcement, the peelable film 1 is removed, and an exposed cured film-like insulating layer is coated with a polyurethane polyurea-based adhesive sheet. And pressure bonding for 30 min.
Peeling between the cured conductive adhesive layer and the polyimide film at 23 ° C. and 50% relative humidity at a pulling speed of 50 mm / min and a peeling angle of 90 °, and the central value of the peeling force is determined as the polyimide film adhesive strength (N / cm).
In the case of Comparative Examples 11 and 12, the measurement was not reinforced.

（２）耐熱性の評価
　幅１０ｍｍ、長さ６０ｍｍの硬化性電磁波シールド性接着性フィルム（又は電磁波シールドフィルム）を用意し、剥離性フィルム２を剥がし、露出した硬化性導電性接着剤層（Ｉ）に、厚さが５０μｍのポリイミドフィルム（東レ・デュポン社製「カプトン２００ＥＮ」）を１５０℃、１ＭＰａ、及び３０ｍｉｎの条件で圧着し、導電性接着剤層（Ｉ）及びフィルム状絶縁性組成物（II）を硬化させた。
　圧着後、剥離性フィルム１を除去し、１８０℃の電気オーブンで３ｍｉｎ、次いで２８０℃の電気オーブンで９０ｓｅｃ加熱処理した。加熱処理後の試料の外観を目視で観察し、発泡、浮き、及び／又は剥がれ等の外観不良の有無を評価した。
　それぞれ５回ずつ試験をおこない、外観不良が発生した回数で評価した。 (2) Evaluation of heat resistance A curable electromagnetic shielding adhesive film (or electromagnetic shielding film) having a width of 10 mm and a length of 60 mm is prepared, the peeling film 2 is peeled off, and the exposed curable conductive adhesive layer (I ), A polyimide film having a thickness of 50 μm (“Kapton 200EN” manufactured by Toray DuPont) is pressure-bonded at 150 ° C., 1 MPa, and 30 min to form a conductive adhesive layer (I) and a film-like insulating composition. (II) was cured.
After pressure bonding, the peelable film 1 was removed, and heat treatment was performed in an electric oven at 180 ° C. for 3 minutes and then in an electric oven at 280 ° C. for 90 seconds. The appearance of the sample after the heat treatment was visually observed, and the presence or absence of appearance defects such as foaming, floating, and / or peeling was evaluated.
Each test was conducted 5 times, and the evaluation was made by the number of appearance defects.

　○：外観不良発生せず
　△：外観不良発生が２回以内
　×：外観不良発生が３回以上 ○: Appearance failure does not occur △: Appearance failure occurs within 2 times ×: Appearance failure occurs 3 times or more

（３）耐屈曲性の評価
　幅６ｍｍ、長さ１２０ｍｍの硬化性電磁波シールド性接着性フィルム（又は電磁波シールドフィルム）から剥離性フィルム２を剥がし、露出した硬化性導電性接着剤層（Ｉ）を、別に作製したフレキシブルプリント配線板（厚み２５μｍのポリイミドフィルム上に、厚み１２μｍの銅箔からなる回路パターンが形成されており、更に回路パターン上に、接着剤付きの、厚み４０μｍのカバーフィルムが積層されてなる配線板）のカバーフィルム面に１５０℃、１ＭＰａ、及び３０ｍｉｎの条件で圧着し、導電性接着剤層（Ｉ）及びフィルム状絶縁性組成物（II）を硬化させた。
　剥離性フィルム１を除去し、曲率半径０．３８ｍｍ、荷重５００ｇ、及び速度１８０回／ｍｉｎの条件でＭＩＴ屈曲試験機にかけ、回路パターンが断線するまでの回数により耐屈曲性を評価した。評価基準は以下の通りである。
　○：３０００回以上
　△：１５００回以上３０００回未満
　×：１５００回未満 (3) Evaluation of bending resistance The peelable film 2 is peeled off from the curable electromagnetic shielding adhesive film (or electromagnetic shielding film) having a width of 6 mm and a length of 120 mm, and the exposed curable conductive adhesive layer (I) is removed. A separately prepared flexible printed wiring board (a circuit pattern made of a 12 μm thick copper foil is formed on a polyimide film having a thickness of 25 μm, and a cover film having a thickness of 40 μm with an adhesive is laminated on the circuit pattern. The conductive adhesive layer (I) and the film-like insulating composition (II) were cured by pressure bonding to the cover film surface of the printed wiring board) at 150 ° C., 1 MPa, and 30 min.
The peelable film 1 was removed and subjected to an MIT bending tester under conditions of a radius of curvature of 0.38 mm, a load of 500 g, and a speed of 180 times / min, and the bending resistance was evaluated by the number of times until the circuit pattern was disconnected. The evaluation criteria are as follows.
○: 3000 times or more Δ: 1500 times or more and less than 3000 times ×: less than 1500 times

