Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
  • C09J9/02—Electrically-conducting adhesives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • H—ELECTRICITY
  • 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
  • H05K3/30—Assembling printed circuits with electric components, e.g. with resistors
  • H05K3/32—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
• • 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
  • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to a conductive adhesive film. Further, the present invention relates to an electromagnetic wave shield, an electronic device, and a wiring board using a conductive adhesive film.
• the conductive adhesive film may be used for the purpose of imparting an electromagnetic wave shielding function to a mounting portion at the same time as bonding a reinforcing member of a flexible printed wiring board accompanied by mounting a component such as a camera module of a mobile phone.
• the conductive adhesive film in order to exhibit sufficient conductivity, it is required to fill a certain amount or more of the conductive filler, but if the blending amount of the conductive filler is increased, there is a problem that the adhesiveness is inferior. ..
• the present invention has been made in view of the above circumstances, and is a conductive adhesive film having excellent conductivity and good adhesive performance, and an electromagnetic wave shield, an electronic device, and a wiring board using the conductive adhesive film.
• the purpose is to provide.
• the present inventor has excellent conductivity and good adhesive performance by containing a specific polymer resin in the thermosetting resin composition constituting the conductivity. We have found that it is possible to provide a conductive adhesive film, and have completed the present invention.
• the conductive layer contains a thermosetting resin composition and contains The thermosetting resin composition contains (a) an epoxy resin, (b) a polymer resin having a glass transition temperature of 25 ° C. or lower or a liquid at 25 ° C., (c) a curing agent, and (d) a conductive filler. death, (D) A conductive adhesive film in which the component is at least one selected from metal particles selected from silver, copper and nickel, and metal-coated particles selected from silver, copper and nickel. .. [2] The conductive adhesive film according to [1], wherein the component (a) is an epoxy resin having an aromatic structure.
• the component (b) is selected from the group consisting of a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisobutylene structure, a polyisobutylene structure, a polycarbonate structure, a poly (meth) acrylate structure, and a polysiloxane structure.
• An electromagnetic wave shield containing a cured product of the thermosetting resin composition of the conductive adhesive film according to any one of [1] to [7].
• An electronic device comprising a cured product of the thermosetting resin composition of the conductive adhesive film according to any one of [1] to [7].
• a wiring board provided with a cured product of the thermosetting resin composition layer of the conductive adhesive film according to any one of [1] to [7].
• the wiring board according to [10] which is a flexible wiring board.
• the present invention it is possible to provide a conductive adhesive film having excellent conductivity and good adhesive performance, and an electromagnetic wave shield, an electronic device, and a wiring board using the conductive adhesive film.
• the conductive adhesive film of the present invention the electromagnetic wave shield using the conductive adhesive film, the electronic device, and the wiring board will be described in detail.
• the conductive adhesive film of the present invention includes a support and a conductive layer, and in one embodiment, the conductive adhesive film includes a support and a conductive layer bonded to the support.
• the conductive layer contains a thermosetting resin composition, and usually contains only a thermosetting resin composition.
• the thermosetting resin composition contains (a) an epoxy resin, (b) a polymer resin having a glass transition temperature of 25 ° C. or lower or a liquid at 25 ° C., (c) a curing agent, and (d) a conductive filler. do.
• each layer constituting the conductive adhesive film will be described in detail.
• the conductive adhesive film of the present invention includes a support.
• the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
• the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET”) or polyethylene naphthalate (hereinafter abbreviated as “PEN”).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PC polycarbonate
• acrylics such as polymethylmethacrylate (PMMA)
• PMMA polymethylmethacrylate
• TAC triacetylcellulose
• PES polyethersulfide
• polyethers examples thereof include ketones and polyimides.
• polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
• the metal foil When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferable.
• the copper foil a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.
• the metal foil one in which a plurality of metal foils are laminated may be used.
• the support may be matted or corona-treated on the surface to be joined to the conductive layer.
• a support with a release layer having a release layer on the surface to be joined to the conductive layer may be used.
• the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. ..
• a commercially available product may be used.
• “SK-1” and “SK-1” manufactured by Lintec Corporation which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include “AL-5", “AL-7", and “Lumirror T6AM” manufactured by Toray Industries, Inc.
• the thickness of the support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, and more preferably in the range of 10 ⁇ m to 60 ⁇ m.
• the thickness of the entire support with a release layer is preferably in the above range.
• the conductive adhesive film of the present invention includes a conductive layer, and the conductive layer is composed of a thermosetting resin composition.
• the thermosetting resin composition contains (a) an epoxy resin, (b) a polymer resin having a glass transition temperature of 25 ° C. or lower or a liquid at 25 ° C., (c) a curing agent, and (d) a conductive filler.
• the thermosetting resin composition may further contain (e) a curing accelerator, (f) and other additives, if necessary.
