WO2014010524A1 - Composition adhésive électroconductrice durcissable, film de blindage électromagnétique, film adhésif électroconducteur, procédé d'adhésion et carte de circuits imprimés - Google Patents

Composition adhésive électroconductrice durcissable, film de blindage électromagnétique, film adhésif électroconducteur, procédé d'adhésion et carte de circuits imprimés Download PDF

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Publication number
WO2014010524A1
WO2014010524A1 PCT/JP2013/068481 JP2013068481W WO2014010524A1 WO 2014010524 A1 WO2014010524 A1 WO 2014010524A1 JP 2013068481 W JP2013068481 W JP 2013068481W WO 2014010524 A1 WO2014010524 A1 WO 2014010524A1
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conductive adhesive
group
resin
adhesive composition
epoxy resin
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PCT/JP2013/068481
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English (en)
Japanese (ja)
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岩井　靖
寺田恒彦
善治 柳
山本祥久
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タツタ電線株式会社
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Priority to KR1020147035027A priority Critical patent/KR101795127B1/ko
Priority to JP2014524780A priority patent/JP5976112B2/ja
Priority to CN201380036829.0A priority patent/CN104487534B/zh
Publication of WO2014010524A1 publication Critical patent/WO2014010524A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C09J2301/314—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 the adhesive layer and/or the carrier being conductive
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2475/00—Presence of polyurethane
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10227—Other objects, e.g. metallic pieces
    • H05K2201/10371—Shields or metal cases
    • 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 resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives

Definitions

  • the present invention relates to a curable conductive adhesive composition, an electromagnetic wave shielding film, a conductive adhesive film, an adhesion method, and a circuit board.
  • conductive adhesives are often used (Patent Documents 1 to 3). These conductive adhesives are used to bond the electromagnetic wave shielding film to the conductive circuit of the flexible substrate, and to impart electromagnetic wave shielding performance to the metallic reinforcing plate, the reinforcing plate and the conductive circuit of the flexible substrate. It can be used for adhesion when connecting.
  • the flexible substrate may be uneven.
  • an electromagnetic wave shielding film or a reinforcing plate is bonded on such a concavo-convex shape, it is important that the resin flows appropriately in the hot press process for bonding.
  • Patent Document 4 describes a curable polyurethane polyurea adhesive composition containing a polyurethane polyurea resin, two types of epoxy resins, and a conductive filler.
  • a curable polyurethane polyurea adhesive composition containing a polyurethane polyurea resin, two types of epoxy resins, and a conductive filler.
  • Patent Document 5 describes that an adhesive composition containing a polyurethane polyurea resin and an epoxy resin is used for bonding a reinforcing plate and a flexible substrate. However, there is no description about making the reinforcing plate have electromagnetic wave shielding performance by making the adhesive composition conductive.
  • an object of the present invention is to provide a curable conductive adhesive composition that can control the resin flow and ensure the embedding property.
  • the present invention relates to a polyurethane resin (A) having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group, and two or more epoxy groups per molecule.
  • a curable conductive material comprising an epoxy resin (B) having at least one additive (C) selected from the group consisting of a crosslinking agent, a polymerization initiator and a tin-based metal catalyst, and a conductive filler (D) It is an adhesive composition.
  • the present invention is selected from the group consisting of a polyurethane resin (A ′) having a carboxyl group, an epoxy resin (B) having two or more epoxy groups per molecule, an isocyanate compound, a blocked isocyanate compound and an oxazoline compound.
  • the curable conductive adhesive composition is characterized by containing at least one additive (C ′) and a conductive filler (D).
  • At least one of the polyurethane resin (A) and the polyurethane resin (A ′) preferably has an acid value of 3 to 100 mgKOH / g. At least one of the polyurethane resin (A) and the polyurethane resin (A ′) preferably has a weight average molecular weight of 1,000 to 1,000,000.
  • the epoxy resin (B) is preferably composed of at least one of an epoxy resin (B1) having an epoxy equivalent of 800 to 10,000 and an epoxy resin (B2) having an epoxy equivalent of 90 to 300.
  • the epoxy resin (B1) is a bisphenol type epoxy resin and the epoxy resin (B2) is a novolac type epoxy resin.
  • the conductive filler (D) is preferably at least one selected from the group consisting of silver powder, silver-coated copper powder and copper powder.
  • the conductive filler (D) preferably has an average particle size of 3 to 50 ⁇ m.
  • This invention is also an electromagnetic wave shielding film characterized by laminating
  • This invention is also an electromagnetic wave shielding film characterized by laminating a conductive adhesive layer, a metal layer, and a protective layer using the above-described curable conductive adhesive composition.
  • the thickness of the conductive adhesive layer is preferably 3 to 30 ⁇ m.
  • the present invention also has a conductive adhesive layer formed by the electromagnetic wave shielding film described above, and the conductive adhesive layer is also connected to a ground circuit of a printed circuit board. .
  • This invention is also a conductive adhesive film characterized by having an adhesive layer obtained by using the curable conductive adhesive composition described above.
  • the conductive adhesive film preferably has a thickness of 15 to 100 ⁇ m.
  • the present invention includes a step (1) of temporarily bonding the above-described conductive adhesive film on a substrate to be bonded (X) which is a reinforcing plate or a flexible substrate, and a conductive adhesive film obtained by the step (1). It is also an adhesion method comprising a step (2) of superimposing a substrate to be adhered (Y), which is a flexible substrate or a reinforcing plate, on the adhesive substrate (X) and hot pressing.
  • the present invention is a circuit board having at least a portion where a flexible substrate, a conductive adhesive layer, and a conductive reinforcing plate are laminated in this order, and the conductive adhesive layer is formed by the conductive adhesive film described above. It is also a circuit board characterized by being made.
  • the circuit board may have a surface other than the reinforcing plate on the surface of the flexible substrate covered with an electromagnetic wave shielding film.
  • the curable conductive adhesive composition of the present invention has excellent performance by flowing appropriately during bonding. Thereby, excellent adhesion can be performed even on a substrate having an uneven shape. In addition, there is an advantage that the embedding property can be secured.
  • circuit board obtained by using the conductive adhesive of this invention as an electromagnetic wave shield layer. It is an example of the circuit board obtained by using the conductive adhesive of this invention as an electromagnetic wave shield layer. It is an example of the circuit board obtained by using the conductive adhesive of this invention as a conductive adhesive film. It is a schematic diagram which shows the 90 degree peel strength measuring method of an Example. It is an example of the connection resistance measurement test piece of an Example. It is a schematic diagram which shows the 180 degree peel strength measuring method of an Example. It is a schematic diagram which shows the mode of the resin flow of an Example.
  • the curable conductive adhesive composition of the present invention comprises a polyurethane resin (A) having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group; An epoxy resin (B) having two or more epoxy groups in the molecule, at least one additive (C) selected from the group consisting of a crosslinking agent, a polymerization initiator and a tin-based metal catalyst, and a conductive filler (D) It contains.
  • A polyurethane resin having at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group
  • polyurethane resin (A) Polyurethane resin (A)
  • polyurethane means a general term for polyurethane and polyurethane-urea.
  • the “polyurethane” may be a product obtained by reacting an amine component as necessary.
  • the polyurethane resin (A) used in the present embodiment has a carboxyl group and at least one functional group selected from the group consisting of a hydroxyl group, a carbon-carbon unsaturated bond and an alkoxysilyl group as a reactive functional group. .
  • the resin flow can be controlled by the effect that it becomes possible to control the heat softening temperature in the hot press step described later.
  • At least one functional group selected from the group consisting of a hydroxyl group, a carbon-carbon unsaturated bond, and an alkoxysilyl group is present in the main chain even if it is present in the side chain of the polyurethane resin. Alternatively, it may be present as a terminal group.
  • the polyurethane resin (A) used in the present invention comprises a polyol compound (1) containing a carboxyl group, a polyol (2), a short-chain diol compound (3) if necessary, and a polyamine compound (4) if necessary. And a polyisocyanate compound (5). More preferably, the polyurethane resin (A) is a polyol compound (1) containing a carboxyl group, a polyol (2), a short-chain diol compound (3) and / or a diamine compound (4) used as necessary.
  • the active hydrogen-containing group (excluding the carboxyl group of the polyol compound (1)) and the isocyanate group (5) are reacted in an equivalent ratio of 0.5 to 1.5.
  • a method for introducing a reactive functional group other than a carboxyl group into the polyurethane resin (A) used in the present invention a single monomer having a reactive functional group to be introduced in the above components (1) to (5) is used.
  • polyol compound (1) containing a carboxyl group examples include dimethylol alkanoic acid such as dimethylolpropanoic acid and dimethylolbutanoic acid; alkylene oxide low-mole adduct of dimethylolalkanoic acid (number by terminal functional group quantification).