（４）硬化性電磁波シールド性接着性フィルムのＰＣＴ耐性の評価
　幅２０ｍｍ、長さ５０ｍｍの硬化性電磁波シールド性接着性フィルム（又は電磁波シールドフィルム）から剥離性フィルム２を剥がし、露出した硬化性導電性接着剤層（Ｉ）を、別に作製したフレキシブルプリント配線板（厚み１２．５μｍのポリイミドフィルム上に、厚み１８μｍの銅箔からなり、電気的に接続されてはいない回路２Ａ、２Ｂが形成されており、回路２Ａ上に、接着剤付きの、厚み３７．５μｍ、直径１．６ｍｍのスルーホールを有するカバーフィルムが積層されてなる配線板）に１５０℃、１ＭＰａ、及び３０ｍｉｎの条件で圧着し、導電性接着剤層（Ｉ）及びフィルム状絶縁性組成物（II）を硬化させた（図１参照）。
　圧着後、剥離性フィルム１を除去し、図１（３）に示す２Ａ－２Ｂ間の抵抗値を三菱化学製「ロレスターＧＰ」の四探針プローブを用いて、ＰＣＴ（１２１℃、１００％ＲＨ、及び２気圧）の前後で測定した。評価基準は以下の通りである。
　○：５００ｍΩ未満
　△：５００ｍΩ以上１０００ｍΩ未満
　×：１０００ｍΩ以上 (4) Evaluation of PCT resistance of curable electromagnetic shielding adhesive film Exfoliation film 2 was peeled off from the curable electromagnetic shielding adhesive film (or electromagnetic shielding film) having a width of 20 mm and a length of 50 mm, and exposed curable conductivity. Circuit board 2A, 2B made of a copper foil with a thickness of 18 μm and not electrically connected to a flexible printed wiring board (with a thickness of 12.5 μm formed on the conductive adhesive layer (I). The circuit board 2A is pressure-bonded to the circuit 2A on a circuit board (with a cover film having a through hole having a thickness of 37.5 μm and a diameter of 1.6 mm) with an adhesive at 150 ° C., 1 MPa, and 30 min. The conductive adhesive layer (I) and the film-like insulating composition (II) were cured (see FIG. 1).
After the pressure bonding, the peelable film 1 is removed, and the resistance value between 2A and 2B shown in FIG. 1 (3) is set to PCT (121 ° C., 100% RH) using a four-point probe of “Lorestar GP” manufactured by Mitsubishi Chemical. , And 2 atm). The evaluation criteria are as follows.
○: Less than 500 mΩ Δ: 500 mΩ or more and less than 1000 mΩ ×: 1000 mΩ or more

