WO2014003159A1 - 導電性接着剤組成物、導電性接着フィルム、接着方法及び回路基板 - Google Patents
導電性接着剤組成物、導電性接着フィルム、接着方法及び回路基板 Download PDFInfo
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- WO2014003159A1 WO2014003159A1 PCT/JP2013/067776 JP2013067776W WO2014003159A1 WO 2014003159 A1 WO2014003159 A1 WO 2014003159A1 JP 2013067776 W JP2013067776 W JP 2013067776W WO 2014003159 A1 WO2014003159 A1 WO 2014003159A1
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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
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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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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- 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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- 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
- H05K1/03—Use of materials for the substrate
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- 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
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
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- 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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Definitions
- the present invention relates to a conductive adhesive composition, a conductive adhesive film, an adhesion method, and a circuit board.
- a conductive adhesive composition or a conductive adhesive film obtained by molding the conductive adhesive composition is often used.
- a conductive adhesive contains a curable resin and a conductive filler.
- Patent Documents 1 to 3 describe a polyurethane polyurea resin and a curable polyurethane polyurea adhesive composition containing an epoxy group. In such an adhesive composition, it is necessary to further improve the above-described physical properties and at the same time sufficiently control the processing characteristics.
- the cured film has a high crosslinking density.
- a resin having a high crosslink density it is necessary to increase the number of reaction points. From such a viewpoint, it is necessary to use an epoxy compound having a large amount of functional groups.
- an epoxy resin having a large amount of functional groups generally has a low molecular weight, and therefore has a problem that it is easy to bleed out when used as a conductive adhesive film and is difficult to handle. That is, it is necessary to bond as shown in FIG. 2, but when bleeding out, the resin flows out of the bonded portion as shown in FIG.
- Cited Document 1 describes that two types of epoxy resins are used in combination. However, the selection of the resin here is not performed from the viewpoint as described above, but is for imparting flexibility by using a resin having a low softening point and a resin having a high softening point in combination. . Therefore, the examination from the viewpoint of increasing the crosslink density of the cured product as in the present invention has not been made, and is not intended to solve the above-described problems.
- an electromagnetic wave shielding ability can be imparted to the reinforcing plate by bonding the conductive reinforcing plate with a conductive adhesive and electrically connecting the ground layer and the reinforcing plate. It has been broken. An example of such a circuit board is shown in FIG. In such applications, the above-described improvements in various physical properties and workability are particularly required.
- JP 2010-143981 A International Publication No. 2007/032463 JP 2007-189091 A JP 2005-317946 A
- the present invention can increase the crosslink density and improve the physical properties of the adhesive layer after curing, and also has a conductive adhesive composition and conductive adhesive having excellent properties in processing performance.
- the object is to provide a film.
- the present invention provides a bisphenol type epoxy resin (A) having two or more epoxy groups per molecule and solid at room temperature, A novolac epoxy resin (B) having two or more epoxy groups per molecule and solid at room temperature,
- a conductive adhesive composition containing the resin (C) having a carboxyl group and the conductive filler (D) contains at least one selected from the group consisting of a carboxyl group-containing polyurethane resin (C-1) and a carboxyl group-containing polyacrylic resin (C-2). It is a conductive adhesive composition.
- the ratio of the bisphenol type epoxy resin (A) to the novolac type epoxy resin (B) is preferably 85:15 to 99: 1.
- the bisphenol type epoxy resin (A) preferably has an epoxy equivalent of 800 to 10,000.
- the novolac type epoxy resin (B) preferably has an epoxy equivalent of 90 to 300.
- 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.
- the conductive adhesive composition of the present invention does not contain a curing agent other than the bisphenol type epoxy resin (A), the novolac type epoxy resin (B), and the resin (C) having a carboxyl group. It is also an adhesive composition.
- this invention is also a conductive adhesive film which laminated
- the conductive adhesive composition preferably has a thickness of 15 to 100 ⁇ m.
- the present invention is also a conductive adhesive film characterized in that a peel strength when thermocompression bonding is performed after a week has elapsed after temporary bonding with a press machine is 10 N / cm or more.
