WO2017204218A1 - 導電性接着剤組成物 - Google Patents
導電性接着剤組成物 Download PDFInfo
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- WO2017204218A1 WO2017204218A1 PCT/JP2017/019210 JP2017019210W WO2017204218A1 WO 2017204218 A1 WO2017204218 A1 WO 2017204218A1 JP 2017019210 W JP2017019210 W JP 2017019210W WO 2017204218 A1 WO2017204218 A1 WO 2017204218A1
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- conductive adhesive
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- conductive
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- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/80—Masked polyisocyanates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- 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
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- 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
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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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0271—Arrangements for reducing stress or warp in rigid printed circuit boards, e.g. caused by loads, vibrations or differences in thermal expansion
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
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- 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
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- 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
- C09J2301/304—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 being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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- C09J2463/00—Presence of epoxy resin
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- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- C09J2475/00—Presence of polyurethane
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/07—Electric details
- H05K2201/0707—Shielding
- H05K2201/0715—Shielding provided by an outer layer of PCB
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- H—ELECTRICITY
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- 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
Definitions
- the present invention relates to a conductive adhesive composition used for a printed wiring board.
- a conductive adhesive obtained by adding a conductive filler to an adhesive resin composition has been used to attach a reinforcing plate or an electromagnetic wave shielding film to a printed wiring board.
- an opening is formed in the coverlay of the printed wiring board to expose a circuit made of copper foil, and the opening is filled with a conductive adhesive.
- the circuit is electrically connected to the reinforcing plate and the electromagnetic shielding film.
- a conductive adhesive for example, an adhesive in which a thermosetting resin is mixed with a conductive filler and silica particles having a predetermined specific surface area is disclosed. And it is described by mix
- an adhesive sheet made of an adhesive composition containing a polyurethane polyurea resin having a predetermined acid value and an epoxy resin is disclosed. And it is described that reflow resistance improves by using such an adhesive sheet (for example, refer patent document 2).
- the conductivity and the adhesion to the printed wiring board are lowered, so that the reflow resistance (withstands the reflow process).
- High heat resistance and high adhesion between the printed circuit board and the conductivity after the reflow process are required.
- the hole diameter of the opening provided in the cover lay also tends to be small.
- Patent Document 1 has a problem in that, when silica particles are added, the ratio of the thermosetting resin is reduced, so that the adhesiveness to the reinforcing plate and the printed wiring board is reduced.
- the present invention has been made in view of the above problems, and an object thereof is to provide a conductive adhesive composition that can ensure excellent conductivity and adhesion to a printed wiring board even after reflow.
- the conductive adhesive composition of the present invention contains a thermosetting resin having a functional group capable of reacting with an epoxy group, an epoxy resin, and a conductive filler, and has an average particle size. Is 4 ⁇ m or more and 13 ⁇ m or less, and further contains urethane resin particles having a type A durometer hardness of 55 or more and 90 or less measured in accordance with JIS K 6253.
- the conductive adhesive composition of the present invention is a conductive adhesive composition containing a thermosetting resin, a conductive filler (H), and urethane resin particles (I).
- Thermosetting resin is not particularly limited, and polyamide resin, polyimide resin, acrylic resin, phenol resin, epoxy resin, polyurethane resin, polyurethane urea resin, melamine resin, alkyd resin, etc. are used. can do. These may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining excellent reflow resistance, the thermosetting resin is preferably a thermosetting resin having a functional group capable of reacting with an epoxy group.
- thermosetting resins include epoxy group-modified polyester resins, epoxy group-modified polyamide resins, epoxy group-modified acrylic resins, epoxy group-modified polyurethane polyurea resins, carboxyl group-modified polyester resins, carboxyl group-modified polyamide resins, and carboxyl group-modified resins.
- examples thereof include acrylic resins and carboxyl group-modified polyurethane polyurea resins.
- a carboxyl group-modified polyester resin, a carboxyl group-modified polyamide resin, and a carboxyl group-modified polyurethane polyurea resin are preferable.
- the acid value is preferably 2 to 100 mgKOH / g, more preferably 2 to 50 mgKOH / g, and 3 to 30 mgKOH / g. Is more preferable.
- the acid value is 2 mgKOH / g or more, the epoxy resin described below is sufficiently cured, so that the heat resistance of the conductive adhesive composition is improved.
- cures enough with the epoxy resin mentioned later as an acid value is 100 mgKOH / g or less, the peel strength of a conductive adhesive composition becomes favorable.
- the carboxyl group-modified polyester resin can be obtained, for example, by reacting a hydroxyl group-containing polyester resin with a polybasic acid having 3 or more carboxyl groups in the molecule or an anhydride thereof.
- the hydroxyl group-containing polyester resin can be obtained by reacting a diol with a dibasic acid, a dibasic acid anhydride, or a dialkyl ester of a dibasic acid.
- diol examples include linear or branched aliphatic diols having 2 to 12 carbon atoms, specifically, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4 -Trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-diethyl-1,3-propanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, or 3-methyl-1,5-pentanediol, or the number of carbon atoms
- dibasic acid or dibasic acid anhydride to be reacted with the diol examples include aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid, and anhydrides thereof.
- aromatic dicarboxylic acid or its anhydride examples include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, and (anhydrous) phthalic acid.
- (anhydrous) phthalic acid collectively means phthalic acid and phthalic anhydride.
- Examples of the alicyclic dicarboxylic acid or its anhydride include tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, 1,4-cyclohexanedicarboxylic acid, and the like.
- Examples of the aliphatic dicarboxylic acid or anhydride thereof include (anhydrous) succinic acid, fumaric acid, (anhydrous) maleic acid, adipic acid, sebacic acid, azelaic acid, and hymic acid.
- dialkyl ester of the dibasic acid to be reacted with the diol examples include an esterified product of the dibasic acid and a linear or branched alkyl alcohol having 1 to 18 carbon atoms.
- Examples of the linear or branched alkyl alcohol having 1 to 18 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n- Mention may be made of amyl alcohol, acetyl isopropyl alcohol, neohexyl alcohol, isohexyl alcohol, n-hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol or octadecyl alcohol.
- Preferred compounds as dialkyl esters of dibasic acids are dimethylphthalic acid and dimethylisophthalic acid.
- the carboxyl group-containing polyester resin can be obtained by reacting a polyester resin having a hydroxyl group with a polybasic acid having 3 or more (preferably 3 or 4) carboxyl groups in the molecule or an anhydride thereof. .
- polybasic acids having 3 or more carboxyl groups in the molecule or anhydrides thereof include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, or ethylene glycol bistrimellitate dianhydride. Can do.