• thermosetting resin composition contains (a) an epoxy resin as a component (a).
• an epoxy resin having an aromatic structure from the viewpoint of remarkably obtaining the effect of the present invention.
• the aromatic structure is a chemical structure generally defined as an aromatic, and also includes a polycyclic aromatic and an aromatic heterocycle.
• the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, and naphthol novolac type.
• Epoxy resin phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisilylenol type epoxy resin, glycidylamine type epoxy resin with aromatic structure, fragrance It has a glycidyl ester type epoxy resin having a group structure, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin having an aromatic structure, an epoxy resin having a butadiene structure having an aromatic structure, and an aromatic structure.
• examples thereof include an epoxy resin and a tetraphenylethane type epoxy resin having an aromatic structure.
• the epoxy resin may be used alone or in combination of two or more. Above all, the component (a) is preferably one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a biphenyl type epoxy resin.
• the epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule.
• the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule.
• the epoxy resin preferably contains a solid epoxy resin at a temperature of 20 ° C. Among them, one molecule has two or more epoxy groups, and a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and one molecule have three or more epoxy groups. It is preferable to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C.
• liquid epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, and glycidylamine type epoxy resin having an aromatic structure.
• Phenol novolak type epoxy resin, alicyclic epoxy resin having an ester skeleton having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, and epoxy resin having a butadiene structure having an aromatic structure are preferable, and bisphenol A is preferable.
• Type epoxy resin bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are further preferable.
• Specific examples of the liquid epoxy resin include "HP4032", “HP4032D” and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, and "828US” and “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.
• solid epoxy resin examples include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene.
• Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin are preferable.
• a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are further preferable.
• the solid epoxy resin include "HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalen type tetrafunctional epoxy resin), and "N-690” manufactured by DIC.
• Cresol novolak type epoxy resin Cresol novolak type epoxy resin
• N-695" cresol novolak type epoxy resin
• HP-7200 dicyclopentadiene type epoxy resin
• HP-7200HH high-7200H
• EXA7311 EXA7311-G3
• EXA7311-G4S EXA7311-G4S
• HP6000 naphthylene ether type epoxy resin
• EPPN-502H trisphenol type epoxy resin
• NC7000L naphthol novolac type epoxy resin
• NC3000H N3000
• NC3000L N3100
• ESN475V naphthol type epoxy resin
• Mitsubishi Chemical's YX4000H"
• the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is in the range of 1: 0.1 to 1:20 in terms of mass ratio. preferable.
• the form of the conductive adhesive film provides appropriate adhesiveness when used in the form of the conductive adhesive film, ii) the form of the conductive adhesive film.
• the quantitative ratio of the liquid epoxy resin to the solid epoxy resin is in the range of 1: 0.3 to 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 9 is even more preferable.
• the content of the (a) epoxy resin in the thermosetting resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 6 from the viewpoint of obtaining a conductive layer exhibiting good mechanical strength. It is mass% or more.
• the upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 40% by mass or less.
• the content of each component in the thermosetting resin composition is a value when the non-volatile component in the thermosetting resin composition is 100% by mass, unless otherwise specified.
• the epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000.
• the epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.
• the weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500.
• the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.
• thermosetting resin composition contains (b) a polymer resin which is liquid at a glass transition temperature of 25 ° C. or lower or 25 ° C. as a component (b).
• a polymer resin which is liquid at a glass transition temperature of 25 ° C. or lower or 25 ° C.
• the component (b) only a polymer resin having a glass transition temperature of 25 ° C. or lower may be used, or only a polymer resin liquid at 25 ° C. may be used, and the glass transition temperature is as high as 25 ° C. or less.
• a molecular resin and a polymer resin that is liquid at 25 ° C. may be used in combination.
• the glass transition temperature (Tg) of the component (b) is 25 ° C. or lower, and the glass transition temperature of the polymer resin is preferably 20 ° C. or lower, more preferably 15 ° C. or lower.
• the lower limit of the glass transition temperature of the component (b) is not particularly limited, but may be usually ⁇ 15 ° C. or higher.
• the component (b) preferably has a functional group capable of reacting with the component (a). That is, the component (b) is preferably a resin having a functional group having a glass transition temperature of 25 ° C. or lower, and one or more resins selected from the resin having a functional group which is liquid at 25 ° C. Is preferable.
• the functional group of the component (b) is one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. Is.
• a hydroxyl group, an acid anhydride group, an epoxy group and a phenolic hydroxyl group are preferable, and a hydroxyl group, an acid anhydride group and an epoxy group are more preferable.
• an epoxy group is contained as a functional group, it is preferable that the component (b) does not have an aromatic structure.