- This invention has the electroconductive adhesive film obtained by the process (1) and the process (1) which temporarily adheres the electroconductive adhesive film mentioned above on the to-be-adhered base material (X) which is an electroconductive reinforcement board or a flexible substrate. It is also an adhesion method consisting of a step (2) in which a substrate to be adhered (X) is overlaid with a substrate to be adhered (Y) which is a flexible substrate or a conductive reinforcing plate and is hot-pressed.
- 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. It is preferable that the circuit board has a surface other than the reinforcing plate on the surface of the flexible substrate covered with an electromagnetic wave shielding film.
- the conductive adhesive composition of the present invention has excellent performance in heat resistance, physical strength, water resistance, moisture resistance, electrical properties, and at the same time, bleed-out of components in the film after the pressing process, etc. It has the property of not producing. Moreover, even when it is used for attaching a substrate having a step, suitable adhesion can be performed. Furthermore, even after storing for a long time after temporary bonding, good bonding performance can be maintained in the bonding step by hot pressing.
- the present invention is described in detail below.
- the conductive adhesive composition of the present invention has two or more epoxy groups per molecule, bisphenol type epoxy resin (A) that is solid at room temperature, and two or more epoxy groups per molecule, A novolak epoxy resin (B) that is solid at room temperature, a resin (C) having a carboxyl group and a conductive filler (D), and the resin (C) having a carboxyl group is a carboxyl group-containing polyurethane resin (C- 1) and at least one selected from the group consisting of carboxyl group-containing polyacrylic resins (C-2).
- Such an adhesive layer formed by the conductive adhesive composition of the present invention has a uniform crosslink density after curing and a high crosslink density.
- an adhesive layer having excellent properties in moisture resistance, water resistance, heat resistance, physical strength, electrical properties, and the like can be formed. Further, it has excellent processing characteristics without causing problems such as bleeding out during processing. Furthermore, even after storing for a long time after temporary bonding, good bonding performance can be maintained in the bonding step by hot pressing.
- the epoxy resin (A) used in the present invention is a bisphenol type epoxy resin that has two or more epoxy groups per molecule and 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. If the adhesive layer is made only of a novolac type epoxy resin, there is a problem in that the adhesion and film forming property are not sufficient, and therefore the bisphenol type epoxy resin (A) is essential. Moreover, in order to make workability favorable, it is necessary to use a solid thing at normal temperature.
- Such bisphenol type epoxy resin (A) is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin and the like. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use bisphenol A type epoxy resin or bisphenol F type epoxy resin from the viewpoint of high adhesion and heat resistance.
- the bisphenol type epoxy resin (A) one having an epoxy equivalent of 800 to 10,000 is preferably used. This 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.
- epoxy resins that can be used as the bisphenol type epoxy resin (A) 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) can be exemplified.
- the novolac type epoxy resin (B) is a novolac type epoxy resin having two or more epoxy groups per molecule and solid at room temperature. Although 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. Among these, it is preferable to use a phenol novolac type epoxy resin or a cresol novolac type epoxy resin from the viewpoint of high adhesion and heat resistance.
- the novolac type epoxy resin (B) 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.
- epoxy resins that can be used as the novolak type epoxy resin (B) as described above include EPICLONN-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-700-2, YDCN- 00-3, YDCN-700-5, YDCN-700-7
- the conductive adhesive layer of the conductive adhesive composition of the present invention contains the bisphenol type epoxy resin (A) and the novolac type epoxy resin (B) in a ratio of 85:15 to 99: 1 by weight. It is preferable. By setting it as the said ratio, the adhesive force to a reinforcement board is ensured and the heat resistance which can endure the reflow process at the time of component mounting can be provided. Further, if the ratio of the bisphenol type epoxy resin (A) is larger than 99: 1 in the above ratio, it is not preferable in that it may not be able to endure the reflow process at the time of component mounting, and it is not preferable than 85:15. An increase in the proportion of the type epoxy resin (B) is not preferable in terms of a decrease in adhesion to an adherend (Ni-SUS, SUS, gold-plated electrode, polyimide resin, etc.).
- epoxy equivalent in this specification is a value measured by potentiometric titration.
- the conductive adhesive composition of the present invention may further contain at least one selected from the group consisting of a carboxyl group-containing polyurethane resin (C-1) and a carboxyl group-containing polyacrylic resin (C-2). preferable. That is, since the curing is performed by a reaction between a carboxyl group and an epoxy group, preferable performance can be obtained in terms of improving heat resistance and improving adhesion to an adherend. Moreover, although a carboxyl group may have at the terminal of a chain
- the polyurethane resin (C-1) having a carboxyl group will be described below.