  • ⁇ -caprolactone low molar adduct of dimethylol alkanoic acid (number average molecular weight less than 500 by terminal functional group quantification); half esters derived from acid anhydride of dimethylol alkanoic acid and glycerin; Examples thereof include compounds obtained by free radical reaction of a hydroxyl group of dimethylolalkanoic acid, a monomer having an unsaturated bond, and a monomer having a carboxyl group and an unsaturated bond.
  • dimethylolpropanoic acid and dimethylolalkanoic acid such as dimethylolbutanoic acid are preferred from the viewpoints of availability, ease of adjustment of acid value, and the like.
  • the content of the polyol compound (1) in the polyurethane resin (A) is such that the resulting polyurethane resin (A) is cross-linked with the epoxy resin (B), thereby improving heat resistance and durability, and flexibility and adhesion. It is set from the viewpoint of both. More specifically, the content of the polyol compound (1) in the reaction component is preferably such that the acid value of the resulting polyurethane resin (A) is 3 to 100 mgKOH / g, and 3 to 50 mgKOH / g. More preferably, the amount is g.
  • the polyol (2) is a component having two or more hydroxyl groups, and those having a number average molecular weight of 500 to 3000 can be preferably used. In addition, the said polyol (2) points out only what does not correspond to the said polyol compound (1).
  • the polyol (2) is not particularly limited, and a conventionally known polyol used for urethane synthesis can be used. Specific examples of the polyol (2) include polyester polyol, polyether polyol, polycarbonate polyol, and other polyols.
  • Polyester polyols include aliphatic dicarboxylic acids (eg succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid etc.) and / or aromatic dicarboxylic acids (eg isophthalic acid, terephthalic acid etc.), low Molecular weight glycol (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, etc. ) And those obtained by condensation polymerization.
  • aliphatic dicarboxylic acids eg succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid etc.
  • aromatic dicarboxylic acids eg isophthalic acid, terephthalic acid etc.
  • low Molecular weight glycol for example, ethylene glycol, 1,2-prop
  • polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, polyneopentyl / hexyl adipate diol, poly-3- Examples thereof include methylpentane adipate diol, polybutylene isophthalate diol, polycaprolactone diol, and poly-3-methylvalerolactone diol.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random / block copolymers thereof.
  • polycarbonate polyol examples include polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyneopentyl carbonate diol, polyhexamethylene carbonate diol, poly (1,4-cyclohexanedimethylene carbonate) diol, and random / Examples thereof include a block copolymer.
  • polystyrene resin examples include dimer diol, polybutadiene polyol and its hydrogenated product, polyisoprene polyol and its hydrogenated product, acrylic polyol, epoxy polyol, polyether ester polyol, siloxane-modified polyol, ⁇ , ⁇ -polymethyl Examples thereof include methacrylate diol, ⁇ , ⁇ -polybutyl methacrylate diol, and the like.
  • the number average molecular weight (Mn, determined by terminal functional group determination) of the polyol (2) is not particularly limited, but is preferably 500 to 3,000. If the number average molecular weight (Mn) of the polyol (2) is more than 3,000, the cohesive force of urethane bonds is hardly expressed and the mechanical properties tend to be lowered. In addition, a crystalline polyol having a number average molecular weight of more than 3,000 may cause a whitening phenomenon when formed into a film. In addition, a polyol (2) can be used individually by 1 type or in combination of 2 or more types.
  • a reaction component for obtaining a polyurethane resin (A) it is also preferable to use a short chain diol component (3) and / or a diamine component (4) as needed. This makes it easy to control the hardness and viscosity of the polyurethane resin (A).
  • Specific examples of the short chain diol component (3) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol and the like.
  • Aliphatic glycols and their alkylene oxide low molar adducts (number average molecular weight less than 500 by terminal functional group determination); cycloaliphatic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol And its alkylene oxide low molar adduct (number average molecular weight less than 500, same as above); aromatic glycol such as xylylene glycol and its alkylene oxide low mole adduct (number average molecular weight less than 500, same as above); bisphenol A, thiobisphenol, Sulfonbispheno Bisphenols and alkylene oxide low molar adducts such as Le (number average molecular weight of less than 500, supra); and alkyl dialkanolamine such as alkyl diethanolamine of C1 ⁇ C18 can be mentioned.
  • cycloaliphatic glycols such as 1,4-bishydroxymethylcyclohexane and
  • diamine compound (4) examples include aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine and octamethylene diamine; phenylene diamine and 3,3′-dichloro.
  • Aromatic diamine compounds such as -4,4'-diaminodiphenylmethane, 4,4'-methylenebis (phenylamine), 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone; cyclopentyldiamine, cyclohexyldiamine, 4 And alicyclic diamine compounds such as 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, and isophoronediamine.
  • hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide can be used as the diamine compound (4).
  • long-chain ones include long-chain alkylene diamines, polyoxyalkylene diamines, terminal amine polyamides, and siloxane-modified polyamines. These diamine compounds (4) can be used singly or in combination of two or more.
  • polyisocyanate compound (5) a conventionally known polyisocyanate used in the production of polyurethane can be used.
  • Specific examples of the polyisocyanate (5) include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene.
  • the polyisocyanate compound (5) may have a blocking group at the terminal portion. That is, it may be formed by forming an isocyanate terminal by reacting with an excess of an isocyanate group, and blocking the terminal by reacting the isocyanate terminal with a monofunctional group compound.
  • mono- and diamines having a hydroxyl group can be used, and the monoamine can introduce a hydroxyl group into the polyurethane resin chain using a diamine as a chain extender at the end of the polyurethane resin.
  • a polyhydric alcohol containing two or more hydroxyl groups in the molecule can also introduce a hydroxyl group at the end of the polyurethane resin by reacting an excess amount with the prepolymer.
  • Examples of the monoamine having a hydroxyl group include monoethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, and N-hydroxyethylpiperazine.
  • Examples of the diamine having a hydroxyl group include N-aminoethyl.
  • Examples include ethanolamine and N-aminoethylisopropanolamine.
  • Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,3-butanediol, N-methyldiethanolamine, triethanolamine, glycerin, trimethylolpropane and the like. be able to.
  • the hydroxyl value is preferably 3 to 300 mgKOH / g.
  • monools and diols having an unsaturated bond can be used as the compound for introducing an unsaturated bond.
  • the monool is used at the end of the polyurethane resin, and the diol is used as a chain extender. Unsaturated bonds can be introduced.
  • the compound that introduces an unsaturated bond include monoallyl having an unsaturated bond, allyl alcohol, hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA) (hereinafter, acrylic and methacryl are combined ( Meth) acryl), and ethylene oxide, propylene oxide, or ⁇ -caprolactone adducts thereof, hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin di (meth) acrylate, Examples thereof include trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the diol includes glycerin monoallyl ether, glycerin mono (meth) acrylate, poly Taj diol, such as dimer diol can be mentioned.
  • glycidyl (meth) acrylate is added thereto, and the carboxyl group of the polyurethane resin and the epoxy group of glycidyl (meth) acrylate are reacted to form a side chain of the polyurethane resin. It is also possible to introduce an unsaturated bond into.
  • the unsaturated bond equivalent is preferably 300 to 10,000 g / eq.
  • Mono- and diamines having an alkoxysilyl group, or thiols can be used as the compound for introducing an alkoxysilyl group.
  • the monoamine and thiol are used at the end of the polyurethane resin, and the diamine is used as a chain extender.
  • Alkoxysilyl groups can be introduced into the resin chain.
  • Specific examples of the compound for introducing an alkoxysilyl group include monoamino having an alkoxysilyl group, such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
  • diamine examples include N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane
  • thiols having an alkoxysilyl group examples include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.
  • the amount introduced is preferably 0.01 to 10% by weight in terms of the amount of silicon atoms in the resin.
  • An active hydrogen group such as a polyol compound (1), a polyol (2), a short-chain diol compound (3), if necessary, a polyamine compound (4), etc.
  • the equivalent ratio of the polyisocyanate compound (5) to the isocyanate group of (1) which does not contain a carboxyl group) is preferably 0.5 to 1.5. Within the above range, it is preferable in that a polyurethane resin (A) having high heat resistance and high mechanical strength can be obtained.
  • the polyurethane resin (A) can be produced by a conventionally known polyurethane production method. Specifically, first, in the presence or absence of an organic solvent containing no active hydrogen in the molecule, a polyol compound (1) containing a carboxyl group, a polyol (2), and a chain extender as necessary. A reaction comprising: a short-chain diol compound (3) used as necessary; a polyamine compound (4) used as needed; a functional group-introducing component serving as a reaction point used as needed; and a polyisocyanate (5). The components are reacted to obtain a reactant (eg, a prepolymer).
  • a reactant eg, a prepolymer
  • the reaction component may be a blended composition in which a prepolymer having a terminal isocyanate group is formed.
  • the reaction may be carried out by a one-shot method or a multi-stage method, usually at 20 to 150 ° C., preferably 60 to 110 ° C. until the theoretical isocyanate percentage is reached.