• the component (b) contains a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, a poly (meth) acrylate structure, and a polysiloxane from the viewpoint of obtaining a conductive layer having excellent adhesiveness. It is preferable to have one or more structures selected from the group consisting of structures, and more preferably to have one or more structures selected from the group consisting of a polybutadiene structure and a poly (meth) acrylate structure.
• (meth) acrylate refers to methacrylate and acrylate.
• the polyalkylene structure is preferably a polyalkylene structure having 2 to 15 carbon atoms, more preferably a polyalkylene structure having 3 to 10 carbon atoms, and more preferably a polyalkylene structure having 5 to 6 carbon atoms.
• the polyalkylene oxy structure is preferably a polyalkylene oxy structure having 2 to 15 carbon atoms, more preferably a polyalkylene oxy structure having 3 to 10 carbon atoms, and more preferably a polyalkylene oxy structure having 5 to 6 carbon atoms. be.
• a preferred embodiment of the component (b) is a butadiene resin.
• the butadiene resin is preferably a butadiene resin that is liquid at 25 ° C or has a glass transition temperature of 25 ° C or less, and is a hydrided polybutadiene skeleton-containing resin (for example, a hydride polybutadiene skeleton-containing epoxy resin), a hydroxy group-containing butadiene resin, or a phenolic hydroxyl group-containing butadiene.
• a resin (a resin having a polybutadiene structure and a phenolic hydroxyl group), a carboxy group-containing butadiene resin, an acid anhydride group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin, and a urethane group-containing butadiene resin.
• a resin a resin having a polybutadiene structure and a phenolic hydroxyl group
• a carboxy group-containing butadiene resin an acid anhydride group-containing butadiene resin
• an epoxy group-containing butadiene resin an isocyanate group-containing butadiene resin
• urethane group-containing butadiene resin a urethane group-containing butadiene resin.
• the "butadiene resin” refers to a resin containing a polybutadiene structure, and in these resins, the polybutadiene structure may be contained in the main chain or the side chain.
• the polybutadiene structure may be partially or wholly hydrogenated.
• the "hydrogenated polybutadiene skeleton-containing resin” refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin.
• the number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, still more preferably 10,000 to. It is 15,000.
• the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).
• the functional group equivalent is preferably 100 to 10000, more preferably 200 to 5000.
• the functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group.
• the epoxy group equivalent can be measured according to JIS K7236.
• the hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.
• butadiene resin examples include “Ricon 657” (polybutadiene containing an epoxy group), “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 131MA5", “Ricon 131MA10”, and “Ricon 131MA10” manufactured by Clay Valley.
• a resin having an imide structure can also be used.
• a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials polyimide described in JP-A-2006-37083, International Publication No. 2008/153208,. And so on.
• the content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass.
• the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.
• a more preferred embodiment of the component (b) is a polyimide resin having a polybutadiene structure, a urethane structure, and an imide structure in the molecule, and the polyimide resin preferably has a phenol structure at the molecular terminal.
• the number average molecular weight (Mn) of the polyimide resin is preferably 1000 to 100,000, more preferably 10,000 to 15,000.
• the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).
• the acid value of the polyimide resin is preferably 1 KOH / g to 30 KOH / g, more preferably 10 KOH / g to 20 KOH / g.
• the content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass.
• the acrylic resin preferably has a glass transition temperature (Tg) of 25 ° C. or lower, and is preferably a hydroxy group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, or an epoxy group.
• Tg glass transition temperature
• One or more resins selected from the group consisting of a contained acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin are more preferable.
• the "acrylic resin” refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or the side chain.
• the number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000.
• the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).
• the functional group equivalent is preferably 1000 to 50,000, more preferably 2500 to 30,000.
• acrylic resin examples include Teisan resin "SG-70L”, “SG-708-6", “WS-023”, “SG-700AS”, and “SG-280TEA” (carboxy group) manufactured by Nagase ChemteX Corporation. Containing acrylic acid ester copolymer resin, acid value 5 to 34 mgKOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5 ° C), "SG-80H”, “SG-80H-3", “SG” -P3 "(epoxide group-containing acrylic acid ester copolymer resin, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12 ° C.),” SG-600TEA ",” SG-790 "” (Hydroxy group-containing acrylic acid ester copolymer resin, hydroxyl value 20 to 40 mgKOH / g, weight average molecular weight 500,000 to 1.2 million, Tg-37
• a preferred embodiment of the component (b) is a carbonate resin.
• the carbonate resin preferably has a glass transition temperature of 25 ° C. or lower, and is preferably a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, or an epoxy group-containing carbonate resin.
• One or more resins selected from the group consisting of isocyanate group-containing carbonate resins and urethane group-containing carbonate resins are preferred.
• the "carbonate resin” refers to a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or the side chain.
• the number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferable range is also the same.
• carbonate resin examples include “T6002” and “T6001” (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and “C-1090", “C-2090” and “C-3090” (polycarbonate diol) manufactured by Kuraray. And so on.