- the polyurethane resin (C-1) having a carboxyl group is a resin containing a carboxyl group in the molecule.
- the polyol compound (1) having a carboxyl group, the polyol (2), and a short-chain diol compound (if necessary) It is obtained by reacting 3), if necessary, a polyamine compound (4) and a polyisocyanate compound (5).
- a polyurethane resin (C-1) having a carboxyl group can be suitably obtained by using a polyol compound (1) having a carboxyl group.
- polyurethane means a general term for polyurethane and polyurethane-urea.
- the “polyurethane” may be a product obtained by reacting an amine component as necessary.
- active hydrogen-containing group in the present specification means a functional group having active hydrogen having reactivity with an isocyanate group. Specific examples of such “active hydrogen-containing group” include a hydroxyl group, a mercapto group, a carboxyl group, and an amino group.
- the polyol compound (1) containing a carboxyl group is a compound containing at least one carboxyl group and two or more hydroxyl groups.
- Specific examples include dimethylolalkanoic acids such as dimethylolpropanoic acid and dimethylolbutanoic acid; alkylene oxide low-mole adducts of dimethylolalkanoic acid (number average molecular weight of less than 500 by terminal functional group determination); dimethylolalkanoic acid ⁇ -caprolactone low molar adduct (number average molecular weight less than 500 by terminal functional group determination); half ester derived from dimethylolalkanoic acid anhydride and glycerin; hydroxyl group of dimethylolalkanoic acid and unsaturated bond And a compound obtained by subjecting a monomer having a free radical reaction to a monomer having a carboxyl group and an unsaturated bond.
- the content of the polyol compound (1) in the polyurethane resin (C-1) is such that the resulting polyurethane resin (C-1) is crosslinked with the epoxy to improve heat resistance and durability, as well as 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 an amount such that the acid value of the resulting polyurethane resin (C-1) is 3 to 100 mgKOH / 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 (C-1) it is also preferable to use a short-chain diol component (3) and a polyamine component (4) if necessary. This makes it easy to control the hardness and viscosity of the polyurethane resin.
- 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
- polyamine compound (4) examples include aliphatic diamine compounds such as methylene diamine, ethylene diamine, trimethylene diamine, hexamethylene diamine, and octamethylene diamine; phenylene diamine, 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 polyamine 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.
- Active hydrogen groups (however, (1) such as the polyol compound (1) having the carboxyl group, the polyol (2), the short-chain diol compound (3) as necessary, and the polyamine compound (4) as necessary.
- the equivalent ratio of the polyisocyanate compound (5) to the isocyanate group is preferably 0.5 to 1.5. By setting it within the above range, it is preferable in that a urethane having high heat resistance and high mechanical strength can be obtained.
- a blocking group in the terminal part 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.
- the polyurethane resin (C-1) 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.
- the reaction component (for example, prepolymer) is obtained by reacting a short-chain diol compound (3) used as needed, a reaction component comprising a polyamine compound (4) and, if necessary, a polyisocyanate (5).
- 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 polyamine 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 the isocyanate group (2) of the polyisocyanate compound (5) are preferably reacted at an equivalent ratio of 0.5 to 1.5.
- the polyurethane resin (C-1) obtained as described above has a weight average molecular weight (Mw) of 1,000 to 1,000,000, which indicates that the polyurethane has flexibility, adhesion, heat resistance, and coating. It is preferable because properties such as 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. .
- 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 (C-1) 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 acrylic resin (C-2) that can be used in the present invention is a resin containing a carboxyl group in the molecule and causes a crosslinking reaction with the epoxy resin.
- This acrylic resin (C-2) is obtained by polymerizing a polymerizable monomer (6) having a carboxyl group and another polymerizable monomer (7) by a usual polymerization method such as radical polymerization, cationic polymerization, and anionic polymerization. Can be obtained.
- Examples of the polymerizable monomer (6) having a carboxyl group include acrylic acid, methacrylic acid, and an acrylic ester having a carboxyl group, such as 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2 -Acryloyloxyethyl-phthalic acid, methacrylic acid ester having a carboxyl group, such as 2-methacryloyloxyethyl-succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl-phthalic acid, etc.