- the carboxyl group-modified polyamide resin is synthesized by, for example, a condensation reaction from a polycarboxylic acid component such as dicarboxylic acid, tricarboxylic acid, or tetracarboxylic dianhydride and an organic diisocyanate or diamine.
- a polycarboxylic acid component such as dicarboxylic acid, tricarboxylic acid, or tetracarboxylic dianhydride and an organic diisocyanate or diamine.
- polyvalent carboxylic acid examples include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid and other aliphatic dicarboxylic acids, isophthalic acid, terephthalic acid, phthalic acid, naphthalene
- Aromatic dicarboxylic acids such as dicarboxylic acid, diphenylsulfone dicarboxylic acid, oxydibenzoic acid, aromatic carboxylic acid anhydrides such as trimellitic acid, pyromellitic acid, diphenylsulfone tetracarboxyl dianhydride, benzophenone tetracarboxyl dianhydride, etc. Can be mentioned. In addition, these can be used individually or in combination of 2 or more types.
- organic diisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane Aromatic diisocyanates such as diisocyanate, p-phenylene diisocyanate, m-xylene diisocyanate, m-tetramethylxylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate Aliphatic isocyanates such as transcyclohexane-1,4-diisocyanate, hydrogenated m-xylene diisocyanate, and lysine diisocyanate Such as over doors and the like. These can
- a diamine can also be used in place of the organic diisocyanate.
- the diamine include phenylenediamine, diaminodiphenylpropane, diaminodiphenylmethane, benzidine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, diaminodiphenyl ether, and the like.
- the carboxyl group-modified polyurethane polyurea resin comprises a urethane prepolymer (D) obtained by reacting a polyol compound (A), a diisocyanate compound (B) and a diol compound (C) having a carboxyl group, and a polyamino compound (E).
- a polyurethane polyurea resin (F) obtained by reacting is preferred.
- the polyol compound in this invention is not specifically limited, The well-known polyol used for urethane synthesis can be used. Examples of such polyols include polyester polyols, polyether polyols, polycarbonate polyols, 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 compound (A) is not particularly limited, but is preferably 500 to 3,000.
- the number average molecular weight (Mn) of the polyol compound (A) is less than 500, the cohesive force of urethane bonds is hardly expressed and the mechanical properties tend to be lowered.
- a crystalline polyol having a number average molecular weight of more than 3,000 may cause a whitening phenomenon when formed into a film.
- a polyol compound (A) can be used individually or in combination of 2 or more types.
- reaction component for obtaining a urethane prepolymer (D) it is also preferable to use a short chain diol component and / or a diamine component as needed. This makes it easy to control the hardness and viscosity of the polyurethane polyurea resin (F).
- the short chain diol component include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol and the like.
- alkylene oxide low molar adducts number average molecular weight less than 500 by terminal functional group determination
- alicyclic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol and alkylene thereof Oxide low mole adduct (number average molecular weight less than 500, same as above); aromatic glycol such as xylylene glycol and its alkylene oxide low mole adduct (less than number average molecular weight less than 500, same as above); bisphenol A, thiobisphenol, sulfone bisphenol, etc. Bisphenol and alkylene oxide low mol adduct (number average molecular weight of less than 500, supra); and C1 ⁇ C18 alkyl dialkanolamine such as alkyl diethanolamine and the like.
- diamine compound examples include, as short-chain compounds, aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and octamethylene diamine; phenylene diamine, 3,3′-dichloro-4, Aromatic diamine compounds such as 4′-diaminodiphenylmethane, 4,4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone; cyclopentyldiamine, cyclohexyldiamine, 4,4 ′ And alicyclic diamine compounds such as diaminodicyclohexylmethane, 1,4-diaminocyclohexane and isophoronediamine.
- aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and oct
- hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide can be used as the diamine compound.
- long-chain ones include long-chain alkylene diamines, polyoxyalkylene diamines, terminal amine polyamides, and siloxane-modified polyamines. These diamine compounds can be used alone or in combination of two or more.
- ⁇ Diisocyanate compound (B)> Although the diisocyanate compound (B) in this invention is not specifically limited, The conventionally well-known diisocyanate compound currently used for manufacture of a polyurethane can be used. Specific examples of the diisocyanate compound (B) include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene.
- the diol compound (C) having a carboxy group in the present invention is not particularly limited, and examples thereof include dimethylol alkanoic acids such as dimethylolpropanoic acid and dimethylolbutanoic acid; alkylene oxide low molar adducts of dimethylolalkanoic acid (terminal functional groups).
- ⁇ -caprolactone low molar adduct of dimethylol alkanoic acid (number average molecular weight of less than 500 by terminal functional group quantification); derived from acid anhydride of dimethylol alkanoic acid and glycerin Half esters: 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 can be exemplified. Among them, dimethylolpropanoic acid and dimethylolalkanoic acid such as dimethylolbutanoic acid are preferable from the viewpoints of availability, ease of adjustment of acid value, and the like.
- the urethane prepolymer (D) of the present invention is obtained by reacting the above-described polyol compound (A), diisocyanate compound (B) and diol compound (C) having a carboxyl group.
- the equivalent ratio of the diisocyanate compound (B) to the hydroxyl group of the polyol compound (A) and the diol compound (C) having a carboxyl group is preferably 1.1 to 2.5. By setting it within the above range, it is preferable in that a conductive adhesive composition having high heat resistance and high mechanical strength can be obtained.
- the reaction temperature is not particularly limited, an embodiment in which the reaction is performed at 60 to 100 ° C. can be mentioned.
- reaction terminator When obtaining the urethane prepolymer (D) by reacting the polyol compound (A), the diisocyanate compound (B) and the diol compound (C) having a carboxyl group, it is necessary for the purpose of adjusting the molecular weight of the urethane prepolymer.
- a reaction terminator can be used accordingly.
- a monoalcohol compound, a monoamine compound, an alkanolamine compound, or the like can be used.
- the monoalcohol for example, methanol, ethanol, butanol, isopropanol and the like can be used.
- butylamine, dibutylamine, etc. can be used as a monoamine compound.
- alkanolamine monoethanolamine, diethanolamine, etc. can be used.
- polyamino compound (E) in this invention is not specifically limited, The conventionally well-known polyamino compound currently used for manufacture of a polyurea resin can be used. Specific examples of the polyamino compound (E) include ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-dimethyl-4.
- aminoethylethanolamine aminopropylethanolamine, aminohexylethanolamine, aminoethyl Examples include compounds such as aminoalkylalkanolamines such as propanolamine, aminopropylpropanolamine, and aminohexylpropanolamine.
- the weight average molecular weight of the polyurethane polyurea resin (F) in the present invention is usually 50,000 to 100,000.