• a linear polyimide (PCT / JP2016 / 053609) made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used.
• the content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass.
• the description of PCT / JP2016 / 053609 can be referred to, and the contents thereof are incorporated in the present specification.
• a preferred embodiment of the further component (b) is a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, an isoprene resin, or an isobutylene resin.
• the polysiloxane resin is a resin containing a polysiloxane structure.
• Specific examples of the polysiloxane resin include "SMP-2006”, “SMP-2003PGMEA”, “SMP-5005PGMEA” manufactured by Shinetsu Silicone Co., Ltd., an amine group-terminated polysiloxane, and a linear polyimide made from tetrabasic acid anhydride. International Publication No. 2010/053185) and the like can be mentioned.
• the alkylene resin is a resin containing a polyalkylene structure.
• alkylene resin examples include "PTXG-1000” and “PTXG-1800” manufactured by Asahi Kasei Fibers Corporation, "YX-7180” manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond), and the like. ..
• the alkyleneoxy resin is a resin containing a polyalkyleneoxy structure.
• Specific examples of the alkyleneoxy resin include "EXA-4850-150", “EXA-4816” and “EXA-4822” manufactured by DIC Corporation, "EP-4000", “EP-4003” and “EP-4010” manufactured by ADEKA.
• the isoprene resin is a resin containing a polyisoprene structure.
• Specific examples of the isoprene resin include “KL-610" and “KL613” manufactured by Kuraray.
• the isobutylene resin is a resin containing a polyisobutylene structure.
• isobutylene resin examples include “SIBSTAR-073T” (styrene-isobutylene-styrene triblock copolymer) and “SIBSTAR-042D” (styrene-isobutyrene block copolymer) manufactured by Kaneka.
• acrylic rubber particles, polyamide fine particles, silicone particles and the like can be mentioned.
• the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber.
• XER-91 manufactured by Nippon Synthetic Rubber Co., Ltd.
• Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 all manufactured by Ganz Kasei Co., Ltd.
• Pararoid EXL2655, EXL2602 manufactured by Kureha Chemical Industry Co., Ltd.
• the polyamide fine particles include aliphatic polyamides such as nylon, and any flexible skeleton such as polyamide-imide.
• VESTOSINT 2070 manufactured by Daicel Huls
• SP500 manufactured by Toray Industries, Inc.
• the component (b) has high compatibility with components other than the component (b). That is, it is preferable that the component (b) is dispersed in the conductive layer. Further, the component (b) may be dispersed by forming a domain in the conductive layer.
• the average maximum diameter of the domain is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, or not dispersed (the average maximum diameter of the domain is 0 ⁇ m).
• the average maximum diameter of the domain can be measured as follows. A cross section of the conductive layer of the conductive adhesive film heat-cured at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology). Make an observation. Specifically, a cross section in a direction perpendicular to the surface of the conductive adhesive film is cut out by a FIB (focused ion beam), and a cross-section SEM image (observation width 60 ⁇ m, observation magnification 2,000 times) is acquired.
• FIB focused ion beam
• the content of the component (b) is not particularly limited, but when the non-volatile component in the thermosetting resin composition is 100% by mass, it is preferably 13% by mass or less, more preferably 12% by mass or less, still more preferably 11. It is less than mass%.
• the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more.
• thermosetting resin composition contains (c) a curing agent as a component (c).
• the curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. Examples thereof include an agent and a carbodiimide-based curing agent.
• the curing agent may be used alone or in combination of two or more.
• the component (c) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent, preferably a phenol-based curing agent, a naphthol-based curing agent, and the like. And one or more selected from the active ester-based curing agents are preferable.
• a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance.
• a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.
• a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.
• phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700”, “MEH-7810", “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and “NHN” manufactured by Nippon Kayaku Co., Ltd. "CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475", “SN485", “SN495V”, “SN375”, “SN395", DIC Corporation “TD-2090", “LA-7052", “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”, "HPC-9500” and the like.
• an active ester-based curing agent is also preferable from the viewpoint of obtaining a conductive layer having excellent adhesiveness.
• the active ester-based curing agent is not particularly limited, but generally contains an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used.
• the active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
• an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
• the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
• phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-.
• the "dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.
• an active ester compound containing a dicyclopentadiene-type diphenol structure an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable.
• an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable.
• the "dicyclopentadiene-type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.
• benzoxazine-based curing agent examples include “HFB2006M” manufactured by Showa High Polymer Co., Ltd., “Pd” and “FA” manufactured by Shikoku Chemicals Corporation.
• cyanate ester-based curing agent examples include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4.
• Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined.
• Specific examples of the cyanate ester-based curing agent include "PT30" and “PT60” (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and “BA230S75” (part of bisphenol A dicyanate) manufactured by Ronza Japan.