- acrylic acid and methacrylic acid are preferable from the viewpoint of reactivity and availability (hereinafter, “acryl” and “methacryl” are also referred to as “(meth) acryl”). ).
- (meth) acrylic acid monomers are preferred.
- Specific examples of such (meth) acrylic acid monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl (meth) acrylate
- the acrylic resin (C-2) has a higher cross-linking point and higher heat resistance as the acid value is higher.
- the conductive adhesive composition obtained by using an acrylic resin (C-2) having an acid value that is too high as a component is too hard to be reduced in flexibility, and the carboxyl group cannot be completely reacted with epoxy or the like. Tend to decrease. Therefore, the acid value of the acrylic resin (C-2) is preferably 3 to 100 mgKOH / g.
- the glass transition point (Tg) of the resulting acrylic resin (C-2) tends to decrease.
- an acrylic resin (C-2) having a low glass transition point (Tg) is used, a conductive adhesive composition excellent in flexibility and adhesion can be obtained.
- an ester of (meth) acrylic acid and a short chain alcohol, (meth) acrylic acid, styrene, or acrylonitrile is used as the polymerizable monomer, the glass transition point (Tg) of the resulting acrylic resin (C-2) is obtained. ) Tend to increase.
- a conductive adhesive composition having excellent heat resistance and durability can be obtained. That is, by selecting the type and ratio of the polymerization component so that the glass transition point (Tg) of the acrylic resin (C-2) is an appropriate value, flexibility, adhesion, heat resistance, and durability can be improved. Obtainable. Specifically, it is preferable to use two or more kinds of (meth) acrylic acid monomers as the double bond-containing component.
- the glass transition point (Tg) of the acrylic resin (C-2) is preferably ⁇ 20 to 30 ° C. When the glass transition point (Tg) of the acrylic resin (C-2) is more than 30 ° C., flexibility and adhesion tend to be lowered. On the other hand, when the glass transition point (Tg) of the acrylic resin (C-2) is less than ⁇ 20 ° C., heat resistance and durability tend to be lowered.
- the acrylic resin (C-2) is a conventional polymerization monomer (6) having a carboxyl group and another polymerizable monomer (7) such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization. It can be obtained by polymerizing by a known polymerization method. For example, in solution polymerization, a polymerization component may be polymerized in an appropriate solvent in the presence of a polymerization initiator.
- the kind of solvent used in the solution polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction.
- the solvent include water; methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethylene Alcohol solvents such as glycol, propylene glycol and diethylene glycol; aliphatic hydrocarbon solvents such as petroleum ether, hexane and heptane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; diethyl ether, dibutyl ether and tetrahydrofuran Ether solvents such as (THF) and dioxane; methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-h
- the amount of solvent used is appropriately determined depending on the conditions of the polymerization reaction. Usually, the mass ratio is about 0.1 to 100 times, preferably about 0.2 to 20 times the polymerization component. In addition, these solvents can be used individually by 1 type or in combination of 2 or more types.
- polymerization initiators can be used.
- specific examples of the polymerization initiator include peroxides such as benzoyl peroxide, dibutyl peroxide and cumene hydroperoxide; azo-based polymerization such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). Mention may be made of initiators. These polymerization initiators can be used singly or in combination of two or more.
- the amount of the polymerization initiator used is not particularly limited, but is usually about 0.1 to 10% by mass with respect to the polymerization component.
- the temperature of the polymerization reaction is appropriately set depending on the reaction conditions. Usually, the temperature may be from room temperature (25 ° C.) to the boiling point of the solvent used.
- a chain transfer agent such as mercaptans or a polymerization inhibitor such as hydroquinone may be added to the polymerization reaction system.
- the acrylic resin (C-2) thus obtained has a weight average molecular weight (Mw) of 1 in order to satisfy various performances such as adhesion, heat resistance, durability, compatibility, and coating performance. It is preferably from 1,000 to 1,500,000, and more preferably from 5,000 to 1,000,000.