  • the obtained reaction product may be chain-extended so as to have a desired molecular weight by reacting the diamine compound (4), if necessary, and at the same time, a compound having the above-described functional group is used. Then, a functional group serving as a reaction point may be introduced. Further, the total active hydrogen-containing group of the polyol compound (1), polyol (2), short chain diol compound (3), and polyamine compound (4) containing a carboxyl group (excluding the carboxyl group of the compound (1)). And the isocyanate group (2) of the polyisocyanate compound (5) are preferably reacted at an equivalent ratio of 0.5 to 1.5.
  • the weight average molecular weight (Mw) of the polyurethane resin (A) obtained as described above is preferably 1,000 to 1,000,000, and more preferably 2,000 to 1,000,000. Polyurethane is preferred because the properties such as flexibility, adhesion, heat resistance, and coating performance are more effectively exhibited.
  • the number average molecular weight (Mn) of the polyurethane resin (A) obtained as described above is preferably 400 to 450,000, and more preferably 850 to 450,000. It is preferable because properties such as heat resistance and coating performance are more effectively exhibited.
  • “weight average molecular weight (Mw)” and “number average molecular weight (Mn)” mean values in terms of polystyrene measured by gel permeation chromatography (GPC) unless otherwise specified. .
  • the higher the acid value the more the crosslinking points and the higher the heat resistance.
  • the polyurethane resin (A) having an acid value that is too high may be too hard to reduce flexibility, and the carboxyl group may not be reacted with an epoxy group or the like, resulting in reduced durability. Therefore, the acid value of the polyurethane resin (A) is preferably 3 to 100 mgKOH / g, and more preferably 3 to 50 mgKOH / g.
  • a catalyst can be used as necessary in the urethane synthesis.
  • salts of metals and organic and inorganic acids such as dibutyltin laurate, dioctyltin laurate, stannous octoate, zinc octylate, tetra-n-butyl titanate, organic metal derivatives, organic amines such as triethylamine, diaza Bicycloundecene catalysts and the like can be mentioned.
  • the polyurethane resin (A) may be synthesized without using a solvent or may be synthesized with an organic solvent.
  • an organic solvent inert to the isocyanate group or an organic solvent less active than the reaction component with respect to the isocyanate group can be used.
  • organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; toluene, xylene, swazole (trade name, manufactured by Cosmo Oil Co., Ltd.), Solvesso (trade name, manufactured by Exxon Chemical Co., Ltd.) Aromatic hydrocarbon solvents such as n-hexane; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; Ether solvents such as dioxane and tetrahydrofuran; Ethyl acetate, butyl acetate and isobutyl acetate Ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc. Ether-based solvents; dimethylformamide,
  • the termination reaction of the isocyanate group can be performed using a compound having reactivity with the isocyanate group.
  • a monofunctional compound such as monoalcohol or monoamine; a compound having two kinds of functional groups having different reactivity with respect to isocyanate can be used.
  • Such compounds include monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; monoethylamine, n-propylamine, diethylamine And monoamines such as di-n-propylamine and di-n-butylamine; alkanolamines such as monoethanolamine and diethanolamine. Of these, alkanolamine is preferable because of easy control of the reaction.
  • the polyurethane resin (A) having a hydroxyl group in addition to the carboxyl group can obtain the effects of the present invention by performing a crosslinking reaction with an isocyanate crosslinking agent, a blocked isocyanate crosslinking agent, or the like.
  • the isocyanate crosslinking agent a burette type, an adduct type, a nurate type, a prepolymer type, and a block body thereof can be used.
  • the mass ratio of the hydroxyl group in the polyurethane resin (A) to the isocyanate crosslinking agent, the blocked isocyanate crosslinking agent, etc. is in the range of 0.5 to 200 parts by mass with respect to 100 parts by mass of the resin component of the polyurethane resin. Is preferred.
  • the polyurethane resin (A) having an unsaturated bond can undergo a crosslinking reaction between the unsaturated bonds by ultraviolet rays or electron beams in the presence or absence of various photopolymerization initiators.
  • a crosslinking reaction can be performed by a thermal reaction in the presence of a known polymerization initiator such as a peroxide or an azo compound.
  • the polyurethane resin (A) having an unsaturated bond can undergo a crosslinking reaction between the unsaturated bonds by heat treatment with peroxide as an initiator or with oxygen in the presence of a catalyst. .
  • the polyurethane resin (A) having an alkoxysilyl group is hydrolyzed in the presence or absence of a catalyst, and silanol groups are further condensed to form a siloxane bond. Furthermore, it can also be made to react with such a crosslinking agent by using together an isocyanate crosslinking agent, a blocked isocyanate crosslinking agent, etc.
  • a polyisocyanate compound which can be used what was illustrated as a polyisocyanate compound mentioned above can be used.
  • epoxy resin (B) The curable conductive adhesive composition of the present invention further contains an epoxy resin (B). It does not specifically limit as an epoxy resin (B) to be used, The arbitrary well-known thing which has a 2 or more epoxy group in 1 molecule can be used.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, terpene type epoxy resin , Glycidyl ether type epoxy resins such as tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane, glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, tetrabromobisphenol A type epoxy resins, cresol novolac type epoxy resins, Novolak type epoxy such as phenol novolak type epoxy resin, ⁇ -naphthol novolak type epoxy resin, brominated phenol novolak type epoxy resin
  • the sheet resin can be used.
  • the same type of epoxy resins (B) having different epoxy equivalents may be mixed and used, or different types of epoxy resins (B) may be used in combination. May be.
  • the two epoxy resins (B) are those having an epoxy equivalent of 800 to 10,000 (epoxy resin (B1)) and those having an epoxy equivalent of 90 to 300 (epoxy resin (B2)). It is preferable to use it in combination.
  • the epoxy resin (B1) and the epoxy resin (B2) may be the same type or may have different chemical structures.
  • the epoxy resin (B1) one having an epoxy equivalent of 800 to 10,000 is preferably used. This is preferable in that the adhesion with a reinforcing plate or an adherend (Ni-SUS, SUS, gold plating electrode, polyimide resin, etc.) is further improved.
  • the lower limit of the epoxy equivalent is more preferably 1000, and still more preferably 1500.
  • the upper limit of the epoxy equivalent is more preferably 5000, and still more preferably 3000.
  • epoxy resins that can be used as the epoxy resin (B1) include EPICLON 4050, 7050, HM-091, HM-101 (trade name, manufactured by DIC Corporation), jER1003F, 1004, 1004AF, 1004FS, 1005F, 1006FS, 1007, 1007FS, 1009, 1009F, 1010, 1055, 1256, 4250, 4275, 4004P, 4005P, 4007P, 4010P (trade names, manufactured by Mitsubishi Chemical Corporation) and the like.
  • the epoxy resin (B2) particularly preferably has an epoxy equivalent of 90 to 300. As a result, the effect of increasing the heat resistance of the resin is obtained.
  • the lower limit of the epoxy equivalent is more preferably 150, and even more preferably 170.
  • the upper limit of the epoxy equivalent is more preferably 250, and still more preferably 230.
  • the epoxy resin (B2) is more preferably a novolak type epoxy resin.
  • novolac epoxy resin has high epoxy resin density, it has good miscibility with other epoxy resins and has little reactivity difference between epoxy groups. High crosslink density can be achieved uniformly.
  • the novolak type epoxy resin is not particularly limited, and examples thereof include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, an ⁇ -naphthol novolak type epoxy resin, and a brominated phenol novolak type epoxy resin.
  • epoxy resins that can be used as the epoxy resin (B2) as described above include EPICLON® N-660, N-665, N-670, N-673, N-680, N-695, N-655.
  • the said epoxy resin (B1) when using a novolak-type epoxy resin as said epoxy resin (B2), the said epoxy resin (B1) can use the bisphenol-type epoxy resin which is solid at normal temperature. This is because sufficient adhesion can be obtained by using the novolac type epoxy resin (B2) and the bisphenol type epoxy resin (B1) in combination.
  • the curable conductive adhesive composition of the present embodiment preferably contains the epoxy resin (B1) and the epoxy resin (B2) in a weight ratio of 85:15 to 99: 1.
  • Heat resistance that can withstand the reflow process when mounting components by ensuring the adhesion to reinforcing plates and adherends (Ni-SUS, SUS, gold-plated electrodes, polyimide resins, etc.), etc. Is preferable in terms of imparting.
  • the ratio of the epoxy resin (B1) is larger than 99: 1, it is not preferable in that it may not be able to endure the reflow process at the time of component mounting.
  • An increase in the ratio of B2) is not preferable in terms of a decrease in adhesion to an adherend (Ni-SUS, SUS, gold plating electrode, polyimide resin, etc.).
  • epoxy equivalent in this specification is a value measured by potentiometric titration.
  • the mixing ratio of the polyurethane resin (A) and the epoxy resin (B) is preferably 70:30 to 30:70 as the mass ratio of the polyurethane resin (A) and the epoxy resin (B).