• a prepolymer in which all of the triazine is converted into a trimer can be mentioned.
• carbodiimide-based curing agent examples include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.
• the amount ratio of (a) epoxy resin and (c) curing agent is the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent] from 1: 0.01 to 1: The range of 2 is preferable, 1: 0.015 to 1: 1.5 is more preferable, and 1: 0.02 to 1: 1 is even more preferable.
• the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent.
• the total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all the curing agents.
• thermosetting resin composition As one embodiment of the thermosetting resin composition, (a) a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (liquid epoxy resin: the mass ratio of the solid epoxy resin is preferably 1: 0.1). ⁇ 1: 20, more preferably 1: 0.3 to 1:10, still more preferably 1: 0.6 to 1: 9), (c) as a curing agent, a phenol-based curing agent, a naphthol-based curing agent, and an activity. It is preferable to contain at least one selected from the group consisting of an ester-based curing agent and a cyanate ester-based curing agent.
• the content of the curing agent is not particularly limited, but when the non-volatile component in the thermosetting resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably. It is 20% by mass or less.
• the lower limit is not particularly limited, but is preferably 2% by mass or more.
• thermosetting resin composition contains (d) a conductive filler as a component (d).
• the conductive filler is at least one selected from metal particles selected from silver, copper and nickel, and metal-coated particles selected from silver, copper and nickel. Examples of the metal particles include silver particles, copper particles, and nickel particles. Examples of the metal-coated particles include metal-coated metal particles in which the metal particles are coated with metal, metal-coated resin particles in which resin particles such as polyamide and polybenzoguanamine are coated with metal, and the like.
• the metal-coated particles include silver-coated particles such as silver-coated metal particles and silver-coated resin particles; copper-coated particles such as copper-coated metal particles and copper-coated resin particles; and nickel such as nickel-coated metal particles and nickel-coated resin particles. Coated particles; etc.
• metal particles selected from copper and nickel, and metal-coated particles selected from copper and nickel are preferable, and nickel particles or nickel-coated particles are particularly preferable, from the viewpoint of cost. ..
• metal particles selected from silver and copper, and metal-coated particles selected from silver and copper are preferable from the viewpoint of resistance value, and silver particles or silver-coated particles are particularly preferable.
• the shape of the conductive filler is preferably flake-like (scale-like) or filament-like (dendritic).
• the conductive filler may be used alone or in combination of two or more.
• the average particle size of the conductive filler is preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less, still more preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less from the viewpoint of film forming property and conductivity.
• the lower limit of the average particle size is not particularly limited, but is preferably 0.001 ⁇ m or more, more preferably 0.005 ⁇ m or more, still more preferably 0.01 ⁇ m or more.
• the average particle size of the conductive filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the conductive filler on a volume basis using a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size.
• a conductive filler dispersed in water by ultrasonic waves can be preferably used.
• the laser diffraction / scattering type particle size distribution measuring device "LA-500" manufactured by HORIBA, Ltd. or the like can be used.
• conductive filler Commercially available products can be used as the conductive filler.
• Commercially available conductive fillers include, for example, "EA0101” manufactured by Metallow Co., Ltd. as Ag particles, average particle diameter 6.8 ⁇ m, specific surface area 0.28 m 2 / g; and "AACU-3001” manufactured by Metallow Co., Ltd. as silver-coated copper particles. , Average particle size 5.8 ⁇ m, specific surface area 0.61 m 2 / g; “NI-613” manufactured by Shoei Chemical Industry Co., Ltd. as nickel particles, average particle size 1.0 ⁇ m, specific surface area 1.0 m 2 / g; as nickel particles.
• the conductive filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a silane-based surface treatment agent such as a system coupling agent; a polyester-based dispersant; and the like.
• a silane-based surface treatment agent such as a system coupling agent; a polyester-based dispersant; and the like.
• silane-based surface treatment agents examples include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd.
• polyester dispersants include, for example, Solspers 11200, 12000, 13240, 13940, 17000, 18000, 20000, 24000, 26000, 28000, etc. manufactured by Ajinomoto Fine Techno Co., Ltd., Ajinomoto Fine Techno Co., Ltd. Examples thereof include hydrangea PB822, hydrangea PB821, hydrangea PB880, hydrangea PB882, hydrangea PB881 and the like. Further, as the polyester-based dispersant, one synthesized by using a commercially available material may be used.
• the content of the conductive filler is preferably 40% by mass or more, more preferably 45% by mass or more when the non-volatile component in the thermosetting resin composition is 100% by mass from the viewpoint of obtaining a conductive layer having a low resistance value. , More preferably 50% by mass or more.
• the upper limit of the content of the conductive filler in the thermosetting resin composition is preferably 98% by mass or less, more preferably 95% by mass or less, from the viewpoint of the adhesiveness of the conductive layer.