（５）延性試験
　厚さが１２５μｍ、幅２０ｍｍ、長さ３０ｍｍの「小」ポリイミドフィルム（Ａ）を、幅５０ｍｍ、長さ５０ｍｍの「大」ポリイミドフィルム（Ｂ）のほぼ中央に置いた。
　幅５０ｍｍ、長さ６０ｍｍの硬化性電磁波シールド性接着性フィルム（又は電磁波シールドフィルム）を用意し、剥離性フィルム２を剥がし、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）で、前記「小」ポリイミドフィルム（Ａ）の全体を含めて前記「大」ポリイミドフィルム（Ｂ）の全面を覆い、１５０℃、１ＭＰａ、及び３０ｍｉｎの条件で圧着し、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた。
　圧着後、剥離性フィルム１を除去し、硬化後の電磁波シールドフィルムと前記「大」ポリイミドフィルム（Ｂ）との間に挟まれた前記「小」ポリイミドフィルム（Ａ）の各辺部分（段差による突起部分）を、硬化後の電磁波シールドフィルムの絶縁層を通して、肉眼で及び５０倍のマイクロスコープで観察し、段差による突起部分の硬化後の導電性接着剤層が透けて見える程度を評価した。
　○：肉眼及びマイクロスコープのいずれにおいても、導電性接着剤層が透けて見えることはなかった。
　△：肉眼では導電性接着剤層が透けて見えることはなかったが、マイクロスコープでは導電性接着剤層が透けて見えた。
　×：肉眼及びマイクロスコープのいずれにおいても、導電性接着剤層が透けて見えた。 (5) Ductility test A “small” polyimide film (A) having a thickness of 125 μm, a width of 20 mm, and a length of 30 mm was placed almost at the center of a “large” polyimide film (B) having a width of 50 mm and a length of 50 mm.
A curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) having a width of 50 mm and a length of 60 mm was prepared, the peelable film 2 was peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I), The entire surface of the “large” polyimide film (B) including the whole of the “small” polyimide film (A) is covered and pressure-bonded under conditions of 150 ° C., 1 MPa, and 30 min, and a curable conductive polyurethane polyurea adhesive layer (I ) And the curable insulating polyurethane polyurea resin composition layer (II).
After crimping, the peelable film 1 is removed, and each side portion of the “small” polyimide film (A) sandwiched between the cured electromagnetic wave shielding film and the “large” polyimide film (B) (depending on the level difference) The projection portion) was observed with the naked eye and with a 50 × microscope through the insulating layer of the cured electromagnetic wave shielding film, and the degree to which the conductive adhesive layer after the projection portion was cured due to the step was seen through was evaluated.
○: The conductive adhesive layer was not seen through both with the naked eye and with a microscope.
Δ: Although the conductive adhesive layer was not seen through with the naked eye, the conductive adhesive layer was seen through with the microscope.
X: The conductive adhesive layer was seen through both in the naked eye and in the microscope.