  • the curable conductive adhesive composition of the present embodiment is a curable adhesive composition whose durability is further improved by adding an additive (C) (for example, a polymerization initiator, a crosslinking agent, a reaction catalyst, etc.). Can be obtained.
  • an additive (C) capable of reacting with a carboxyl group and a reactive functional group present in the molecule of the polyurethane resin (A) to cause the polyurethane resin (A) to undergo a crosslinking reaction.
  • the additive (C) is intended to contribute to the reaction of the carboxyl group and the reactive functional group present in the molecule of the polyurethane resin (A), which simultaneously contributes to the reaction of the epoxy resin (B). It does not matter even if it does.
  • organic peroxide polymerization initiators such as cumene hydroperoxide and t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutylnitrile, 2,2′-azobis (2 , 4-dimethylvaleronitrile) and other azo polymerization initiators can be used.
  • organic peroxide polymerization initiators include Parkmill H and Parkmill O (manufactured by NOF Corporation), and commercially available azo polymerization initiators include ABN-R and ABN-V (manufactured by Nippon Finechem Co., Ltd.). ) And the like.
  • crosslinking agent conventionally well-known crosslinking agents, such as an isocyanate compound, a block isocyanate compound, a carbodiimide compound, an oxazoline compound, a melamine, a metal complex type crosslinking agent, can be used.
  • crosslinking agents an isocyanate compound, a blocked isocyanate compound, a carbodiimide compound, and an oxazoline compound are preferable.
  • examples of commercially available isocyanate compounds that can be used as a crosslinking agent include duranate (manufactured by Asahi Kasei Chemicals Corporation).
  • commercially available carbodiimide compounds include carbodilite (Nisshinbo Chemical Co., Ltd.).
  • commercially available oxazoline compounds include Epocross (manufactured by Nippon Shokubai Co., Ltd.).
  • a tin-based metal catalyst such as monobutyl stannic acid or stannous octylate can be used.
  • examples of commercially available products include MBTO and stanoct (manufactured by API Corporation).
  • additives (C) are effective in improving heat resistance and durability if they are in appropriate amounts. However, when there is too much usage-amount of an additive (C), a softness
  • an isocyanate compound (including a blocked isocyanate compound) is a crosslinking agent generally used for polyurethane resins, but in addition to a carboxyl group, a polyurethane resin having a hydroxyl group (A ) Reacts with the hydroxyl group to become a particularly effective crosslinking agent.
  • the curable conductive adhesive composition of this embodiment contains a conductive filler (D).
  • the conductive filler (D) is not particularly limited, and for example, a metal filler, a metal-coated resin filler, a carbon filler, and a mixture thereof can be used.
  • the metal filler include copper powder, silver powder, nickel powder, silver-coated copper powder, gold-coated copper powder, silver-coated nickel powder, and gold-coated nickel powder. These metal powders can be electrolyzed, atomized, or reduced. It can be produced by the method.
  • the average particle size of the conductive filler (D) is preferably 3 to 50 ⁇ m.
  • the shape of the conductive filler (D) include a spherical shape, a flake shape, a dendritic shape, and a fibrous shape.
  • the curable conductive adhesive composition includes a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, and an antifoaming agent as long as the solder reflow resistance is not deteriorated.
  • a silane coupling agent an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, and an antifoaming agent as long as the solder reflow resistance is not deteriorated.
  • Leveling regulators, fillers, flame retardants and the like may be added.
  • the conductive adhesive layer of this embodiment may be an anisotropic conductive adhesive layer or an isotropic conductive adhesive layer, and can be any of these depending on the purpose.
  • attaching with a reinforcement board it is preferable to set it as an isotropic electroconductive adhesive layer.
  • an isotropic conductive adhesive layer it is preferable that it is an anisotropic conductive adhesive layer.
  • the conductive filler can be either an anisotropic conductive adhesive layer or an isotropic conductive adhesive layer depending on the blending amount of the conductive filler (D).
  • the conductive filler is preferably 5% by weight or more and less than 40% by weight in the total solid content of the curable conductive adhesive composition.
  • the conductive filler (D) is preferably 40% by weight or more and 90% by weight or less in the total solid content of the curable conductive adhesive composition.
  • the curable conductive adhesive composition of the present invention can also be used as a conductive adhesive layer in an electromagnetic wave shielding film.
  • Such an electromagnetic wave shielding film is also one aspect of the present invention.
  • the electromagnetic wave shielding film of the present invention preferably has a conductive adhesive layer and a protective layer.
  • the conductive adhesive layer is obtained from a curable conductive adhesive composition. It does not specifically limit as a protective layer, A well-known arbitrary thing can be used.
  • the protective layer may use a resin component (excluding the conductive filler) used in the above-described conductive adhesive layer.
  • the thickness of the conductive adhesive layer is preferably in the range of 3 to 30 ⁇ m. If the thickness is less than 3 ⁇ m, sufficient connection with the ground circuit may not be obtained, and if it exceeds 30 ⁇ m, it is not preferable in that the demand for thinning cannot be met.
  • a protective layer resin composition is coated and dried on one surface of a peelable film, a protective layer is formed, and the curable conductive adhesive composition is coated and dried on the protective layer, and then conductive. And the like, and the like.
  • an electromagnetic wave shielding film in a laminated state of conductive adhesive layer / protective layer / peelable film can be obtained.
  • a method of providing a conductive adhesive layer and a protective layer conventionally known coating 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 It can be performed by a method, a spray coating method, a bar coating method, a spin coating method, a dip coating method, or the like.
  • the electromagnetic wave shielding film can be adhered on the substrate by hot pressing.
  • the conductive adhesive layer is softened by heating and flows into the ground portion from which the insulator layer has been removed by pressurization. Thereby, it is electrically connected to the ground circuit.
  • FIG. 1 A circuit board using such a conductive adhesive is shown in FIG.
  • a conductive adhesive layer 3 and a protective layer 1 are formed so as to be in contact with the ground portion 4. Since the conductive adhesive layer 3 of the present invention has appropriate fluidity, the embedding property is good, and a good electrical connection can be made at the ground portion 4.
  • the electromagnetic wave shielding film of the present invention may have a metal layer. By having a metal layer, better electromagnetic shielding performance can be obtained.
  • the metal material forming the metal layer include nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium, zinc, and an alloy containing any one or more of these materials. Can do.
  • the metal material and thickness of the metal layer may be appropriately selected according to the required electromagnetic shielding effect and repeated bending / sliding resistance, but the thickness may be about 0.1 ⁇ m to 8 ⁇ m. .
  • Examples of the method for forming the metal layer include an electrolytic plating method, an electroless plating method, a sputtering method, an electron beam evaporation method, a vacuum evaporation method, a CVD method, and a metal organic.
  • the metal layer may be a metal foil.
  • the electromagnetic wave shielding film having such a metal layer can be produced by the same method as the electromagnetic wave shielding film described above, and preferably has a configuration of conductive adhesive layer / metal layer / protective layer / peelable film. .
  • FIG. 2 A circuit board using an electromagnetic wave shielding film having a metal layer is shown in FIG.
  • the metal layer 2 is electrically connected to the ground portion 4 through the conductive adhesive layer 3 to obtain electromagnetic shielding performance.
  • the conductive adhesive layer 3 has appropriate fluidity, the embedding property is good, and a good electrical connection can be made in the ground portion 4.
  • a flexible substrate that is repeatedly bent can be given as a representative example. Of course, it can also be applied to rigid printed wiring boards. Further, not only a single-sided shield but also a double-sided shield is included.
  • the electromagnetic wave shielding film can be bonded onto the substrate by heating and pressing. Such hot pressing under heat and pressure can be performed under normal conditions, for example, under conditions of 1 to 5 MPa, 140 to 190 ° C., and 15 to 90 minutes.
  • the present invention is also a conductive adhesive film having a conductive adhesive layer obtained using the curable conductive adhesive composition described above. Such a film can be used for bonding the conductive reinforcing plate and the circuit board main body to impart electromagnetic wave shielding performance to the reinforcing plate.
  • the conductive adhesive film of the present invention may be a single layer or may include a peelable film and a conductive adhesive layer formed on the surface of the peelable film.
  • the coating method and drying conditions of the conductive adhesive film of the present invention can be performed by known methods.
  • the conductive adhesive film of the present invention can be produced by coating a peelable film with a curable conductive adhesive composition to form a conductive adhesive layer.
  • the coating method is not particularly limited, and a coating method used in the above-described method for producing a conductive adhesive layer in the electromagnetic wave shielding film can be employed.
  • a peelable film For the peelable film, use is made of a base film such as polyethylene terephthalate or polyethylene naphthalate coated with a silicon-based or non-silicon-based release agent on the surface on which the conductive adhesive layer is formed. be able to.
  • the thickness of a peelable film is not specifically limited, It determines suitably considering the ease of use.