• the mixing ratio (mass ratio) of the component (d) and the component (b) is ((d) component / (b) component), preferably 5 or more, more preferably, from the viewpoint of simultaneously achieving adhesiveness and conductivity. Is 6 or more, more preferably 7 or more, preferably 45 or less, more preferably 35 or less, still more preferably 25 or less.
• the thermosetting resin composition may contain (e) a curing accelerator as an optional component.
• a curing accelerator examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing agents.
• a curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are more preferable.
• the curing accelerator may be used alone or in combination of two or more.
• Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate.
• Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
• amine-based curing accelerator examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,0) -Undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -Undecene are preferable.
• imidazole-based curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like.
• imidazole-based curing accelerator a commercially available product may be used, and examples thereof include "P200-H50” manufactured by Mitsubishi Chemical Corporation.
• guanidine-based curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine.
• the metal-based curing accelerator examples include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
• organic metal complex examples include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
• Examples thereof include an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate.
• organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.
• the content of the curing accelerator in the thermosetting resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the total amount of the non-volatile components of the epoxy resin and the curing agent is 100% by mass.
• thermosetting resin composition may further contain other additives, if necessary, and examples of such other additives include polymer resins other than the component (b), thickeners, and the like. Examples thereof include a defoaming agent, a leveling agent, an adhesion-imparting agent, and a resin additive such as a colorant.
• the thermosetting resin composition may contain a polymer resin other than the component (b) within the range in which the effect of the present invention is achieved.
• the polymer resin other than the component (b) include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin and the like.
• the content of the polymer resin other than the component (b) is 100% by mass of the non-volatile component in the thermosetting resin composition.
• it is 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
• the lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more.
• the thickness of the conductive layer is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m or less, still more preferably 40 ⁇ m or less or 20 ⁇ m or less from the viewpoint of thinning the wiring board.
• the lower limit of the thickness of the conductive layer is not particularly limited, but is preferably 2 ⁇ m or more, and more preferably 5 ⁇ m or more.
• the conductive adhesive film may contain other layers, if necessary.
• a protective film similar to the support may be further laminated as the outermost surface on the surface of the conductive layer that is not bonded to the support (that is, the surface opposite to the support). can.
• the thickness of the protective film is not particularly limited, but is, for example, 1 ⁇ m to 40 ⁇ m.
• a film made of a plastic material is preferable.
• the plastic material include polyesters such as polyethylene terephthalate (hereinafter, may be abbreviated as “PET”) and polyethylene naphthalate (hereinafter, may be abbreviated as “PEN”), polyethylene, and polyolefins such as polypropylene.
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• polyethylene polyethylene
• polyolefins such as polypropylene.
• PC polycarbonate
• acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyetherketones, polyimides and the like.
• PC polycarbonate
• PMMA polymethylmethacrylate
• TAC triacetylcellulose
• PES polyethersulfide
• polyetherketones polyimides and the like.
• a support with a release layer having a release layer on the surface to be joined to the conductive layer may be used.
• the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. ..
• a commercially available product may be used.
• “SK-1” and “SK-1” manufactured by Lintec Corporation which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include “AL-5", “AL-7", and “Lumirror T6AM” manufactured by Toray Industries, Inc.
• the thickness of the protective film is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, and more preferably in the range of 10 ⁇ m to 60 ⁇ m.
• the thickness of the entire support with a release layer is preferably in the above range.
• the method for producing the conductive adhesive film is not particularly limited as long as it includes the support and the conductive layer bonded to the support.
• a resin varnish in which a thermosetting resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like, and further dried to obtain a conductive layer.
• organic solvent examples include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like.
• ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone
• acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like.
• carbitols aromatic hydrocarbons such as toluene and xylene
• amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and
• Drying may be carried out by a known method such as heating or blowing hot air.
• the drying conditions are not particularly limited, but the organic solvent is dried so that the content of the organic solvent in the conductive layer is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the conductive layer is dried at 50 ° C. to 150 ° C. for 3 to 15 minutes. Can be formed.
• the conductive adhesive film can be rolled up and stored. If the conductive adhesive film has a protective film, it can be used by peeling off the protective film.
• thermosetting resin composition for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition after thermosetting)).
• thermosetting resin composition after thermosetting Indicates a good resistance value (25 ° C.). That is, it provides a conductive layer showing a good resistance value.
• the resistance value of the thermosetting resin composition after curing at 25 ° C. is 100 ⁇ or less, preferably 50 ⁇ or less, and more preferably 10 ⁇ or less.
• the resistance value can be measured according to the method described in ⁇ Resistance value evaluation> described later.
• a cured product obtained by thermally curing a thermosetting resin composition for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition after thermosetting)).