- epoxy resin in this invention is not specifically limited, The well-known epoxy resin which has a 2 or more epoxy group in 1 molecule can be used.
- examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol type epoxy resins such as bisphenol S type epoxy resins, spirocyclic epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, Terpene type epoxy resin, glycidyl ether type epoxy resin such as tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane, glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane, tetrabromobisphenol A type epoxy resin, cresol novolak Epoxy resin, phenol novolac epoxy resin, ⁇ -naphthol novolac epoxy resin, brominated phenol no
- the epoxy equivalent of the epoxy resin is preferably 800 to 100,000. Thereby, it is preferable at the point that the adhesive force with a reinforcement board improves more.
- an epoxy resin having an epoxy equivalent of 800 to 10,000 and an epoxy resin having an epoxy equivalent of 90 to 300 are preferably used in combination.
- the epoxy resin having an epoxy equivalent of 800 to 10,000 and the epoxy resin having an epoxy equivalent of 90 to 300 may be the same type or different in chemical structure.
- An epoxy resin having an epoxy equivalent of 800 to 10000 is preferable in that the adhesion with the reinforcing plate 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.
- As the epoxy resin having an epoxy equivalent of 800 to 10,000 it is preferable to use a resin that is solid at room temperature. Being solid at room temperature means a solid state having no fluidity in a solvent-free state at 25 ° C.
- epoxy resins that can be used as an epoxy resin having an epoxy equivalent of 800 to 10,000 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 can be given.
- An epoxy resin having an epoxy equivalent of 90 to 300 is preferable in that 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.
- As the epoxy resin having an epoxy equivalent of 90 to 300 it is preferable to use a resin that is solid at room temperature.
- the epoxy resin having an epoxy equivalent of 90 to 300 is more preferably a novolac 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 epoxy resins having an epoxy equivalent of 90 to 300 as described above include EPICLON N-660, N-665, N-670, N-673, N-680, N- 695, N-655-EXP-S, N-662-EXP-S, N-665-EXP, N-665-EXP-S, N-672-EXP, N-670-EXP-S, N-685 EXP, N-673-80M, N-680-75M, N-690-75M, N-740, N-770, N-775, N-740-80M, N-770-70M, N-865, N- 865-80M (trade name, manufactured by DIC Corporation), jER152, 154, 157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), YDPN-638, YDCN-700, YDCN- 00-2, YDCN-700-3, YDCN-700-5, YDCN-700-7,
- the epoxy resin having an epoxy equivalent of 800 to 10,000 is an epoxy other than a novolac type epoxy resin that is solid at room temperature. It is preferable to use a resin. If the adhesive layer is composed only of a novolac type epoxy resin, there is a problem in that the adhesion is not sufficient. Therefore, an epoxy resin having an epoxy equivalent of 800 to 10,000 is not limited to such a novolac type epoxy resin. It is preferable to use one.
- the ratio of the thermosetting resin having a functional group capable of reacting with an epoxy group and the epoxy resin is such that the epoxy resin is based on 100 parts by mass of the thermosetting resin having a functional group capable of reacting with an epoxy group.
- the amount is preferably 50 to 500 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 50 to 200 parts by mass when paying attention to the adhesion after the main adhesion.
- the epoxy resin is 50 parts by mass or more, so that reflow resistance, adhesion after main bonding, and adhesion with a resin plate
- the adhesiveness to metal materials such as gold plating is improved by being 500 parts by mass or less.
- the conductive adhesive film of the present invention contains a conductive filler (H).
- the conductive filler (H) 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. Can be created by law.
- the average particle diameter of the conductive filler is preferably 3 to 50 ⁇ m in order to facilitate contact between the fillers.
- examples of the shape of the conductive filler include a spherical shape, a flake shape, a dendritic shape, and a fibrous shape.
- the conductive filler (H) is preferably at least one selected from the group consisting of silver powder, silver-coated copper powder, and copper powder from the viewpoint of connection resistance and cost.
- the conductive filler (H) is preferably contained in a proportion of 40 to 90% by mass with respect to the total amount of the conductive adhesive composition.
- silane coupling agents for conductive adhesive films, silane coupling agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, leveling regulators are used as long as solder reflow resistance is not deteriorated. , Fillers, flame retardants, etc. may be added.
- the urethane resin particles (I) contained in the conductive adhesive composition of the present invention are those having an average particle diameter of 4 ⁇ m or more and 13 ⁇ m or less, and preferably 5 ⁇ m or more and 7 ⁇ m or less.
- the “average particle size” referred to here means a 50% particle size (D50), and a particle size distribution measuring apparatus (Nanotrack (registered trademark) particle size measuring apparatus manufactured by Nikkiso Co., Ltd.) applying the laser Doppler method. UPA-EX150) etc.
- the urethane resin particles (I) of the present invention have a hardness (type A durometer hardness) measured by a type A durometer in accordance with JIS K-6253. In the range of 55 to 90. This is because when the hardness is less than 55, the reflow resistance may be insufficient, and when the hardness is greater than 90, the adhesion strength may be insufficient. .
- the average particle diameter of the urethane resin particles (I) is set to 4 ⁇ m or more and 13 ⁇ m or less, and the hardness of the urethane resin particles (I) is set to 55 or more and 90 or less. Therefore, even after reflow, it is possible to obtain a conductive adhesive composition having excellent conductivity and excellent adhesion to a printed wiring board.
- the blending amount of the urethane resin particles (I) with respect to the total amount of the conductive adhesive composition is preferably 3 to 30% by mass. This is because when the blending amount is less than 3% by mass and the blending amount is greater than 10% by mass, the connection resistance value may become unstable.
- the conductive adhesive film of the present invention may contain a curing agent as necessary. It does not specifically limit as said hardening
- 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 blocked isocyanate compound a compound obtained by blocking the above-described isocyanate compound by a 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, butyl glycolate
- the carbodiimide compound is not particularly limited, and examples thereof include those obtained by the above-described decarboxylation condensation reaction of isocyanate compounds.
- the oxazoline compound is not particularly limited.
- the amount of the curing agent used is preferably 0.1 to 200 parts by mass or less with respect to 100 parts by mass of the resin component of the thermosetting resin having a functional group capable of reacting with an epoxy group. More preferably, the amount is from 100 parts by mass.
- the conductive adhesive film of the present invention may be used in combination with an imidazole-based curing accelerator in order to accelerate the curing of the curing agent.
- the curing accelerator is not particularly limited.
- 2-phenyl-4,5-dihydroxymethylimidazole, 2-heptadecylimidazole, 2,4-diamino-6- (2′-undecylimidazolyl) ethyl-S -Triazine 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 5-cyano-2-phenylimidazole, 2,4-diamino-6- [2'methylimidazolyl- (1 ')]-ethyl-S- Imidazoles such as triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 1-cyanoethyl-2
- the use amount of the curing accelerator is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the resin component of the thermosetting resin having a functional group capable of reacting with the epoxy group.