  • the thickness of the conductive adhesive film is preferably 15 to 100 ⁇ m. Such a thickness is preferable in that it can be deformed into a shape that fills the concave portion by appropriately flowing when the substrate has irregularities, and can be bonded with good adhesion.
  • the conductive adhesive film of the present invention can be used, for example, to bond a reinforcing plate and a circuit board body.
  • the reinforcing plate is made of metal
  • the reinforcing plate is used not only for bonding the metal reinforcing plate but also for electrically connecting with the ground electrode in the circuit board body.
  • the adhesion method for use in such applications will be described in detail below.
  • the material of the circuit board body may be any material as long as it has insulating properties and can form an insulating layer, and a typical example thereof is polyimide resin.
  • a metal plate is preferably used as the conductive reinforcing plate, and a stainless plate, an iron plate, a copper plate, an aluminum plate, or the like can be used as the metal plate. Among these, it is more preferable to use a stainless steel plate. By using a stainless steel plate, it has sufficient strength to support an electronic component even with a thin plate thickness.
  • the thickness of the conductive reinforcing plate is not particularly limited, but is preferably 0.025 to 2 mm, and more preferably 0.1 to 0.5 mm. If the conductive reinforcing plate is within this range, it can be easily built into a small device and has sufficient strength to support the mounted electronic component.
  • examples of the electronic component here include a chip component such as a resistor, a capacitor, and a camera module in addition to a connector and an IC.
  • the conductive adhesive film obtained by the step (1) and the step (1) of temporarily bonding the above-described conductive adhesive film onto the adherend substrate (X) which is a reinforcing plate or a flexible substrate is a bonding method comprising a step (2) of overlaying a substrate to be bonded (X) having a flexible substrate or a substrate to be bonded (Y) as a reinforcing plate and hot pressing.
  • the conductive adhesive film described above can be particularly suitably used for bonding the flexible substrate and the reinforcing plate. That is, as described in Patent Document 3, a conductive material such as a metal plate is used as a reinforcing plate, and this is adhered to a flexible substrate with a conductive adhesive film, so that the electromagnetic shielding performance by the reinforcing plate can be obtained. Getting is done.
  • the conductive adhesive film of the present invention has a particularly excellent effect in that good adhesive performance is obtained when the reinforcing plate is bonded. That is, when temporary bonding is performed and stored for a certain period of time, and then main bonding is performed by hot pressing, an appropriate curing reaction proceeds during storage, so that the bonding performance of the main bonding does not deteriorate. Furthermore, since there is a moderate fluidity, even if the flexible substrate has a step, a high degree of adhesion can be obtained without causing a gap when the resin flows appropriately.
  • a conductive adhesive film is temporarily bonded onto the adherend substrate (X).
  • the adherend substrate (X) may be a reinforcing plate or a flexible substrate, but is preferably a reinforcing plate.
  • the conditions for temporary bonding are not particularly limited, as long as the conductive adhesive film is fixed on the substrate to be bonded and can be bonded without slipping, but it is not point bonding but surface bonding. It is preferable to do. That is, it is preferable to temporarily bond the entire bonding surface.
  • the temporary adhesion can be performed, for example, with a press (condition temperature: 120 ° C. pressure: 0.5 MPa time: 5 seconds).
  • the adherend substrate (X) to which the conductive adhesive film has been temporarily bonded in the step (1) described above may be immediately used for the step (2), or for one week before being used for the step (2). It may be stored to some extent.
  • the adhesive composition of the present invention is preferable in this respect because the adhesive performance does not deteriorate even after being partially cured.
  • Step (2) is a step in which the adherend substrate (Y), which is a flexible substrate or a reinforcing plate, is stacked on the adherend substrate (X) having the conductive adhesive film obtained in the step (1), and then hot-pressed. is there.
  • One of the adherend substrate (X) and the adherend substrate (Y) is a reinforcing plate and the other is a flexible substrate.
  • Hot pressing can be performed under normal conditions, for example, under conditions of 1 to 5 MPa, 140 to 190 ° C., and 15 to 90 minutes.
  • the circuit board of the present invention is a circuit board having at least a portion where a flexible substrate, a conductive adhesive film, and a conductive reinforcing plate are laminated in this order.
  • a circuit board may be bonded by the above-described bonding method, or may be obtained by other bonding methods.
  • a schematic diagram of such a circuit board is shown in FIG. In FIG. 3, the circuit board and the reinforcing plate 5 are bonded by the conductive adhesive film of the present invention and are also electrically connected.
  • the conductive reinforcing plate is preferably present only in a part of the circuit board. That is, it is preferable that the portion having the electronic component has a reinforcing plate.
  • the circuit board of the present invention may be a circuit board in which the reinforcing plate is bonded to the substrate by the above-described conductive adhesive of the present invention and is covered with an electromagnetic wave shielding film in a portion having no reinforcing plate. Good.
  • Such a circuit board is also one aspect of the present invention.
  • the electromagnetic wave shielding film of this invention mentioned above may be sufficient as the electromagnetic wave shielding film used here, a well-known electromagnetic wave shielding film can be used, without being limited to it.
  • the electromagnetic wave shielding film is preferably connected to a ground circuit (not shown).
  • the polyurethane resin (A ′) used in the present embodiment has a carboxyl group. By having such a reactive functional group, the resin flow can be controlled by the effect that the thermal softening temperature can be controlled.
  • the polyurethane resin (A ′) used in the present embodiment includes a polyol compound (1) containing a carboxyl group, a polyol (2), a short-chain diol compound (3) if necessary, and a polyamine compound (if necessary). It is obtained by reacting 4) with the polyisocyanate compound (5). More preferably, the polyurethane resin (A ′) is a polyol compound (1) containing a carboxyl group, a polyol (2), a short-chain diol compound (3) and / or a diamine compound (4) used as necessary.
  • Active hydrogen-containing groups excluding the carboxyl group of the polyol compound (1)
  • the isocyanate group of the polyisocyanate compound (5) are reacted in an equivalent ratio of 0.5 to 1.5.
  • these compounds (1) to (5) those mentioned in the first embodiment are preferably used.
  • the polyurethane resin (A ′) of the present embodiment can be produced by a conventionally known polyurethane production method. Specifically, first, in the presence or absence of an organic solvent containing no active hydrogen in the molecule, a polyol compound (1) containing a carboxyl group, a polyol (2), and a chain extender as necessary. Reaction product comprising a short-chain diol compound (3) used as needed, a polyamine compound (4) used as necessary, and a polyisocyanate compound (5) to react with each other (for example, polyurethane resin, prepolymer) Get.
  • the prepolymer may be a compounding composition that forms a prepolymer having a terminal isocyanate group.
  • the reaction may be carried out by a one-shot method or a multi-stage method, usually at 20 to 150 ° C., preferably 60 to 110 ° C. until the theoretical isocyanate percentage is reached.
  • the obtained reaction product may be chain-extended so as to have a desired molecular weight by reacting the diamine compound (4), if necessary. Further, the total active hydrogen-containing group of the polyol compound (1), polyol (2), short chain diol compound (3), and polyamine compound (4) containing a carboxyl group (excluding the carboxyl group of the compound (1)). And an isocyanate group of the polyisocyanate compound (5) are preferably reacted at an equivalent ratio of 0.5 to 1.5.
  • the polyurethane resin obtained as described above preferably has a weight average molecular weight (Mw) of 1,000 to 1,000,000, more preferably 2,000 to 1,000,000. Since characteristics, such as a softness
  • weight average molecular weight (Mw)” and “number average molecular weight (Mn)” mean values in terms of polystyrene measured by gel permeation chromatography (GPC) unless otherwise specified. .
  • the acid value of the urethane resin is higher, the crosslinking point is increased and the heat resistance is improved.
  • a urethane resin having an acid value that is too high may be too hard to reduce flexibility, or may not be able to react with an epoxy resin or a curing agent, resulting in reduced durability.
  • the acid value of the urethane resin is preferably 3 to 100 mgKOH / g, and more preferably 3 to 50 mgKOH / g.
  • a catalyst can be used as needed in the urethane synthesis.
  • salts of metals and organic and inorganic acids such as dibutyltin laurate, dioctyltin laurate, stannous octoate, zinc octylate, tetra-n-butyl titanate, organic metal derivatives, organic amines such as triethylamine, diaza Bicycloundecene catalysts and the like can be mentioned.
  • the polyurethane resin may be synthesized without using a solvent or may be synthesized with an organic solvent.
  • an organic solvent inert to the isocyanate group or an organic solvent less active than the reaction component with respect to the isocyanate group can be used.
  • organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; toluene, xylene, swazole (trade name, manufactured by Cosmo Oil Co., Ltd.), Solvesso (trade name, manufactured by Exxon Chemical Co., Ltd.) Aromatic hydrocarbon solvents such as n-hexane; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; Ether solvents such as dioxane and tetrahydrofuran; Ethyl acetate, butyl acetate and isobutyl acetate Ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc. Ether-based solvents; dimethylformamide,
  • the termination reaction of the isocyanate group can be performed using a compound having reactivity with the isocyanate group.