- the mixing ratio of the mixture of the bisphenol type epoxy resin (A) and the novolac type epoxy resin (B) to the polyurethane resin (C-1) and the acrylic resin (C-2) is 70: 30-30. : 70 is preferable. By setting it within the above-mentioned range, it is preferable in terms of facilitating imparting film formability and adjusting heat resistance.
- the conductive adhesive composition of the present invention it is preferable not to add components involved in the curing reaction other than the above-described (A), (B) and (C). That is, it is preferable not to contain an epoxy curing agent that is usually used in combination with an epoxy compound.
- the conductive adhesive composition of the present invention can be particularly suitably used for adhesion between a substrate and a conductive reinforcing material in a flexible wiring board. When used for such applications, it is preferable not to contain the epoxy curing agent described above.
- blend in this invention is used in order to accelerate
- curing agents include isocyanate compounds, hydroxyl group-containing compounds, carbodiimide compounds, oxazoline compounds, silanol compounds, aziridine compounds, acid anhydride compounds, tertiary amine compounds, phosphine compounds, imidazole compounds, It is not limited to this.
- the curing agent may be added as long as the peel strength after the bonding step by the hot press, which is a feature of the present invention, satisfies the condition of 10 N / cm or more.
- blending amounts include a range of 0.1% by weight or less with respect to the total amount of the components (A) to (C).
- the conductive adhesive composition of the present invention 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. Can be created by law.
- the average particle diameter of the conductive filler is preferably 3 to 50 ⁇ m.
- 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 (D) 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 (D) is preferably contained in a proportion of 40 to 90% by weight with respect to the total amount of the conductive adhesive composition.
- the conductive adhesive composition includes a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, an antifoaming agent, and a leveling as long as the solder reflow resistance is not deteriorated.
- Conditioners, fillers, flame retardants, etc. may be added.
- the conductive adhesive composition of the present invention is obtained by reacting the above-described components to obtain a conductive adhesive composition, which is then applied onto a substrate to form a coating film, thereby forming a conductive adhesive. It is used as an agent.
- a conductive adhesive composition is applied onto a substrate to form a coating film, the conductive adhesive composition is dissolved or dispersed in a solvent.
- the manufacturing method etc. which use for a drying process and form a coating film according to it can be employ
- the conductive adhesive film of the present invention can be produced by coating a release film with a conductive adhesive.
- the coating method is not particularly limited, and a known device such as a coating device represented by die coating, lip coating, or comma coating can be used.
- the drying conditions in this case may be set to optimum conditions from the viewpoint of productivity.
- the release 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 release film is not specifically limited, It determines suitably considering the ease of use.
- the thickness of the conductive adhesive layer formed on the release film is preferably 15 to 100 ⁇ m. If it is thinner than 15 ⁇ m, the embedding property becomes insufficient, and if it is thicker than 100 ⁇ m, it is disadvantageous in cost and cannot meet the demand for thinning. 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 is not particularly limited in its application, but is used, for example, to bond a reinforcing plate to a circuit board.
- the reinforcing plate is conductive, it is used not only for bonding the metal reinforcing plate but also for electrically connecting the ground electrode in the circuit board body and the metal reinforcing plate. .
- the material of the circuit board main 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 electronic components 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.
- chip components such as a resistor and a capacitor
- the conductive adhesive film described above can be suitably used particularly for bonding the flexible substrate and the reinforcing plate in the flexible circuit substrate. That is, as described in the cited document 4, a conductive metal plate or the like is used as a reinforcing plate, and this is adhered to a flexible circuit board with a conductive adhesive composition, whereby an electromagnetic wave generated by the reinforcing plate. Obtaining shielding ability 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, since the curing reaction proceeds slowly when stored for a certain period after temporary bonding, the bonding performance does not deteriorate when performing main bonding by hot pressing.
- a conductive adhesive film is temporarily bonded onto the adherend substrate (X).
- the adherend substrate (X) may be either a reinforcing plate, a flexible substrate or a reinforcing plate, but is preferably a reinforcing plate.
- Temporary bonding is not particularly limited in terms of conditions, and it is sufficient that the conductive adhesive film is fixed on the substrate to be bonded and 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.
- Temporary bonding can be performed with a press, and examples of bonding conditions include temperature: 120 ° C., time: 5 seconds, and pressure: 0.5 MPa.
- 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).
- the above may be stored.