- the conductive adhesive film 1 of the present invention coats the peelable substrate 2 (release film) and the surface of the peelable substrate 2 with the above-described conductive adhesive composition.
- the conductive adhesive layer 4 formed by this is provided.
- the coating method is not particularly limited, and known coating equipment represented by die coating, lip coating, comma coating and the like can be used. In addition, what is necessary is just to set suitably the conditions at the time of coating the mold release base material 2 with a conductive adhesive composition.
- the releasable substrate 2 is formed by applying a silicon-based or non-silicon-based release agent on the surface on which the conductive adhesive layer 4 is formed on a base film such as polyethylene terephthalate or polyethylene naphthalate. Can be used. Note that the thickness of the releasable substrate 2 is not particularly limited, and is appropriately determined in consideration of ease of use.
- the thickness of the conductive adhesive layer 4 is preferably 15 to 100 ⁇ m. If the thickness is less than 15 ⁇ m, the embedding property becomes insufficient, and sufficient connection with the ground circuit may not be obtained. If the thickness is more than 100 ⁇ m, it is disadvantageous in cost and cannot meet the demand for thinning. By setting to such a thickness, when the substrate has irregularities, it flows appropriately, so that it can be deformed into a shape that fills the recess and can be bonded with good adhesion.
- the conductive adhesive composition of the present invention can be used as an anisotropic conductive adhesive layer or an isotropic conductive adhesive layer depending on the purpose of use.
- the conductive adhesive composition of the present invention when used as a conductive adhesive film for bonding to a reinforcing plate, it can be used as an isotropic conductive adhesive layer.
- an electromagnetic wave shielding film having a metal layer it can be used as an isotropic conductive adhesive layer or an anisotropic conductive adhesive layer, but it should be used as an anisotropic conductive adhesive layer. Is preferred.
- the conductive filler (H) can be used as any adhesive layer depending on the blending amount of the conductive filler (H).
- the conductive filler is preferably 5% by mass or more and less than 40% by mass in the total solid content of the conductive adhesive composition.
- the conductive filler (H) is preferably 40% by mass or more and 90% by mass or less in the total solid content of the conductive adhesive composition.
- the conductive adhesive film using the conductive adhesive of the present invention is excellent in adhesion to the printed wiring board, and the adhesion to the printed wiring board is to a resin board such as a polyimide film. And adhesion to metal materials such as gold-plated copper foil and conductive reinforcing plate are included.
- the electromagnetic wave shielding film 20 using the conductive adhesive composition of the present invention includes a conductive adhesive layer 4 and a protective layer 13 provided on the surface of the conductive adhesive layer 4.
- the protective layer 13 is not particularly limited as long as it has insulating properties (that is, a layer formed of an insulating resin composition), and a known layer can be used. Further, as the protective layer 13, the resin component (excluding the conductive filler) used for the conductive adhesive layer 4 described above may be used. Further, the protective layer 13 may be a laminate of two or more layers having different materials or physical properties such as hardness or elastic modulus.
- the thickness of the protective layer 13 is not particularly limited and can be appropriately set as necessary, but is 1 ⁇ m or more (preferably 4 ⁇ m or more), 20 ⁇ m or less (preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less). It can be.
- the protective layer 13 may include a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, and a viscosity as necessary.
- a regulator, an antiblocking agent, etc. may be included.
- this electromagnetic wave shielding film 20 forms the protective layer 13 by coating the resin composition for protective layers on one side of a peelable film, for example, and drying, Next, on the protective layer 13 There is a method of forming the conductive adhesive layer 4 by coating the above-mentioned conductive adhesive composition and drying it.
- a conventionally known coating method such as a gravure coating method, a kiss coating method, a die coating method, a lip coating method, a comma coating method, a blade coating method, or a roll coating method.
- a knife coating method, a spray coating method, a bar coating method, a spin coating method, a dip coating method, or the like can be used.
- the electromagnetic wave shielding film 20 can be adhered on the printed wiring board by hot pressing.
- the conductive adhesive layer 4 of the electromagnetic wave shielding film 20 becomes soft by heating and flows into a ground portion provided on the printed wiring board by pressurization. Thereby, the ground circuit and the conductive adhesive are electrically connected, and the shielding effect can be enhanced.
- this electromagnetic wave shielding film 20 can be used for the shield printed wiring board 30 shown in FIG. 2, for example.
- the shield printed wiring board 30 includes a printed wiring board 40 and an electromagnetic wave shielding film 20.
- the printed wiring board 40 includes a base substrate 41, a printed circuit (ground circuit) 42 formed on the base substrate 41, and an insulating adhesive layer 43 provided on the base substrate 41 adjacent to the printed circuit 42. And an insulating cover lay 44 provided to cover the insulating adhesive layer 43.
- the insulating adhesive layer 43 and the cover lay 44 constitute an insulating layer of the printed wiring board 40, and the insulating adhesive layer 43 and the cover lay 44 have openings for exposing a part of the printed circuit 42. A portion 45 is formed.
- the base substrate 41, the insulating adhesive layer 43, and the coverlay 44 are not particularly limited, and may be, for example, a resin film. In this case, it can be formed of a resin such as polypropylene, cross-linked polyethylene, polyester, polybenzimidazole, polyimide, polyimide amide, polyether imide, or polyphenylene sulfide.
- the printed circuit 42 can be, for example, a copper wiring pattern formed on the base substrate 41.
- the electromagnetic wave shielding film 20 is placed on the printed wiring board 40 and pressurized while being heated by a press. A part of the adhesive layer 4 softened by heating flows into the opening 45 by pressurization. Thereby, the electromagnetic wave shielding film 20 is attached to the printed wiring board 40 via the adhesive layer 4.
- the electromagnetic wave shielding film of the present invention may have a metal layer. By having a metal layer, more excellent electromagnetic shielding performance can be obtained.
- the electromagnetic wave shielding film 21 using the conductive adhesive composition of the present invention includes a metal layer (shield layer) 14 and a first surface of the metal layer 14.
- the conductive adhesive layer 4 provided on the side and the protective layer 13 provided on the second surface side opposite to the first surface of the metal layer 14 are provided.
- Examples of the metal material for forming the metal layer 14 include nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium, zinc, and an alloy containing any one or more of these materials. It can be selected as appropriate according to the required electromagnetic shielding effect and repeated bending / sliding resistance.
- the thickness of the metal layer 14 is not particularly limited, and can be set to 0.1 ⁇ m to 8 ⁇ m, for example.