  • a monofunctional compound such as monoalcohol or monoamine; a compound having two kinds of functional groups having different reactivity with respect to isocyanate can be used.
  • monoalcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol.
  • the additive (C ′) of the present embodiment is a compound that does not correspond to the polyurethane resin (A ′) or the epoxy resin (B) described above, and is used for the curing reaction of the curable conductive adhesive composition of the present embodiment. It refers to a compound having a functional group involved. In particular, it is preferable to be able to react with a carboxyl group in the polyurethane resin (A ′) or a hydroxyl group in the epoxy resin (B) from the viewpoint of improving heat resistance and adhesion.
  • the compound that can be used as such an additive (C ′) is not particularly limited.
  • conventionally known additives such as an isocyanate compound, a blocked isocyanate compound, a carbodiimide compound, an oxazoline compound, a melamine, and a metal complex crosslinking agent are used.
  • an isocyanate compound, a blocked isocyanate compound, a carbodiimide compound, and an oxazoline compound are preferable.
  • These are compounds having two or more reactive groups such as an isocyanate group, a blocked isocyanate group, a carbodiimide group, and an oxazoline group.
  • Examples of commercially available isocyanate compounds that can be used as additives include duranate (manufactured by Asahi Kasei Chemicals Corporation).
  • Examples of commercially available carbodiimide compounds include carbodilite (Nisshinbo Chemical Co., Ltd.).
  • Examples of commercially available oxazoline compounds include Epocross (manufactured by Nippon Shokubai Co., Ltd.). Two or more of these compounds may be used in combination.
  • isocyanate compound examples include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4 -Butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4'-methylenebis (phenylene isocyanate) (MDI), durylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene Aromatic diisocyanates such as diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl; methylene diisocyanate Aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate,
  • the compound which blocked the isocyanate compound of the isocyanate compound mentioned above by the well-known method can be used.
  • the blocking compound is not particularly limited, and phenols such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; aceto Active methylenes such as ethyl acetate and acetylacetone; methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol Mono 2-ethylhexyl ether, propylene glycol monomethyl ether, methyl glycolate, buty
  • the oxazoline compound is not particularly limited.
  • the additive (C ′) is preferably not an aziridine compound. That is, it is preferable not to use an aziridine compound since mutagenicity (Ames) is positive.
  • the amount of the additive (C ′) used is preferably 0.1 to 200 parts by mass or less and preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the resin component of the polyurethane resin (A ′). More preferably. By setting it within the above range, it is preferable in terms of easy adjustment of heat resistance.
  • the curable conductive adhesive composition according to the second embodiment can also be used in the electromagnetic wave shielding film, the circuit board, and the bonding method in the same manner as in the first embodiment.
  • DMPA dimethylolpropionic acid
  • Placcel CD220 polyhexamethylene carbonate diol
  • Blenmer GLM glycerol monomethacrylate
  • DMF dimethylformamide
  • N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name “KBM-603”, Shin-Etsu Chemical Co., Ltd.) 21.0 g (manufactured by Kogyo Co., Ltd.) was added dropwise to react with the NCO group of the urethane prepolymer.
  • the number average molecular weight and weight average molecular weight in Table 1 are values measured under the following conditions. 1) Equipment: HLC-8020 (Tosoh Corporation) 2) Column (manufacturing company, column name): (Tosoh Corporation TSKgel G2000HXL, (G3000HXL, G4000GXL) 3) Solvent: THF 4) Flow rate: 1.0 ml / min 5) Sample concentration: 2 g / L 6) Injection volume: 100 ⁇ l 7) Temperature: 40 ° C 8) Detector: RI-8020 Standard material: TSK standard polystyrene (Tosoh Corporation)
  • Electromagnetic wave shielding film A peelable film coated with a release agent was coated with a protective layer resin and dried to form a protective layer having a thickness of 5 ⁇ m.
  • each material was blended as shown in Table 2 to prepare a curable conductive adhesive composition.
  • the curable conductive adhesive composition was hand-coated using a doctor blade (plate-like spatula) and dried at 100 ° C. for 3 minutes to prepare a conductive adhesive layer.
  • the conductive adhesive layer was prepared to have a predetermined thickness.
  • the thickness of a protective layer and a conductive adhesive layer is measured with a micrometer.
  • Conductive filler D-1 Silver powder (average particle size 5 ⁇ m, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.)
  • Conductive filler D-2 Silver-coated copper powder (average particle size 12 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
  • Conductive filler D-3 Silver-coated copper powder (average particle size 18 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
  • Additive C-1 Park Mill H (manufactured by NOF Corporation)
  • Additive C-2 Duranate 24A-100 (Asahi Kasei Chemicals Corporation)
  • Additive C-3 Stanoct (manufactured by API Corporation)
  • the obtained electromagnetic wave shielding film was evaluated based on the following evaluation criteria.
  • the results are shown in Table 4. (180 ° peel strength)
  • the conductive adhesive layer side of the electromagnetic wave shielding film 27 is placed on a test plate (width 10 mm, length 100 mm) via a polyimide film 26 (manufactured by Toray DuPont, Kapton 100H (trade name)).
  • the polyimide film 26 (Kapton 100H) was attached to the protective layer side through an adhesive layer, and was peeled off from the polyimide film at 50 mm / min.
  • the average value with n 5 is shown in the table. If it is 3 N / cm or more, it can be used without problems.
  • the electromagnetic wave shielding film was placed on a flexible substrate simulating a ground having an opening diameter of 1.0 mm and a step of 37.5 ⁇ m, and heated at 170 ° C. for 30 minutes while being pressurized at a pressure of 3 MPa. The connection resistance of the fabricated circuit board was measured. If it is 1 ⁇ or less, electromagnetic wave shielding performance can be secured.
  • Electromagnetic wave shielding film having a metal thin film layer A peelable film coated with a release agent was coated with a protective layer resin and dried to form a protective layer with a thickness of 5 ⁇ m. About 0.1 ⁇ m of a silver thin film layer was formed on the protective layer by vacuum deposition. Each material is mix
  • the conductive adhesive layer was prepared to have a predetermined thickness. In addition, the thickness of a protective layer and a conductive adhesive layer is measured with a micrometer.
  • Conductive filler D-4 Silver powder (average particle size 12 ⁇ m, Fukuda Metal Industry Co., Ltd.)
  • Conductive filler D-5 Silver-coated copper powder (average particle size 20 ⁇ m, Fukuda Metal Industry Co., Ltd.)
  • Conductive filler D-6 Silver-coated copper powder (average particle size 25 ⁇ m, Fukuda Metal Industry Co., Ltd.)
  • the obtained conductive adhesive film was evaluated based on the following evaluation criteria.
  • (Peel strength) The adhesion with the reinforcing plate was measured using a 90 ° peel test. Specifically, as shown in FIG. 4, the surface side of the polyimide layer in the copper-clad laminates 22 and 23 having a stainless steel plate 24 (width 10 mm, length 100 mm), a polyimide layer and a thin-film copper layer, and the book After press bonding as described in the method of using the conductive adhesive film of the above embodiment via the conductive adhesive film 21 of the example, the copper-clad laminate was pulled off in the vertical direction. If it is 10 N / cm or more, it can be used without problems.
  • connection resistance value Electrical evaluation was performed on the circuit board with the metal reinforcing plate 5 manufactured by the above method. Connection resistance of a circuit board with a metal reinforcing plate when a conductive adhesive film is pressed with a reinforcing plate on a flexible substrate simulating a ground having an opening diameter of 1.0 mm and a step of 37.5 ⁇ m (see FIG. 5 between the electrodes 8). If it is 1 ⁇ or less, it is judged that the shielding performance is ensured and the embeddability is good.
  • Table 8 shows the evaluation results of the obtained functional film.
  • the curable conductive property is the same as in the first embodiment except that the polyurethane resin (A ′) and the additive (C ′) are used instead of the polyurethane resin (A) and the additive (C) of the first embodiment.
  • An adhesive composition was prepared. Unless otherwise specified, various measurement conditions and evaluation conditions are the same as those in the first embodiment.
  • Table 9 shows the composition of the obtained polyurethane resin.
  • Electromagnetic wave shielding film An electromagnetic wave shielding film was produced by the same method as the production method of the electromagnetic wave shielding film in the first embodiment except that the composition of each material of the conductive adhesive composition was as shown in Table 10.
  • Cross-linking agent C′-1 carbodiimide compound
  • Carbodilite V-07 Non-styrene-maleic anhydride copolymer
  • Cross-linking agent C′-2 oxazoline compound
  • Epocross RPS-1005 manufactured by Nippon Shokubai Co., Ltd.