• a good adhesive strength 25 ° C.
• Adhesive strength of aluminum foil and glass epoxy at 25 ° C. via a thermosetting resin composition after curing.
• the amount is 0.05 kgf / cm or more, preferably 0.08 kgf / cm or more, more preferably 0.1 kgf / cm or more.
• the method for measuring the aluminum foil / glass epoxy adhesive strength will be described later. It can be measured according to the method described in ⁇ Measurement of Adhesive Strength>.
• thermosetting conditions of the thermosetting resin composition differ depending on the type of the thermosetting resin composition and the like, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C.).
• the curing time can be preferably in the range of 170 ° C. to 200 ° C., and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).
• the thermosetting resin composition Before the thermosetting resin composition is thermally cured, the thermosetting resin composition may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the thermosetting resin composition, it is thermosetting at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). The resin composition may be preheated for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
• the support of the conductive adhesive film may be peeled off after the conductive adhesive film is laminated on the base material and thermoset, or the support may be peeled off before laminating the conductive adhesive film on the base material. good.
• the conductive adhesive film of the present invention can be applied to various electronic devices by using a cured product of the thermosetting resin composition of the conductive adhesive film as a conductive layer.
• the conductive adhesive film can be suitably used as an adhesive film for an electronic device such as a flexible printed wiring board. In this case, it is possible to obtain a wiring board such as a flexible wiring board provided with a cured product of the thermosetting resin composition.
• the conductive adhesive film can also be suitably used as an electromagnetic wave shielding film for an electronic device such as a flexible printed wiring board. In this case, an electromagnetic wave shield containing a cured product of the thermosetting resin composition can be obtained.
• An electronic device manufactured using a conductive adhesive film usually comprises a cured product of a thermosetting resin composition of the conductive adhesive film, and the cured product can be strongly bonded to a member contained in the electronic device.
• the conductive adhesive film (thickness of the conductive layer: 25 ⁇ m) produced in Examples and Comparative Examples was cut into a length of 70 mm and a width of 20 mm, and the cut conductive adhesive film was used as a batch type vacuum laminator (manufactured by Nichigo Morton). , V-160) was used to laminate on the aluminum surface of an aluminum foil / PET composite film [AL1N30 with PET] (aluminum foil 30 ⁇ m, PET 25 ⁇ m: manufactured by Toyo Aluminum Sales Co., Ltd.) having a length of 150 mm and a width of 25 mm.
• the laminating conditions were a temperature of 80 ° C., a reduced pressure time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds. Then, the PET film of the conductive adhesive film is peeled off, and a glass epoxy plate (length 76 mm ⁇ width 26 mm ⁇ thickness 2 mm, FR-4) is further laminated on the exposed conductive layer under the same conditions as above.
• a laminate was prepared by curing at 180 ° C. for 60 minutes in a heat circulation type oven.
• the conductive adhesive film (thickness of the conductive layer: 25 ⁇ m) produced in Examples and Comparative Examples was cut into a length of 20 mm ⁇ a width of 20 mm, and the cut conductive adhesive film was used as a batch type vacuum laminator (manufactured by Nichigo Morton). , V-160) was used to laminate an aluminum foil / PET composite film [AL1N30 with PET] (aluminum foil 30 ⁇ m, PET 25 ⁇ m: a product manufactured by Toyo Aluminum Sales Co., Ltd.) having a length of 150 mm and a width of 25 mm on the aluminum surface.
• the laminating conditions were a temperature of 80 ° C., a reduced pressure time of 30 seconds, and then a pressure of 0.3 MPa for 30 seconds.
• the PET film of the conductive adhesive sheet was peeled off, and the aluminum surface of the aluminum foil / PET composite film [AL1N30 with PET] (aluminum foil 30 ⁇ m, PET 25 ⁇ m: manufactured by Toyo Aluminum Sales Co., Ltd.) was placed on the exposed conductive layer.
• the film was placed in a heat-circulating oven at 180 ° C. for 60 minutes and heat-cured to prepare a laminated body.
• the resistance value was measured on the surface of the aluminum foil with a digital multimeter (R6552 manufactured by Advantest Co., Ltd.), the resistance value of the conductive layer was measured, and the adhesiveness was evaluated according to the following criteria.
• Example 1 71.7 parts of polymer resin A manufactured as shown below, bisphenol type epoxy resin (“ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) 10.7 parts and 2.6 parts of a biphenyl type epoxy resin (“NC3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 291) were heated and dissolved in 15 parts of methyl ethyl ketone (MEK) and 15 parts of cyclohexanone while stirring.