- a formation method of the metal layer 14 there are an electrolytic plating method, an electroless plating method, a sputtering method, an electron beam evaporation method, a vacuum evaporation method, a CVD method, a metal organic, and the like.
- the metal layer 14 may be a metal foil or metal nanoparticles.
- this electromagnetic wave shielding film 21 can be used for the shield printed wiring board 31 shown in FIG. 3, for example.
- the shield printed wiring board 31 includes the above-described printed wiring board 40 and the electromagnetic wave shielding film 21.
- the electromagnetic wave shielding film 21 is placed on the printed wiring board 40 and pressed while being heated by a press machine. A part of the adhesive layer 4 softened by heating flows into the opening 45 by pressurization. As a result, the electromagnetic wave shielding film 21 is attached to the printed wiring board 40 via the adhesive layer 4, and the metal layer 14 and the printed circuit 42 of the printed wiring board 40 are connected via the conductive adhesive. The metal layer 14 and the printed circuit 42 are connected.
- the electroconductive adhesive composition of this invention can be used for a shield printed wiring board provided with a reinforcement board. More specifically, for example, it can be used for the shield printed wiring board 32 shown in FIG.
- the shield printed wiring board 32 includes a printed wiring board 47, a conductive adhesive layer 4, and a conductive reinforcing plate 15.
- the printed wiring board 47 and the conductive reinforcing plate 15 are bonded and electrically connected by the conductive adhesive layer 4 of the present invention.
- a plating layer (for example, a gold plating layer) 46 is provided on a part of the surface of the printed circuit 42, and the plating layer 46 is exposed from the opening 45.
- the printed circuit 42 and the conductive reinforcing plate 15 are connected to each other through the adhesive layer 4 flowing into the opening 45 without providing the plating layer 46.
- a direct connection may be used.
- the portion where the electronic component is mounted is distorted due to the bending of the printed wiring board.
- a conductive metal plate or the like can be used as the conductive reinforcing plate 15.
- a stainless plate, an iron plate, a copper plate, an aluminum plate, or the like can be used as the conductive reinforcing plate 15.
- a stainless steel plate By using a stainless steel plate, it has sufficient strength to support electronic components even with a thin plate thickness.
- the thickness of the conductive reinforcing plate 15 is not particularly limited, but is preferably 0.025 to 2 mm, more preferably 0.1 to 0.5 mm. If the thickness of the conductive reinforcing plate 15 is within this range, the circuit board to which the conductive reinforcing plate 15 is bonded can be reasonably built into a small device, and the strength sufficient to support the mounted electronic component. Have Further, a metal layer such as Ni or Au may be formed on the surface of the conductive reinforcing plate 15 by plating or the like. The surface of the conductive reinforcing plate 15 may be provided with an uneven shape by sandblasting, etching, or the like.
- examples of the electronic component here include a chip component such as a resistor and a capacitor in addition to a connector and an IC.
- a method for manufacturing the shield printed wiring board 32 will be described.
- a conductive adhesive film to be the conductive adhesive layer 4 is placed on the conductive reinforcing plate 15, and a conductive adhesive film with a reinforcing plate is produced by applying pressure while heating with a press.
- a conductive adhesive film with a reinforcing plate is placed on the printed wiring board 47 and pressed while being heated by a press. A part of the adhesive layer 4 softened by heating flows into the opening 45 by pressurization.
- the conductive reinforcing plate 15 is attached to the printed wiring board 47 via the adhesive layer 4, and the conductive reinforcing plate 15 and the printed circuit 42 of the printed wiring board 47 are connected via the conductive adhesive.
- the conductive reinforcing plate 15 and the printed circuit 42 are brought into conduction. Therefore, the electromagnetic wave shielding ability by the conductive reinforcing plate 15 can be obtained.
- the present invention can also be applied to rigid printed wiring boards. Furthermore, the present invention can be applied not only to a single-side shielded wiring board but also to a double-sided shielded wiring board.
- thermosetting resin having a functional group capable of reacting with an epoxy group a mixture of 35 parts by mass of polyurethane polyurea resin having an acid value of 2 and 45 parts by mass of polyurethane polyurea resin having an acid value of 26 is used.
- Epoxy resin (Mitsubishi Chemical Corporation, trade name: jER4275) 20 parts by mass, phenol novolac type epoxy resin (Mitsubishi Chemical Corporation, trade name: jER152) 20 parts by mass, rubber-modified epoxy resin (Asahi Denka ( Co., Ltd., trade name: ERP-4030) 5 parts by mass, Duranate 17B-60PX (Asahi Kasei Chemicals Co., Ltd.) is used as the blocked isocyanate curing agent, and 2MA-OK is used as the imidazole curing accelerator. (Shikoku Kasei Co., Ltd. product) was used.
- urethane beads manufactured by Dainichi Seika Co., Ltd., trade name: dynamic beads
- silica particles Cicilia 360 (Fuji Silysia Chemical Co., Ltd., average particle size: 5 ⁇ m) was used.
- the produced conductive adhesive composition was hand-coated on a polyethylene terephthalate film (separate film) subjected to a release treatment using a doctor blade (plate-like spatula), and dried at 100 ° C. for 3 minutes.
- a conductive adhesive film was produced.
- each electroconductive adhesive film was produced so that it might become the predetermined thickness of Table 1. The thickness of the conductive adhesive film was measured with a micrometer.
- Example 7 Each material shown in Table 1 was blended to prepare a paste-like conductive adhesive composition.
- 220 g / eq, Tg: 90 ° C.) 7 parts by mass was used.
- 10 parts by mass of urethane beads having an average particle diameter of 7 ⁇ m and a hardness of 74 were used as urethane resin particles.
- Example 8 to 13 Paste-like conductivity was obtained in the same manner as in Example 7 except that the acid value and blending amount of the carboxyl group-modified polyamide resin, the blending amount of the epoxy resin, and the hardness of the urethane resin particles were changed as shown in Table 2. An adhesive composition and a conductive adhesive film were prepared.
- Example 14 Each material shown in Table 3 was blended to prepare a paste-like conductive adhesive composition.
- As urethane resin particles 19 parts by mass of urethane beads having an average particle diameter of 7 ⁇ m and a hardness of 58 were used.
- Example 15 to 16 A paste-like conductive adhesive composition and a conductive adhesive film were produced in the same manner as in Example 14 except that the average particle diameter and hardness of the urethane resin particles were changed as shown in Table 3.
- Example 9 A paste-like conductive adhesive was used in the same manner as in Example 14 except that silica particles having an average particle size of 4 ⁇ m (trade name: Cylicia 350, manufactured by Fuji Silysia Chemical Co., Ltd.) were used instead of urethane resin particles. A composition and a conductive adhesive film were prepared.