  • Cross-linking agent C′-3 isocyanate compound
  • Duranate 24A-1000 Asahi Kasei Chemicals Corporation
  • Cross-linking agent C′-4 Block isocyanate compound
  • Duranate 17B-60PX Alsahi Kasei Chemicals Corporation
  • Conductive filler D-1 Silver powder (average particle size 5 ⁇ m, Fukuda Metal Industry Co., Ltd.)
  • Conductive filler D-2 Silver-coated copper powder (average particle size 12 ⁇ m, Fukuda Metal Industry Co., Ltd.)
  • Conductive filler D-3 Silver-coated copper powder (average particle size 18 ⁇ m, Fukuda Metal Industry Co., Ltd.)
  • the 180 ° peel strength, connection resistance value, and reflow resistance of the obtained electromagnetic wave shielding film were evaluated based on the same evaluation criteria as in the first embodiment. The results are shown in Table 12.
  • the metal thin film layer was formed by the same method as the method for producing the electromagnetic wave shielding film having the metal thin film layer in the first embodiment except that the composition of each material of the curable conductive adhesive composition was as shown in Table 13. The electromagnetic shielding film which has was obtained.
  • a conductive adhesive film was produced by the same method as the method for producing a conductive adhesive film in the first embodiment except that the composition of each material of the curable conductive adhesive composition was as shown in Table 15.
  • Conductive filler D-4 Silver powder (average particle size 12 ⁇ m, Fukuda Metal Industry)
  • Conductive filler D-5 Silver-coated copper powder (average particle size 20 ⁇ m, Fukuda Metal Industry)
  • Conductive filler D-6 Silver-coated copper powder (average particle size 25 ⁇ m, Fukuda Metal Industry)
  • the peel strength, connection resistance value, reflow resistance, and resin flow of the obtained conductive adhesive film were evaluated based on the same evaluation criteria as in the first embodiment.
  • Table 16 shows the evaluation results of the obtained functional film.
  • the curable conductive adhesive composition of the present invention can be used particularly preferably in the fields of applications such as bonding a metal reinforcing plate to a flexible substrate and electromagnetic shielding films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
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  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention a pour but de proposer une composition adhésive électroconductrice durcissable avec laquelle un écoulement de résine peut être contrôlé et des propriétés d'incorporation peuvent être assurées. A cet effet, l'invention concerne une composition adhésive électroconductrice durcissable contenant : (A) une résine polyuréthane ayant au moins un groupe fonctionnel choisi dans le groupe consistant en les groupes carboxyle, les liaisons carbone d'hydroxyle-carbone insaturées et les groupes alcoxysilyle ; (B) une résine époxy ayant au moins deux groupes époxy dans la molécule ; (C) au moins un additif choisi dans le groupe consistant en les agents de réticulation, les amorceurs de polymérisation et les catalyseurs métalliques à base d'étain ; et (D) une charge électroconductrice. L'invention concerne une composition adhésive électroconductrice durcissable, caractérisée en ce qu'elle contient : (A') une résine polyuréthane ayant un groupe carboxyle ; (B) une résine époxy ayant au moins deux groupes époxy dans la molécule ; (C') au moins un adhésif choisi dans le groupe consistant en les composés isocyanate, les composés isocyanate à blocs et les composés oxazoline ; et (D) une charge électroconductrice.
PCT/JP2013/068481 2012-07-11 2013-07-05 Composition adhésive électroconductrice durcissable, film de blindage électromagnétique, film adhésif électroconducteur, procédé d'adhésion et carte de circuits imprimés WO2014010524A1 (fr)

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JP2014524780A JP5976112B2 (ja) 2012-07-11 2013-07-05 硬化性導電性接着剤組成物、電磁波シールドフィルム、導電性接着フィルム、接着方法及び回路基板
CN201380036829.0A CN104487534B (zh) 2012-07-11 2013-07-05 硬化导电胶组成物、电磁波屏蔽膜、导电胶膜、黏合方法及线路基板

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Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015068611A1 (fr) * 2013-11-07 2015-05-14 東洋インキＳｃホールディングス株式会社 Adhésif électroconducteur, feuille adhésive électroconductrice, dispositif de câblage et procédé de fabrication d'un dispositif de câblage
JP5854248B1 (ja) * 2015-05-27 2016-02-09 東洋インキＳｃホールディングス株式会社 導電性接着剤、ならびにそれを用いた導電性接着シートおよび電磁波シールドシート
JP5892282B1 (ja) * 2015-04-27 2016-03-23 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、および配線デバイス
JP2016121289A (ja) * 2014-12-25 2016-07-07 大日精化工業株式会社 接着剤
JP2016121285A (ja) * 2014-12-25 2016-07-07 日東シンコー株式会社 絶縁紙
JP2016204628A (ja) * 2016-02-02 2016-12-08 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、および配線デバイス
KR20170008804A (ko) * 2014-08-12 2017-01-24 미쓰비시 쥬시 가부시끼가이샤 투명 점착 시트
WO2017035710A1 (fr) * 2015-08-28 2017-03-09 E.I. Du Pont De Nemours And Company Adhésifs électroconducteurs
WO2017038818A1 (fr) * 2015-09-04 2017-03-09 タツタ電線株式会社 Procédé de production de cartes de circuit imprimé, et film de protection de cartes de circuit imprimé et stratifié en forme de feuille utilisés dans le procédé
JP2017098486A (ja) * 2015-11-27 2017-06-01 株式会社ノリタケカンパニーリミテド 圧電素子用導電性接着剤および圧電素子
JP2017115152A (ja) * 2017-01-18 2017-06-29 藤森工業株式会社 導電性接着剤層、及びｆｐｃ用電磁波シールド材
KR20180016270A (ko) 2016-08-05 2018-02-14 후지모리 고교 가부시키가이샤 Fpc용 도전성 접착 시트 및 fpc
JP6320660B1 (ja) * 2016-05-23 2018-05-09 タツタ電線株式会社 導電性接着剤組成物
JP2018070694A (ja) * 2016-10-25 2018-05-10 株式会社巴川製紙所 導電性接着剤組成物、電磁波シールドシート及びそれを用いた配線デバイス
JP6329314B1 (ja) * 2017-09-28 2018-05-23 タツタ電線株式会社 導電性接着剤シート
TWI627249B (zh) * 2014-06-30 2018-06-21 Tatsuta Electric Wire & Cable Co Ltd Conductive adhesive composition
WO2018211887A1 (fr) * 2017-05-19 2018-11-22 タツタ電線株式会社 Agent adhésif conducteur
JP2019041132A (ja) * 2018-12-13 2019-03-14 東洋インキＳｃホールディングス株式会社 導電性樹脂組成物、導電性接着シート、電磁波シールドシートおよびプリント配線板
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US10611931B2 (en) 2015-08-28 2020-04-07 Dupont Electronics, Inc. Electrically conductive adhesives
JP2020204027A (ja) * 2019-06-12 2020-12-24 東洋インキＳｃホールディングス株式会社 導電性接着剤、及びプリント配線板
WO2021020542A1 (fr) * 2019-08-01 2021-02-04 株式会社カネカ Composition de résine thermodurcissable, film de résine thermodurcissable, film thermodurci, corps multicouche, carte de circuit imprimé et son procédé de production
US10967428B2 (en) 2015-08-28 2021-04-06 Dupont Electronics, Inc. Coated copper particles and use thereof
CN113480963A (zh) * 2021-05-24 2021-10-08 厦门大学 一种导电胶、导电胶带及其制备方法
JP2021195447A (ja) * 2020-06-12 2021-12-27 味の素株式会社 樹脂組成物
CN114702930A (zh) * 2022-02-11 2022-07-05 苏州安洁科技股份有限公司 一种气体扩散层用新型粘接材料及其制备方法和应用方法
WO2023286644A1 (fr) * 2021-07-16 2023-01-19 大日精化工業株式会社 Adhésif
KR20230163499A (ko) 2021-05-12 2023-11-30 토요잉크Sc홀딩스주식회사 금속 보강판 부착 프린트 배선판의 제조 방법, 부재 세트, 및 금속 보강판 부착 프린트 배선판