（６）接着剤層のはみ出し性の評価
　厚さが５０μｍのポリイミドフィルム（東レ・デュポン社製「カプトン２００ＥＮ」）の一方の面に、各実施例及び各比較例に記載の各硬化性導電性ポリウレタンポリウレア接着剤組成物を塗工し、電気オーブンを用い、１００℃で２分、乾燥し、乾燥膜厚が８μｍの硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成し、穴あけ機で直径５ｍｍの穴を、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及びポリイミドフィルムに貫通させて形成した。
　別途、厚さが５０μｍのポリイミドフィルム（東レ・デュポン社製「カプトン２００ＥＮ」）の一方の面に、各実施例及び各比較例に記載の各硬化性絶縁性ポリウレタンポリウレア樹脂組成物を塗工し、電気オーブンを用い、１００℃で２分、乾燥し、乾燥膜厚が１５μｍの硬化性絶縁性ポリウレタンポリウレア組成物層（II）を形成した。
　次いで、穴の開いた硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね、１５０℃、１．０ＭＰａ、及び３０ｍｉｎの条件で圧着処理をした。圧着処理後、硬化後の導電性接着剤層の穴部分を、拡大鏡を用いて観察し、硬化時の導電性接着剤のはみ出し量を測定した。評価基準は以下の通りである。
　○：導電性接着剤層のはみ出し量が０．１ｍｍ未満、すなわち、硬化後の接着剤層（Ｉ）の穴の直径が４．８ｍｍを超えた。
　×：導電性接着剤層のはみ出し量が０．１ｍｍ以上、すなわち、硬化後の接着剤層（Ｉ）の穴の直径が４．８ｍｍ以下であった。 (6) Evaluation of protrusion property of adhesive layer On one surface of polyimide film having a thickness of 50 μm (“Kapton 200EN” manufactured by Toray DuPont), each curable conductive property described in each example and each comparative example The polyurethane polyurea adhesive composition is applied and dried at 100 ° C. for 2 minutes using an electric oven to form a curable conductive polyurethane polyurea adhesive layer (I) having a dry film thickness of 8 μm. A hole having a diameter of 5 mm was formed through the curable conductive polyurethane polyurea adhesive layer (I) and the polyimide film.
Separately, each curable insulating polyurethane polyurea resin composition described in each example and each comparative example was applied to one surface of a polyimide film having a thickness of 50 μm (“Kapton 200EN” manufactured by Toray DuPont). Then, it was dried at 100 ° C. for 2 minutes using an electric oven to form a curable insulating polyurethane polyurea composition layer (II) having a dry film thickness of 15 μm.
Next, the curable conductive polyurethane polyurea adhesive layer (I) having a hole and the curable insulating polyurethane polyurea resin composition layer (II) are stacked and subjected to pressure-bonding treatment at 150 ° C., 1.0 MPa, and 30 min. Did. After the pressure-bonding treatment, the hole portion of the cured conductive adhesive layer was observed using a magnifying glass, and the amount of the conductive adhesive protruding at the time of curing was measured. The evaluation criteria are as follows.
A: The protruding amount of the conductive adhesive layer was less than 0.1 mm, that is, the diameter of the hole of the cured adhesive layer (I) exceeded 4.8 mm.
X: The protruding amount of the conductive adhesive layer was 0.1 mm or more, that is, the diameter of the hole of the cured adhesive layer (I) was 4.8 mm or less.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008

Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010

Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011

Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012

Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013

Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014

Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015

Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016

　各表中の記号は下記の通りである。
Ｂ－１、Ｄ－１：ビスフェノールＡ型エポキシ樹脂、ジャパンエポキシレジン製「ＪＥＲ８２８」、エポキシ当量＝１８９ｇ／ｅｑ。
Ｂ－２、Ｄ－２：ビスフェノールＡ型エポキシ樹脂、ジャパンエポキシレジン製「ＪＥＲ１００２」、エポキシ当量＝６５０ｇ／ｅｑ。
Ｂ－３、Ｄ－３：テトラキス（グリシジルオキシフェニル）エタン型エポキシ樹脂、ジャパンエポキシレジン製「ＪＥＲ１０３１」、エポキシ当量＝１９０ｇ／ｅｑ。
Ｂ－４、Ｄ－４：単官能エポキシ樹脂、ダウ・ケミカル製「ＵＶＲ－６２１６」、エポキシ当量＝２４０ｇ／ｅｑ。
ＰＰＳ：ポリフェニレンサルファイドフィルム。
ＰＥＴ：ポリエチレンテレフタレートフィルム。
 
　以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は本発明の範囲に含まれる。 The symbols in each table are as follows.
B-1, D-1: Bisphenol A type epoxy resin, “JER828” manufactured by Japan Epoxy Resin, epoxy equivalent = 189 g / eq.
B-2, D-2: bisphenol A type epoxy resin, “JER1002” manufactured by Japan Epoxy Resin, epoxy equivalent = 650 g / eq.
B-3, D-3: Tetrakis (glycidyloxyphenyl) ethane type epoxy resin, “JER1031” manufactured by Japan Epoxy Resin, epoxy equivalent = 190 g / eq.
B-4, D-4: Monofunctional epoxy resin, “UVR-6216” manufactured by Dow Chemical, epoxy equivalent = 240 g / eq.
PPS: polyphenylene sulfide film.
PET: Polyethylene terephthalate film.