• bisphenol type epoxy resin (“ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) 10.7 parts and 2.6 parts of a biphenyl type epoxy resin (“NC3000” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 291) were heated and dissolved in 15 parts of methyl ethyl ketone (MEK) and
• the heat-dissolved product is cooled to room temperature, and the active ester compound (“HPC-8000-65T” manufactured by DIC), a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 and a non-volatile content of 65% by mass is added thereto. ) 2.6 parts, curing accelerator (Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", 1-benzyl-2-phenylimidazole) 0.13 parts, and nickel powder (average particle 2.5 ⁇ m, manufactured by Nikko Rika Co., Ltd.
• the rough surface of the protective film (polypropylene film, "Alfan MA-430" manufactured by Oji F-Tex Co., Ltd., thickness 20 ⁇ m) is bonded so as to be bonded to the conductive layer, and the conductive adhesive film is attached.
• the protective film polypropylene film, "Alfan MA-430" manufactured by Oji F-Tex Co., Ltd., thickness 20 ⁇ m
• Example 2 A resin varnish was produced in the same manner as in Example 1 except that 950 parts of copper powder Cu-HWQ (average particles 2.7 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) was used instead of the nickel powder of Example 1. A conductive adhesive film was obtained.
• Cu-HWQ average particles 2.7 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.
• Example 3 5 parts of bisphenol type epoxy resin ("ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), biphenyl type epoxy resin ("NC3000” manufactured by Nippon Kayaku Co., Ltd. " , Epoxy equivalent 291) 40 parts, polybutadiene skeleton-containing epoxy resin (“PB3600” manufactured by Daicel Co., Ltd., number average molecular weight Mn: 5900 g / mol, epoxy equivalent 190), stirred with 15 parts of methyl ethyl ketone (MEK) and 15 parts of cyclohexanone. While heating and dissolving.
• bisphenol type epoxy resin (“ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169)
• biphenyl type epoxy resin (“NC3000” manufactured by Nippon Kayaku Co
• the heat-dissolved product is cooled to room temperature, and then there is a triazine-containing phenol novolac resin (MEK solution having a hydroxyl group equivalent of 125, a nitrogen content of about 12% by weight, and a solid content of 60% by weight).
• MEK solution having a hydroxyl group equivalent of 125, a nitrogen content of about 12% by weight, and a solid content of 60% by weight.
• Example 4 5 parts of bisphenol type epoxy resin ("ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), biphenyl type epoxy resin ("NC3000” manufactured by Nippon Kayaku Co., Ltd.
• Epoxy equivalent 291 40 parts, epoxy group-containing acrylic acid ester copolymer (“SG-80H” manufactured by Nagase ChemteX Corporation, number average molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, solid content 18 mass% 110 parts of the MEK solution) was heated and dissolved in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone with stirring.
• MEK methyl ethyl ketone
• the heat-dissolved product is cooled to room temperature, and a triazine skeleton-containing phenol-based curing agent (“LA-3018-50P” manufactured by DIC, a hydroxyl group equivalent of about 151, a 2-methoxypropanol solution having a solid content of 50%) 20 thereof.
• LA-3018-50P manufactured by DIC, a hydroxyl group equivalent of about 151, a 2-methoxypropanol solution having a solid content of 50%
• naphthol-based curing agent (“HPC-9500” manufactured by DIC, hydroxyl group equivalent 153, MEK solution with solid content of 60% by weight) 25 parts, hardening accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", 1-benzyl Mix 0.06 parts of -2-phenylimidazole, 150 parts of nickel powder (average particle 2.5 ⁇ m, "Type 255" manufactured by Nikko Rika), and 16 parts of methyl ethyl ketone (MEK), and uniformly disperse with a high-speed rotary mixer. Then, a resin varnish was prepared, and a conductive adhesive film was obtained in the same manner as in Example 1.
• HPC-9500 manufactured by DIC, hydroxyl group equivalent 153, MEK solution with solid content of 60% by weight
• hardening accelerator manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ”
• 1-benzyl Mix 0.06 parts of
• the heat-dissolved product is cooled to room temperature, and 54 parts of phenoxy resin ("YX7200B35" manufactured by Mitsubishi Chemical Co., a MEK solution with a solid content of 35% by weight) curing accelerator ("1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.), 1 part of 1-benzyl-2-phenylimidazole, MEK solution with solid content of 3% by mass), 150 parts of nickel powder (average particles 2.5 ⁇ m, "Type 255" manufactured by Nikko Rika), 15 parts of methyl ethyl ketone (MEK).
• the mixture was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish, and a conductive adhesive film was prepared in the same manner as in Example 1.
• Comparative Examples 1 and 2 in which the phenoxy resin was used instead of the component (b) were excellent in conductivity but inferior in adhesiveness. Further, Comparative Example 3 in which artificial graphite powder was used instead of the component (c) was inferior in conductivity and adhesiveness.
• the conductive adhesive film of the present invention is useful as an adhesive film for electronic devices such as flexible printed wiring boards and an electromagnetic wave shielding film.

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