- the adhesion between the gold plating formed on the surface of the copper foil of the copper clad laminate and the conductive adhesive was measured by a 90 ° peel test. More specifically, the conductive adhesive films prepared in Examples 1 to 16 and Comparative Examples 1 to 9 and the metal reinforcing plate made of SUS plate (thickness: 200 ⁇ m) were used at a temperature of 170 ° C. for a time using a press machine. : Heated and pressurized under the conditions of 3 minutes and pressure: 2 MPa, and further heated at 150 ° C. for 1 hour, and then the separate film was peeled off to produce a conductive adhesive film with a metal reinforcing plate.
- a gold plating layer of a copper foil laminated film comprising a base substrate made of polyimide, a copper foil formed on the surface of the base substrate, and a gold plating layer formed on the surface of the copper foil, and a metal reinforcing plate
- the adhesive is further adhered with a press machine under the conditions of temperature: 170 ° C., time: 30 minutes, pressure: 3 MPa, and laminated with a copper foil with metal reinforcing plate A film was prepared.
- the copper foil laminated film was peeled off at room temperature with a tensile tester (manufactured by Shimadzu Corporation, trade name AGS-X50S) at a pulling speed of 50 mm / min and a peeling angle of 90 °, and the maximum peel strength at break was obtained. The value was measured. In addition, the case where peel strength was 9.5 N / cm or more was evaluated as excellent in adhesiveness. The above results are shown in Tables 4 and 5.
- the circuit board with a metal reinforcement board was produced by bonding under conditions of minute and pressure: 3 MPa.
- a flexible substrate as shown in FIG. 5, a copper foil pattern 23 having a gold plating layer 22 formed on a part of its surface is formed on a polyimide film 29, and a cover lay made of a polyimide film is formed thereon. What formed 24 was used. And the conductive adhesive film 25 provided with the metal reinforcement board 26 was adhere
- connection resistance ⁇ Measurement of connection resistance>
- the electrical connection between the two copper foil patterns 23 provided with the gold plating layer 22 was performed.
- the resistance value was measured with a resistance meter 28, and the connectivity between the copper foil pattern 23 and the metal reinforcing plate 26 was evaluated.
- connection resistance was less than 0.1 (ohm) was evaluated as what is excellent in electroconductivity. The above results are shown in Tables 4 and 5.
- connection after reflow was performed by the above-described method.
- the resistance value was measured.
- the case where the connection resistance was less than 0.1 ⁇ was evaluated as having excellent conductivity after reflow.
- Tables 4 and 5 The above results are shown in Tables 4 and 5.
- Examples 1 to 16 using urethane beads having an average particle diameter of 4 ⁇ m to 13 ⁇ m and a hardness of 55 to 90 have excellent conductivity before and after reflow. It can be said that it has excellent adhesion to the copper foil laminated film.
- Comparative Example 1 in which the average particle diameter of the urethane beads is small (that is, 3 ⁇ m), as in Comparative Examples 5 and 7 to 8 in which the urethane beads are not used, the connection resistance is sufficient before and after the reflow. It can be said that it has not declined.
- Comparative Example 2 in which the average particle diameter of the urethane beads is large (that is, 15 ⁇ m) and in Comparative Example 3 in which the hardness of the urethane beads is large (that is, 95), the adhesiveness with the copper foil laminated film ( It can be said that (before reflow) is insufficient.
- the present invention is suitable for a conductive adhesive composition used for a printed wiring board.