As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (27)

　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する硬化性電磁波シールド性接着性フィルムであって、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）とを含有し、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部とを含有し、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有することを特徴とする、硬化性電磁波シールド性接着性フィルム。 A curable electromagnetic shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B), containing a conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B),
The curable insulating polyurethane polyurea resin composition layer (II) comprises a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups A curable electromagnetic wave shielding adhesive film, comprising (D). 　ゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、硬化性電磁波シールド性接着性フィルムであって、
　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤から形成されてなり、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有することを特徴とする、硬化性電磁波シールド性接着性フィルム。 A curable electromagnetic shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and a curable insulating polyurethane polyurea resin composition layer (II). There,
The curable conductive polyurethane polyurea adhesive layer (I) reacts the diol compound (a1) having a carboxyl group, the polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and the organic diisocyanate (a3). The polyurethane polyurea resin (A) obtained by reacting the urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with the polyamino compound (a5), and the epoxy resin (B) having two or more epoxy groups ), The polyurethane polyurea resin (A) and the epoxy resin (B) in a total of 100 parts by weight, the conductive filler: 10 to 700 parts by weight, and the aziridine-based curing agent (E) are added to the polyurethane polyurea resin. (A) aziridinyl group for 1 mol of carboxyl group Is formed from the curable conductive polyurethane polyurea adhesive containing 0.05 to 4 moles of the range will be,
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups A curable electromagnetic wave shielding adhesive film comprising (D). 　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、ゲル分率が３０～９０重量％である、硬化性電磁波シールド性接着性フィルムであって、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤から形成されてなり、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成されてなる、ことを特徴とする、硬化性電磁波シールド性接着性フィルム。 A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight Because
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B), a conductive filler: 10 to 700 parts by weight, and an aziridine-based curing agent (E) with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B), and the polyurethane polyurea An aziridini with respect to 1 mol of carboxyl groups in the resin (A) It is formed from a curable conductive polyurethane-polyurea adhesives containing in the range of from 0.05 to 4 moles of group,
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (F) having a film-forming ability containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). It is not formed from a curable insulating polyurethane polyurea resin composition. , Wherein the curable electromagnetic shielding adhesive film. 　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と、ゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを有する、硬化性電磁波シールド性接着性フィルムであって、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、導電性フィラーとを含有し、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部とを含有し、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有するフィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物から形成されたことを特徴とする、硬化性電磁波シールド性接着性フィルム。 A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight. There,
The curable conductive polyurethane polyurea adhesive layer (I) comprises a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by the reaction with a polyamino compound (a5), and an epoxy resin having two or more epoxy groups ( B) and a conductive filler, containing a conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the polyurethane polyurea resin (A) and the epoxy resin (B),
The curable insulating polyurethane polyurea resin composition layer (II) has a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups Curing having film-forming ability containing (D) and an aziridin-based curing agent (E) in a range of 0.05 to 4 mol of aziridinyl group with respect to 1 mol of carboxyl group in the polyurethane polyurea resin (C). Formed from a conductive insulating polyurethane polyurea resin composition Wherein, the curable electromagnetic shielding adhesive film. 　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が、ポリウレタンポリウレア樹脂（Ａ）１００重量部に対して、エポキシ樹脂（Ｂ）３～２００重量部を含有し、かつ、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が、ポリウレタンポリウレア樹脂（Ｃ）１００重量部に対して、エポキシ樹脂（Ｄ）３～２００重量部を含有することを特徴とする請求項１～４いずれか記載の硬化性電磁波シールド性接着性フィルム。 The curable conductive polyurethane polyurea adhesive layer (I) contains 3 to 200 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A), and the curable insulating polyurethane polyurea resin. 5. The curability according to claim 1, wherein the composition layer (II) contains 3 to 200 parts by weight of the epoxy resin (D) with respect to 100 parts by weight of the polyurethane polyurea resin (C). Electromagnetic shielding adhesive film. 　硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が接触していない表面上に、剥離性フィルム１が積層されていることを特徴とする請求項５記載の硬化性電磁波シールド性接着性フィルム。 