- the conductive adhesive composition of the present invention is preferable in this respect because the adhesive performance does not deteriorate even after partially cured.
- the release film on the conductive adhesive film is peeled off from the adherend base material (X) having the conductive adhesive film obtained in the step (1), and the adhesive base is a flexible substrate or a reinforcing plate.
- This is a process of stacking materials (Y) and hot pressing. Note that 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 composition, 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. 4, the circuit board and the reinforcing plate are bonded by the conductive adhesive composition 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 electromagnetic wave shielding film may cover only a part of the surface other than the reinforcing plate, or may cover the entire surface other than the reinforcing plate. In this case, the electromagnetic wave shielding film may overlap with at least a part of the reinforcing plate. This is preferable in that good electromagnetic shielding performance can be obtained over the entire circuit board.
- the electromagnetic wave shielding film is not particularly limited, but those having an insulating layer / isotropic conductive adhesive layer or those having an insulating layer / metal layer / anisotropic conductive adhesive layer are preferred.
- a mixture of 5 g of methyl methacrylate, 65 g of 2-ethylhexyl methacrylate, 25 g of n-lauryl methacrylate, 5 g of methacrylic acid, and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was prepared. 1/3 of the mixture was added into the reaction vessel, and the rest was dropped into the reaction vessel with a dropping funnel over 1 hour.
- Example film sample manufacturing method The manufacturing method of the electroconductive adhesive film of each Example, each reference example, and each comparative example is demonstrated.
- Each material is blended to create a predetermined paste. This was hand-coated using a doctor blade (plate-like spatula) on a polyethylene terephthalate film subjected to a mold release treatment, and dried at 100 ° C. for 3 minutes to produce a conductive adhesive film.
- each conductive adhesive film was prepared so that the thickness of the conductive adhesive film was a predetermined thickness. The thickness of the conductive adhesive film is measured with a micrometer.
- Conductive filler D-1 Silver powder (average particle size 12 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
- Conductive filler D-2 Silver-coated copper powder (average particle size 20 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
- Conductive filler D-3 Silver-coated copper powder (average particle size 25 ⁇ m, manufactured by Fukuda Metal Foil Powder Co., Ltd.)
- thermocompression bonding is further performed with a press (temperature: 170 ° C., time: 30 minutes, pressure: 3 MPa).
- the adhesion with the reinforcing plate was measured using a 90 ° peel test. Specifically, as shown in FIG. 1, the surface side of a polyimide layer in a copper clad laminate having a stainless steel plate (width 10 mm, length 100 mm), a polyimide layer and a thin film copper layer, and the conductivity of this example. After the press bonding as described in the method of using the conductive adhesive film of the above-described embodiment through the adhesive adhesive film, 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 carried out on the circuit board with metal reinforcing plate prepared by the above method. Connection resistance of the circuit board with the metal reinforcing plate when the conductive adhesive film is pressed between the reinforcing plate and the flexible printed circuit board simulating the ground having a diameter of 1.0 mm in the connection portion (electrode in FIG. 2) Between). In addition, if it is 1 ⁇ or less, shielding performance is secured.
- the resin flow distance was measured about the circuit board with a metal reinforcement board produced by said method.
- the distance between the conductive adhesive end protruding from the bottom of the reinforcing plate and the reinforcing plate end was measured. If it is 300 micrometers or less, it can be used without a problem.
- the conductive adhesive composition of the present invention has good physical properties and electrical properties. Furthermore, it has good adhesion performance even after being stored for a long time after temporary adhesion. Furthermore, good adhesion performance and electrical conductivity can be obtained even when bonded onto a substrate having a step.
- the conductive adhesive composition of the present invention can be used particularly preferably in applications where a metal reinforcing plate is bonded to a flexible substrate.