Abstract
Description
カルボキシル基変性ポリエステル樹脂は、例えば、水酸基含有ポリエステル樹脂と、分子内に3個以上のカルボキシル基を有する多塩基酸もしくはその無水物とを反応させて得ることができる。
カルボキシル基変性ポリアミド樹脂は、例えば、ジカルボン酸、トリカルボン酸、テトラカルボン酸二無水物等の多価カルボン酸成分と有機ジイソシアネート若しくはジアミンから縮合反応により合成される。
カルボキシル基変性ポリウレタンポリウレア樹脂は、ポリオール化合物(A)、ジイソシアネート化合物(B)及びカルボキシル基を有するジオール化合物(C)を反応させて得られるウレタンプレポリマー(D)と、ポリアミノ化合物(E)とを反応させて得られるポリウレタンポリウレア樹脂(F)であることが好ましい。
本発明におけるポリオール化合物は特に限定されず、ウレタン合成に用いられる公知のポリオールを用いることができる。このようなポリオールとしては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール及びその他のポリオールなどを挙げることができる。
本発明におけるジイソシアネート化合物(B)は特に限定されないが、ポリウレタンの製造に用いられている従来公知のジイソシアネート化合物を用いることができる。ジイソシアネート化合物(B)の具体例としては、トルエン-2,4-ジイソシアネート、4-メトキシ-1,3-フェニレンジイソシアネート、4-イソプロピル-1,3-フェニレンジイソシアネート、4-クロル-1,3-フェニレンジイソシアネート、4-ブトキシ-1,3-フェニレンジイソシアネート、2,4-ジイソシアネートジフェニルエーテル、4,4’-メチレンビス(フェニレンイソシアネート)(MDI)、ジュリレンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート(XDI)、1,5-ナフタレンジイソシアネート、ベンジジンジイソシアネート、o-ニトロベンジジンジイソシアネート、4,4’-ジイソシアネートジベンジルなどの芳香族ジイソシアネート;メチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、1,10-デカメチレンジイソシアネートなどの脂肪族ジイソシアネート;1,4-シクロヘキシレンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)、1,5-テトラヒドロナフタレンジイソシアネート、イソホロンジイソシアネート、水添MDI、水添XDIなどの脂環式ジイソシアネート;これらのジイソシアネートと、低分子量のポリオール又はポリアミンとを、末端がイソシアネートとなるように反応させて得られるポリウレタンプレポリマーなどを挙げることができる。
本発明におけるカルボシキル基を有するジオール化合物(C)は特に限定されないが、例えば、ジメチロールプロパン酸、ジメチロールブタン酸などのジメチロールアルカン酸;ジメチロールアルカン酸のアルキレンオキシド低モル付加物(末端官能基定量による数平均分子量500未満);ジメチロールアルカン酸のε-カプロラクトン低モル付加物(末端官能基定量による数平均分子量500未満);ジメチロールアルカン酸の酸無水物とグリセリンとから誘導されるハーフエステル類;ジメチロールアルカン酸の水酸基と、不飽和結合を有するモノマーと、カルボキシル基及び不飽和結合を有するモノマーと、をフリーラジカル反応させて得られる化合物などを挙げることができる。中でも、ジメチロールプロパン酸、及びジメチロールブタン酸などのジメチロールアルカン酸が、入手の容易さ、酸価の調整のしやすさなどの観点から好適である。
本発明のウレタンプレポリマー(D)は、上述のポリオール化合物(A)、ジイソシアネート化合物(B)及びカルボキシル基を有するジオール化合物(C)を反応させて得られる。
ポリオール化合物(A)、ジイソシアネート化合物(B)及びカルボキシル基を有するジオール化合物(C)を反応させてウレタンプレポリマー(D)を得る際、ウレタンプレポリマーの分子量を調整することを目的として、必要に応じて反応停止剤を使用することができる。反応停止剤としては、モノアルコール化合物やモノアミン化合物、アルカノールアミン化合物等を使用することができる。モノアルコールとしては、例えば、メタノール、エタノール、ブタノール、イソプロパノール等を使用することができる。また、モノアミン化合物としては、ブチルアミン、ジブチルアミン等を使用することができる。また、アルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン等を使用することができる。
本発明におけるポリアミノ化合物(E)は特に限定されないが、ポリウレア樹脂の製造に用いられている従来公知のポリアミノ化合物を用いることができる。ポリアミノ化合物(E)の具体例としては、エチレンジアミン、1,6-ヘキサメチレンジアミン、ピペラジン、2,5-ジメチルピペラジン、イソホロンジアミン、4,4’-ジシクロヘキシルメタンジアミン、3,3’-ジメチル-4,4’-ジシクロヘキシルメタンジアミン、1,2-シクロヘキサンジアミン、1,4-シクロヘキサンジアミン、1,2-プロパンジアミン等のジアミン類;アミノエチルエタノールアミン、アミノプロピルエタノールアミン、アミノヘキシルエタノールアミン、アミノエチルプロパノールアミン、アミノプロピルプロパノールアミン、アミノヘキシルプロパノールアミン等のアミノアルキルアルカノールアミン類等の化合物が挙げられる。
本発明におけるポリウレタンポリウレア樹脂(F)の重量平均分子量は、通常、50000~100000である。
本発明におけるエポキシ樹脂は特に限定されないが、一分子に2個以上のエポキシ基を有する公知のエポキシ樹脂を用いることができる。このようなエポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂などのビスフェノール型エポキシ樹脂、スピロ環型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テルペン型エポキシ樹脂、トリス(グリシジルオキシフェニル)メタン、テトラキス(グリシジルオキシフェニル)エタンなどのグリシジルエーテル型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタンなどのグリシジルアミン型エポキシ樹脂、テトラブロムビスフェノールA型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、α-ナフトールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂、ゴム変性エポキシ樹脂等を使用することができる。これらは単独で使用してもよく、2種以上を混合してもよい。
本発明の導電性接着フィルムは、導電性フィラー(H)を含有する。上記導電性フィラー(H)としては特に限定されず、例えば、金属フィラー、金属被覆樹脂フィラー、カーボンフィラー及びそれらの混合物を使用することができる。上記金属フィラーとしては、銅粉、銀粉、ニッケル粉、銀コ-ト銅粉、金コート銅粉、銀コートニッケル粉、金コートニッケル粉があり、これら金属粉は、電解法、アトマイズ法、還元法により作成することができる。
本発明の導電性接着剤組成物に含有されるウレタン樹脂粒子(I)は、4μm以上13μm以下の平均粒子径を有するものが使用され、5μm以上7μm以下であることが好ましい。
本発明の導電性接着フィルムは、必要に応じて硬化剤を含有してもよい。上記硬化剤としては特に限定されず、例えば、イソシアネート化合物、ブロックイソシアネート化合物、カルボジイミド化合物、オキサゾリン化合物、メラミン、金属錯体系架橋剤などの従来公知の硬化剤を用いることができる。
図1に示すように、本発明の導電性接着フィルム1は、剥離性基材2(離型フィルム)と、剥離性基材2の表面上に、上述の導電性接着剤組成物をコーティングすることにより形成された導電性接着剤層4とを備えている。なお、コーティング方法は特に限られず、ダイコート、リップコート、コンマコート等に代表される公知のコーティング機器を用いることができる。なお、離型性基材2に導電性接着剤組成物をコーティングする際の条件は、適宜設定すればよい。
本発明の導電性接着剤組成物は、使用目的に応じて、異方性導電性接着剤層や等方性導電性接着剤層として使用することができる。例えば、補強板と接着するための導電性接着フィルムとして本発明の導電性接着剤組成物を使用する場合には、等方性導電性接着剤層として使用することができる。