The peelable film 1 is laminated on the surface of the curable insulating polyurethane polyurea resin composition layer (II) which is not in contact with the curable conductive polyurethane polyurea adhesive layer (I). The curable electromagnetic wave shielding adhesive film according to claim 5. 　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が接触していない表面上に、剥離性フィルム２が積層されていることを特徴とする請求項５記載の硬化性電磁波シールド性接着性フィルム。 The peelable film 2 is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) which is not in contact with the curable insulating polyurethane polyurea resin composition layer (II). The curable electromagnetic wave shielding adhesive film according to claim 5. 　硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）の、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）が接触していない表面上に、剥離性フィルム２が積層されており、かつ、硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）の、硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）が接触していない表面上に、剥離性フィルム１が積層されていることを特徴とする請求項５記載の硬化性電磁波シールド性接着性フィルム。 The peelable film 2 is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) that is not in contact with the curable insulating polyurethane polyurea resin composition layer (II), and is curable. The peelable film 1 is laminated on the surface of the insulating polyurethane polyurea resin composition layer (II) that is not in contact with the curable conductive polyurethane polyurea adhesive layer (I). 5. The curable electromagnetic wave shielding adhesive film according to 5. 　剥離性フィルム１の一方の表面上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　剥離性フィルム２の一方の表面上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1 And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing,
Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2 A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal thereof with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of conductive filler is formed with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B). And the process of
A method for producing a curable electromagnetic shielding adhesive film, comprising a step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). 　剥離性フィルム１の一方の表面上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 and an organic diisocyanate (c3) other than the carboxyl group-containing diol compound on one surface of the peelable film 1 And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing,
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) And a polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5) and an epoxy having two or more epoxy groups. Curable conductive polyurethane polyurea adhesive containing resin (B) and 10 to 700 parts by weight of conductive filler with respect to 100 parts by weight of the total of polyurethane polyurea resin (A) and epoxy resin (B) Forming layer (I); and
A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I),
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　剥離性フィルム２の一方の表面上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2 A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, Forming a curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B). The process of
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing (D), and
A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　剥離性フィルム２の一方の表面上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 1 with a diol compound having a carboxyl group (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). Contains a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups Forming a curable insulating polyurethane polyurea resin composition layer (II), and
Obtained by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) on one surface of the peelable film 2 A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal with the polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, Conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B), and the polyurethane polyurea resin (A) 0.05-4 mol of aziridinyl group per 1 mol of carboxyl group Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in the range and,
A step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からからゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 1 with a diol compound having a carboxyl group (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). Contains a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal with a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups Forming a curable insulating polyurethane polyurea resin composition layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) Obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5), and an epoxy having two or more epoxy groups. Conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the resin (B), the polyurethane polyurea resin (A) and the epoxy resin (B), and the aziridine-based curing agent (E), Addition of 1 mol of carboxyl group in polyurethane polyurea resin (A) A step of forming a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing a dinyl group in the range of 0.05 to 4 mol. ,as well as,
A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I),
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）とを含有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) are added to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) in the polyurethane polyurea resin (A). Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference,
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups A step of forming a curable insulating polyurethane polyurea resin composition layer (II) containing (D), and
A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程、