US11939455B2 (en) 2018-06-29 2024-03-26 Dow Global Technologies Llc Polyolefin formulation with poly(2-alkyl-2-oxazoline)

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KR102334672B1 (ko) * 2014-06-03 2021-12-06 다이요 잉키 세이조 가부시키가이샤 경화성 조성물 및 전자 부품
JP6457078B2 (ja) * 2015-05-20 2019-01-23 リケンテクノス株式会社 補強テープ、及びこれを用いたフレキシブルフラットケーブル
US10196545B2 (en) * 2015-05-26 2019-02-05 Tatsuta Electric Wire & Cable Co., Ltd. Shielding film and shielded printed wiring board
JP6371460B1 (ja) * 2017-12-06 2018-08-08 タツタ電線株式会社 配線基板用補強板
JP6506461B1 (ja) * 2018-02-01 2019-04-24 積水化学工業株式会社 導電性粘着テープ
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CN109943252B (zh) * 2019-02-28 2020-10-02 苏州金枪新材料股份有限公司 一种银包铜导电胶及其制备方法
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JP6690801B1 (ja) * 2020-01-21 2020-04-28 東洋インキＳｃホールディングス株式会社 電磁波シールドシート、および電磁波シールド性配線回路基板
KR102294673B1 (ko) * 2021-01-26 2021-08-27 88테크 주식회사 측쇄에 수산기와 카르복실기를 갖는 수지의 합성 방법과 그 수지를 포함하는 잉크 조성물의 제조방법 및 적용방법
CN113831876B (zh) * 2021-09-24 2023-05-23 深圳市南科康达科技有限公司 一种导电胶、固态导电胶膜及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006088127A1 (fr) * 2005-02-18 2006-08-24 Toyo Ink Manufacturing Co., Ltd. Film adhésif de protection contre les ondes électromagnétiques, procédé de fabrication de celui-ci et procédé de protection d’une partie adhérée contre les ondes électromagnétiques
WO2009090997A1 (fr) * 2008-01-15 2009-07-23 Toyo Ink Manufacturing Co., Ltd. Film adhésif durcissable à blindage électromagnétique, son procédé de production, son utilisation, procédé de production d'un article à blindage électromagnétique et article à blindage électromagnétique
JP2013159639A (ja) * 2012-02-01 2013-08-19 Toyo Ink Sc Holdings Co Ltd カルボキシル基含有変性ウレタンエステル樹脂を含む熱硬化性樹脂組成物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004043601A (ja) * 2002-07-10 2004-02-12 Bridgestone Corp 異方性導電フィルム
JP4843979B2 (ja) * 2004-03-30 2011-12-21 住友ベークライト株式会社 回路基板
CN1277893C (zh) * 2005-07-11 2006-10-04 大连轻工业学院 一种光固化导电胶及其制法
CN101268163B (zh) * 2005-09-16 2012-11-14 东洋油墨制造株式会社 粘结剂组合物、使用它的粘结剂片及其应用
JP2007189091A (ja) * 2006-01-13 2007-07-26 Tatsuta System Electronics Kk 等方導電性接着シート及び回路基板
KR101473045B1 (ko) * 2008-01-15 2014-12-15 토요잉크Sc홀딩스주식회사 경화성 전자파 차폐성 접착성 필름, 그의 제조방법, 그의 사용방법, 전자파 차폐물의 제조방법 및 전자파 차폐물
JP2010143981A (ja) * 2008-12-17 2010-07-01 Toyo Ink Mfg Co Ltd 硬化性導電性ポリウレタンポリウレア接着剤組成物、硬化性電磁波シールド性接着性フィルムおよびその製造方法
CN106947409B (zh) * 2012-06-29 2018-12-11 大自达电线股份有限公司 导电胶组成物、导电胶膜、黏合方法及线路基板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006088127A1 (fr) * 2005-02-18 2006-08-24 Toyo Ink Manufacturing Co., Ltd. Film adhésif de protection contre les ondes électromagnétiques, procédé de fabrication de celui-ci et procédé de protection d’une partie adhérée contre les ondes électromagnétiques
WO2009090997A1 (fr) * 2008-01-15 2009-07-23 Toyo Ink Manufacturing Co., Ltd. Film adhésif durcissable à blindage électromagnétique, son procédé de production, son utilisation, procédé de production d'un article à blindage électromagnétique et article à blindage électromagnétique
JP2013159639A (ja) * 2012-02-01 2013-08-19 Toyo Ink Sc Holdings Co Ltd カルボキシル基含有変性ウレタンエステル樹脂を含む熱硬化性樹脂組成物

Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015110769A (ja) * 2013-11-07 2015-06-18 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、配線デバイス、および配線デバイスの製造方法
WO2015068611A1 (fr) * 2013-11-07 2015-05-14 東洋インキＳｃホールディングス株式会社 Adhésif électroconducteur, feuille adhésive électroconductrice, dispositif de câblage et procédé de fabrication d'un dispositif de câblage
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KR20170008804A (ko) * 2014-08-12 2017-01-24 미쓰비시 쥬시 가부시끼가이샤 투명 점착 시트
JP2016121285A (ja) * 2014-12-25 2016-07-07 日東シンコー株式会社 絶縁紙
JP2016121289A (ja) * 2014-12-25 2016-07-07 大日精化工業株式会社 接着剤
KR20160127657A (ko) 2015-04-27 2016-11-04 토요잉크Sc홀딩스주식회사 도전성 접착제, 도전성 접착 시트, 및 배선 디바이스
JP2016204567A (ja) * 2015-04-27 2016-12-08 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、および配線デバイス
JP5892282B1 (ja) * 2015-04-27 2016-03-23 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、および配線デバイス
JP2016222748A (ja) * 2015-05-27 2016-12-28 東洋インキＳｃホールディングス株式会社 導電性接着剤、ならびにそれを用いた導電性接着シートおよび電磁波シールドシート
JP5854248B1 (ja) * 2015-05-27 2016-02-09 東洋インキＳｃホールディングス株式会社 導電性接着剤、ならびにそれを用いた導電性接着シートおよび電磁波シールドシート
US10611931B2 (en) 2015-08-28 2020-04-07 Dupont Electronics, Inc. Electrically conductive adhesives
WO2017035710A1 (fr) * 2015-08-28 2017-03-09 E.I. Du Pont De Nemours And Company Adhésifs électroconducteurs
US10967428B2 (en) 2015-08-28 2021-04-06 Dupont Electronics, Inc. Coated copper particles and use thereof
US10629323B2 (en) 2015-08-28 2020-04-21 Dupont Electronics, Inc. Electrically conductive adhesives
JPWO2017038818A1 (ja) * 2015-09-04 2018-04-26 タツタ電線株式会社 プリント配線板の製造方法ならびに該方法に用いられるプリント配線板保護フィルムおよびシート状積層体
CN107852817A (zh) * 2015-09-04 2018-03-27 拓自达电线株式会社 印制布线板的制造方法以及用于所述方法的印制布线板保护膜及片状层叠体
TWI713426B (zh) * 2015-09-04 2020-12-11 日商拓自達電線股份有限公司 印刷電路板的製造方法及該方法所使用之印刷電路板保護薄膜、以及片狀積層體
JP2018197001A (ja) * 2015-09-04 2018-12-13 タツタ電線株式会社 プリント配線板の製造方法に用いられるシート状積層体
WO2017038818A1 (fr) * 2015-09-04 2017-03-09 タツタ電線株式会社 Procédé de production de cartes de circuit imprimé, et film de protection de cartes de circuit imprimé et stratifié en forme de feuille utilisés dans le procédé
JP2017098486A (ja) * 2015-11-27 2017-06-01 株式会社ノリタケカンパニーリミテド 圧電素子用導電性接着剤および圧電素子
JP2016204628A (ja) * 2016-02-02 2016-12-08 東洋インキＳｃホールディングス株式会社 導電性接着剤、導電性接着シート、および配線デバイス
JP6320660B1 (ja) * 2016-05-23 2018-05-09 タツタ電線株式会社 導電性接着剤組成物
US10577524B2 (en) 2016-05-23 2020-03-03 Tatsuta Electric Wire & Cable Co., Ltd. Conductive adhesive composition
KR20190042510A (ko) 2016-08-05 2019-04-24 후지모리 고교 가부시키가이샤 Fpc용 도전성 접착 시트 및 fpc
KR20180016270A (ko) 2016-08-05 2018-02-14 후지모리 고교 가부시키가이샤 Fpc용 도전성 접착 시트 및 fpc
JP2018070694A (ja) * 2016-10-25 2018-05-10 株式会社巴川製紙所 導電性接着剤組成物、電磁波シールドシート及びそれを用いた配線デバイス
JP2017115152A (ja) * 2017-01-18 2017-06-29 藤森工業株式会社 導電性接着剤層、及びｆｐｃ用電磁波シールド材
WO2018211887A1 (fr) * 2017-05-19 2018-11-22 タツタ電線株式会社 Agent adhésif conducteur
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JPWO2018211887A1 (ja) * 2017-05-19 2020-03-19 タツタ電線株式会社 導電性接着剤
US11098227B2 (en) 2017-08-07 2021-08-24 Tatsuta Electric Wire & Cable Co., Ltd. Conductive adhesive
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US10723920B2 (en) 2017-08-07 2020-07-28 Tatsuta Electric Wire & Cable Co., Ltd. Conductive adhesive
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JP2019065069A (ja) * 2017-09-28 2019-04-25 タツタ電線株式会社 導電性接着剤シート
JP6329314B1 (ja) * 2017-09-28 2018-05-23 タツタ電線株式会社 導電性接着剤シート
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WO2019166364A1 (fr) * 2018-02-27 2019-09-06 Covestro Deutschland Ag Composition cosmétique pour améliorer la tenue d'une coiffure
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JPWO2021020542A1 (fr) * 2019-08-01 2021-02-04
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