図2に示すように、本発明の導電性接着剤組成物を用いた電磁波シールドフィルム20は、導電性接着剤層4と、導電性接着剤層4の表面に設けられた保護層13とを有する。保護層13としては、絶縁性を有するもの(即ち、絶縁性樹脂組成物により形成されたもの)であれば特に限定されず、公知のものを使用することができる。また、保護層13として、上述した導電性接着剤層4に使用される樹脂成分(導電性フィラーを除いたもの)を使用してもよい。また、保護層13は、材質又は硬度若しくは弾性率等の物性が異なる2層以上の積層体であってもよい。
また、本発明の電磁波シールドフィルムは、金属層を有するものであってもよい。金属層を有することにより、より優れた電磁波シールド性能を得ることができる。
また、本発明の導電性接着剤組成物は、補強板を備えるシールドプリント配線板に使用できる。より具体的には、例えば、図4に示すシールドプリント配線板32に用いることができる。このシールドプリント配線板32は、プリント配線板47と、導電性接着剤層4と、導電性補強板15とを備えている。そして、プリント配線板47と導電性補強板15とが、本発明の導電性接着剤層4によって接着されるとともに、電気的に接続されている。
<導電性接着フィルムの作製>
表1に示す組成(質量%)を有する実施例1~6及び比較例1~5の導電性接着フィルムを、下記の製造方法により製造した。
表1に示す各材料を配合し、ペースト状の導電性接着剤組成物を作製した。なお、熱硬化性樹脂として、酸価12mgKOH/gのカルボキシル基変性ポリエステル樹脂(数平均分子量:15000、Tg:15℃)83質量部を使用し、エポキシ樹脂として、クレゾールノボラック型エポキシ樹脂(エポキシ当量:220g/eq、Tg:90℃)7質量部を使用した。また、ウレタン樹脂粒子として、平均粒子径7μm、硬度74のウレタンビーズを10質量部使用した。
カルボキシル基変性ポリアミド樹脂の酸価と配合量、エポキシ樹脂の配合量、及びウレタン樹脂粒子の硬度を表2に示すように変更したこと以外は、実施例7と同様にして、ペースト状の導電性接着剤組成物、及び導電性接着フィルムを作製した。
また、ウレタン樹脂粒子の代わりに平均粒子径4μmのシリカ粒子(富士シリシア化学(株)製、商品名:サイリシア350)を使用したこと以外は、実施例7と同様にして、ペースト状の導電性接着剤組成物、及び導電性接着フィルムを作製した。
カルボキシル基変性ポリエステル樹脂の酸価と配合量、及びエポキシ樹脂の配合量を表2に示すように変更するとともに、ウレタン樹脂を使用しなかったこと以外は、実施例7と同様にして、ペースト状の導電性接着剤組成物、及び導電性接着フィルムを作製した。
表3に示す各材料を配合し、ペースト状の導電性接着剤組成物を作製した。なお、熱硬化性樹脂として、酸価18mgKOH/gのカルボキシル基変性ポリアミド樹脂(数平均分子量:2000、Tg:30℃)71質量部使用し、エポキシ樹脂としてクレゾールノボラック型エポキシ樹脂(常温で液体、当量:180g/eq)/ビスフェノールA型エポキシ樹脂(常温で液体、当量:250g/eq)=90/10%の混合樹脂を10質量部使用した。また、ウレタン樹脂粒子として、平均粒子径が7μm、硬度が58のウレタンビーズを19質量部使用した。
ウレタン樹脂粒子の平均粒子径と硬度を表3に示すように変更したこと以外は、実施例14と同様にして、ペースト状の導電性接着剤組成物、及び導電性接着フィルムを作製した。
カルボキシル基変性ポリアミド樹脂の配合量、クレゾールノボラック型エポキシ樹脂/ビスフェノールA型エポキシ樹脂の混合樹脂の配合量を表3に示すように変更するとともに、ウレタン樹脂粒子を使用しなかったこと以外は、実施例14と同様にして、ペースト状の導電性接着剤組成物、及び導電性接着フィルムを作製した。
ウレタン樹脂粒子の代わりに平均粒子径4μmのシリカ粒子(富士シリシア化学(株)製、商品名:サイリシア350)を使用したこと以外は、実施例14と同様にして、ペースト状の導電性接着剤組成物、及び導電性接着フィルムを作製した。
次に、銅張積層板の銅箔の表面に形成された金めっきと導電性接着剤との密着性を、90°ピール試験により測定した。より具体的には、実施例1~16、比較例1~9において作製した導電性接着フィルムとSUS板製金属補強板(厚み:200μm)とを、プレス機を用いて温度:170℃、時間:3分、圧力:2MPaの条件で加熱加圧し、更に150℃で1時間加熱した後、セパレートフィルムを剥離して金属補強板付き導電性接着フィルムを作製した。
次に、実施例1~16、比較例1~9において作製した導電性接着フィルム(セパレートフィルム付き)と金属補強板(SUS板の表面をNiめっきしたもの、厚み:200μm)とを、プレス機を用いて温度:120℃、時間:5秒、圧力:0.5MPaの条件で加熱加圧し、金属補強板付き導電性接着フィルムを作製した。次に、導電性接着フィルム上のセパレートフィルムを剥離し、フレキシブル基板に上記熱圧着と同じ条件で金属補強板付き導電性接着フィルムを接着した後、さらにプレス機で温度:170℃、時間:30分、圧力:3MPaの条件で接着して、金属補強板付き回路基板を作製した。なお、フレキシブル基板としては、図5に示すように、ポリイミドフィルム29上に、表面の一部に金めっき層22が設けられた銅箔パターン23を形成し、その上にポリイミドフィルムからなるカバーレイ24が形成されたものを使用した。そして、このフレキシブル基板に、金属補強板26が設けられた導電性接着フィルム25を接着し、金属補強板付き回路基板を作製した。なお、カバーレイ24に、直径0.8mmのグランド接続部を模擬した開口部27を形成した。
次に、実施例1~16、比較例1~9において作製した金属補強板付き回路基板において、図6に示すように、金めっき層22が設けられた2本の銅箔パターン23間の電気抵抗値を抵抗計28で測定し、銅箔パターン23と金属補強板26との接続性を評価した。なお、接続抵抗が0.1Ω未満の場合を導電性に優れるものとして評価した。以上の結果を表4、表5に示す。
次に、作製した金属補強板付き銅箔積層フィルム(または金属補強板付き回路基板)の耐リフロー性の評価を行った。リフローの条件としては、鉛フリーハンダを想定し、金属補強板付き銅箔積層フィルム(または金属補強板付き回路基板)におけるポリイミドフィルムが265℃に5秒間曝されるような温度プロファイルを設定した。
2 剥離性基材
4 導電性接着剤層
13 保護層
14 金属層
15 導電性補強板
20 電磁波シールドフィルム
21 電磁波シールドフィルム
30 シールドプリント配線板
31 シールドプリント配線板
32 シールドプリント配線板
40 プリント配線板
41 ベース基板
42 プリント回路
43 絶縁性接着剤層
44 カバーレイ
45 開口部
46 めっき層
47 プリント配線板
Claims (6)
- エポキシ基と反応し得る官能基を有する熱硬化性樹脂と、エポキシ樹脂と、導電性フィラーとを含有する導電性接着剤組成物において、
平均粒子径が4μm以上13μm以下であるとともに、JIS K 6253に準拠して測定されたタイプAデュロメータ硬さが55以上90以下であるウレタン樹脂粒子を更に含有することを特徴とする導電性接着剤組成物。 - 前記導電性接着剤組成物の全量に対する前記ウレタン樹脂粒子の配合量が、3~30質量%であることを特徴とする請求項1に記載の導電性接着剤組成物。
- 前記熱硬化性樹脂が、カルボキシル基変性ポリエステル樹脂、カルボキシル基変性ポリアミド樹脂、及びカルボキシル基変性ポリウレタンポリウレア樹脂からなる群より選ばれる1種であることを特徴とする請求項1または請求項2に記載の導電性接着剤組成物。
- 剥離性基材と、該剥離性基材の表面に設けられ、請求項1~請求項3のいずれか1項に記載の導電性接着剤組成物からなる導電性接着剤層とを備えることを特徴とする導電性接着フィルム。
- 絶縁性を有する保護層と、該保護層の表面に設けられ、請求項1~請求項3のいずれか1項に記載の導電性接着剤組成物からなる導電性接着剤層とを備えることを特徴とする電磁波シールドフィルム。
- プリント回路が形成されたベース基板と、請求項1~請求項3のいずれか1項に記載の導電性接着剤組成物からなる導電性接着剤層と、導電性補強板とを備え、
前記ベース基板と前記導電性補強板とが、前記導電性接着剤層によって電気的に接続されていることを特徴とするプリント配線板。
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JPWO2017204218A1 (ja) | 2018-06-07 |
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US20190106607A1 (en) | 2019-04-11 |
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