　を含む、ゲル分率が３０～９０重量％の硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) are added to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) in the polyurethane polyurea resin (A). Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference and,
A step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II);
And a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight. 　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からなるゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程を含む、ゲル分率が３０～９０重量％の硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) Obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5), and an epoxy having two or more epoxy groups. Conductive filler: 10 to 700 parts by weight with respect to a total of 100 parts by weight of the resin (B), the polyurethane polyurea resin (A) and the epoxy resin (B), and the aziridine-based curing agent (E), Addition of 1 mol of carboxyl group in polyurethane polyurea resin (A) A step of forming a curable conductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight and comprising a curable conductive polyurethane polyurea adhesive containing a dinyl group in the range of 0.05 to 4 mol. ,as well as,
A method for producing a curable electromagnetic shielding adhesive film having a gel fraction of 30 to 90% by weight, comprising a step of superposing a peelable film 2 on the curable conductive polyureurethane / polyurea adhesive layer (I). 　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して導電性フィラー：１０～７００重量部と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ａ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する硬化性導電性ポリウレタンポリウレア接着剤からゲル分率が３０～９０重量％の硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｆ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程を含む、ゲル分率が３０～９０重量％の硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A conductive filler: 10 to 700 parts by weight and an aziridine-based curing agent (E) are added to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) in the polyurethane polyurea resin (A). Of aziridinyl group per mole of carboxyl group of Step gel fraction from setting conductive polyurethane-polyurea adhesives containing form 30 to 90% by weight of the curable conductive polyurethane-polyurea adhesive layer (I) in circumference,
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (F) having a film-forming ability containing an aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C). A gel fraction of 30 from the curable insulating polyurethane polyurea resin composition A step of forming 90% by weight of a curable insulating polyurethane polyurea resin composition layer (II), and a step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II), A method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight. 　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）と前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）とを重ね合わせる工程
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing a curable resin (E) in an amount of 0.05 to 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is formed. Process and
A method for producing a curable electromagnetic shielding adhesive film, comprising a step of superposing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). 　剥離性フィルム１の一方の表面に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、及び、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に剥離性フィルム２を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 1 with a carboxyl group-containing diol compound (c1), a polyol (c2) having a number average molecular weight of 500 to 8000 other than a carboxyl group-containing diol compound, and an organic diisocyanate (c3). Polyurethane polyurea resin (C) obtained by reacting an isocyanate group-terminated urethane prepolymer (c4) with a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and aziridine A curable insulating polyurethane polyurea having a film-forming ability, containing a curable resin (E) in an amount of 0.05 to 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups in the polyurethane polyurea resin (C). Curable insulating property with a gel fraction of 30 to 90% by weight from the resin composition Forming re urethane-polyurea resin composition layer (II),
On the curable insulating polyurethane polyurea resin composition layer (II), a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3) ) And a polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (a5) and an epoxy having two or more epoxy groups. Curable conductive polyurethane polyurea adhesive containing resin (B) and 10 to 700 parts by weight of conductive filler with respect to 100 parts by weight of the total of polyurethane polyurea resin (A) and epoxy resin (B) Forming layer (I); and
A step of superposing a peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I),
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　剥離性フィルム２の一方の表面に、カルボキシル基を有するジオール化合物（ａ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ａ２）及び有機ジイソシアネート（ａ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ａ４）と、ポリアミノ化合物（ａ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ａ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｂ）と、前記ポリウレタンポリウレア樹脂（Ａ）と前記エポキシ樹脂（Ｂ）との合計１００重量部に対して１０～７００重量部の導電性フィラーとを含有する硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を形成する工程、
　前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）上に、カルボキシル基を有するジオール化合物（ｃ１）、カルボキシル基含有ジオール化合物以外の数平均分子量５００～８０００のポリオール（ｃ２）及び有機ジイソシアネート（ｃ３）を反応させて得られる末端にイソシアネート基を有するウレタンプレポリマー（ｃ４）と、ポリアミノ化合物（ｃ５）とを反応させて得られるポリウレタンポリウレア樹脂（Ｃ）と、２個以上のエポキシ基を有するエポキシ樹脂（Ｄ）と、アジリジン系硬化剤（Ｅ）を、前記ポリウレタンポリウレア樹脂（Ｃ）中のカルボキシル基１モルに対し、アジリジニル基を０．０５～４モルの範囲で含有する、フィルム形成能を有する硬化性絶縁性ポリウレタンポリウレア樹脂組成物からゲル分率が３０～９０重量％の硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を形成する工程、及び、
　前記硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）上に剥離性フィルム１を重ね合わせる工程、
　を含む、硬化性電磁波シールド性接着性フィルムの製造方法。 Obtained by reacting one surface of the peelable film 2 with a diol compound having a carboxyl group (a1), a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). A polyurethane polyurea resin (A) obtained by reacting a urethane prepolymer (a4) having an isocyanate group at a terminal with a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, A curable conductive polyurethane polyurea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is formed. Process,
On the curable conductive polyurethane polyurea adhesive layer (I), a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3) A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group at the terminal obtained by reacting with a polyamino compound (c5), and an epoxy resin having two or more epoxy groups (D) and an aziridine-based curing agent (E) containing a aziridinyl group in a range of 0.05 to 4 mol with respect to 1 mol of a carboxyl group in the polyurethane polyurea resin (C) and having a film-forming ability. A gel fraction of 30 from a curable insulating polyurethane polyurea resin composition Step of Forming 90 wt% of the curable insulating polyurethane polyurea resin composition layer (II) and,
A step of superposing a peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II);
The manufacturing method of the curable electromagnetic wave shielding adhesive film containing this. 　請求項８記載の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた後に、剥離性フィルム１を剥離することを特徴とする請求項８記載の硬化性電磁波シールド性接着性フィルムの使用方法。 The peelable film 2 of the curable electromagnetic wave shielding adhesive film according to claim 8 is peeled, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superimposed on an adherend, heated, and cured. The curable film according to claim 8, wherein the peelable film 1 is peeled after the conductive conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are cured. How to use an electromagnetic shielding adhesive film. 　請求項８記載の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、剥離性フィルム１を剥離し、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させることを特徴とする請求項８記載の硬化性電磁波シールド性接着性フィルムの使用方法。 The peelable film 2 of the curable electromagnetic wave shielding adhesive film according to claim 8 is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, and the peelable film 1 is attached. 9. The curable electromagnetic wave shield according to claim 8, wherein the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are cured by peeling and heating. To use adhesive adhesive film. 　請求項６記載の硬化性電磁波シールド性接着性フィルムの、露出している硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた後に、剥離性フィルム１を剥離することを特徴とする電磁波遮蔽物の製造方法。 The exposed curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film according to claim 6 is superimposed on an adherend and heated to bond the curable conductive polyurethane polyurea adhesive. A method for producing an electromagnetic wave shielding material, comprising: peeling off the peelable film 1 after curing the agent layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). 　請求項７記載の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させることを特徴とする電磁波遮蔽物の製造方法。 The peelable film 2 of the curable electromagnetic wave shielding adhesive film according to claim 7 is peeled, the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, heated, and cured. A method for producing an electromagnetic wave shielding material, comprising curing a conductive conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II). 請求項８記載の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させた後に剥離性フィルム１を剥離することを特徴とする電磁波遮蔽物の製造方法。 The peelable film 2 of the curable electromagnetic wave shielding adhesive film according to claim 8 is peeled, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superimposed on an adherend, heated, and cured. A method for producing an electromagnetic wave shielding material, comprising: peeling the peelable film 1 after curing the conductive conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). 　請求項８記載の硬化性電磁波シールド性接着性フィルムの、剥離性フィルム２を剥離し、露出した硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）を被着体に重ね合わせ、剥離性フィルム１を剥離し、加熱し、前記硬化性導電性ポリウレタンポリウレア接着剤層（Ｉ）及び硬化性絶縁性ポリウレタンポリウレア樹脂組成物層（II）を硬化させることを特徴とする電磁波遮蔽物の製造方法。 The peelable film 2 of the curable electromagnetic wave shielding adhesive film according to claim 8 is peeled off, and the exposed curable conductive polyurethane polyurea adhesive layer (I) is superposed on the adherend, and the peelable film 1 is attached. A method for producing an electromagnetic wave shielding material, comprising peeling and heating to cure the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). 　請求項２３～２６いずれか記載の製造方法により得られた電磁波遮蔽物。 An electromagnetic shielding material obtained by the production method according to any one of claims 23 to 26.
PCT/JP2009/050467 2008-01-15 2009-01-15 Curable electromagnetic shielding adhesive film, method for producing the same, use of the same, method for producing electromagnetic shielding article, and electromagnetic shielding article Ceased WO2009090997A1 (en)

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