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Abstract
Description
このような回路基板の一例を図4に示す。このような用途においては、上述した各種物性の向上、加工性の向上が特に要求されるものである。
1分子あたり2個以上のエポキシ基を有し、常温で固体であるノボラック型エポキシ樹脂(B)、
カルボキシル基を有する樹脂(C)及び
導電性フィラー(D)を含有する導電性接着剤組成物において、
カルボキシル基を有する樹脂(C)が、カルボキシル基含有ポリウレタン樹脂(C-1)及びカルボキシル基含有ポリアクリル樹脂(C-2)からなる群から選択される少なくとも1つを含有することを特徴とする導電性接着剤組成物である。
上記ビスフェノール型エポキシ樹脂(A)は、エポキシ当量が800~10000であることが好ましい。
上記ノボラック型エポキシ樹脂(B)は、エポキシ当量が90~300であることが好ましい。
導電性フィラー(D)は、平均粒子径が3~50μmであることが好ましい。
また、本発明の導電性接着剤組成物は、ビスフェノール型エポキシ樹脂(A)及びノボラック型エポキシ樹脂(B)並びにカルボキシル基を有する樹脂(C)以外の硬化剤を含有しないことを特徴とする導電性接着性剤組成物でもある。
この場合において、上記導電性接着剤組成物は厚みが15~100μmであることが好ましい。
上記回路基板は、フレキシブル基板表面における補強板以外の面が、電磁波シールドフィルムによって被覆されたものであることが好ましい。
本発明の導電性接着剤組成物は、1分子あたり2個以上のエポキシ基を有し、常温で固体であるビスフェノール型エポキシ樹脂(A)、1分子あたり2個以上のエポキシ基を有し、常温で固体であるノボラック型エポキシ樹脂(B)、カルボキシル基を有する樹脂(C)及び導電性フィラー(D)を含有し、カルボキシル基を有する樹脂(C)が、カルボキシル基含有ポリウレタン樹脂(C-1)及びカルボキシル基含有ポリアクリル樹脂(C-2)からなる群から選択される少なくとも1つを含有することを特徴とするものである。このような本発明の導電性接着剤組成物によって形成される接着層は、硬化後の架橋密度が均一であり、なおかつ、高い架橋密度が得られるものである。これによって、耐湿性、耐水性、耐熱性、物理的強度、電気的性質等において優れた性質を有する接着層を形成することができる。また、加工時にブリードアウト等の問題を生じることもなく、優れた加工特性を有するものである。更に、仮接着後長期間保管した後にも熱プレスによる接着工程において良好な接着性能を保持することができる。
本発明において使用するエポキシ樹脂(A)は、1分子あたり2個以上のエポキシ基を有し、常温で固体であるビスフェノール型エポキシ樹脂である。常温で固体であるとは、25℃において無溶媒状態で流動性を有さない固体状態であることを意味する。上記接着層をノボラック型エポキシ樹脂のみからなるものとすると、密着性や成膜性が充分ではないという点で問題があるため、ビスフェノール型エポキシ樹脂(A)を必須とするものである。また、加工性良好なものとするため、常温で固形のものを使用することが必要となる。
上記ノボラック型エポキシ樹脂としては特に限定されず、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を挙げることができる。これらのうち高接着性、耐熱性の点から、フェノールノボラック型エポキシ樹脂またはクレゾールノボラック型エポキシ樹脂を用いることが好ましい。
本発明の導電性接着剤組成物は、更に、カルボキシル基含有ポリウレタン樹脂(C-1)及びカルボキシル基含有ポリアクリル樹脂(C-2)からなる群から選択される少なくとも1つを含有することが好ましい。
すなわち、カルボキシル基とエポキシ基との反応によって硬化を行うものであることから、耐熱性の向上、被着体との密着力向上という点で好ましい性能が得られるものである。
また、カルボキシル基は鎖の末端に有するものであっても、側鎖として有するものであってもよいが、側鎖として有するものであることが好ましい。
上記カルボキシル基を有するポリウレタン樹脂(C-1)について、以下説明する。
カルボキシル基を有するポリウレタン樹脂(C-1)は、分子内にカルボキシル基を含有する樹脂であり、カルボキシル基を有するポリオール化合物(1)と、ポリオール(2)と必要に応じて短鎖ジオール化合物(3)と、必要に応じてポリアミン化合物(4)と、ポリイソシアネート化合物(5)とを反応させて得られる。このような反応に際して、ポリオール化合物(1)としてカルボキシル基を有するものを使用することで、カルボキシル基を有するポリウレタン樹脂(C-1)を好適に得ることができる。
ポリカーボネートポリオールの具体例としては、ポリテトラメチレンカーボネートジオール、ポリペンタメチレンカーボネートジオール、ポリネオペンチルカーボネートジオール、ポリヘキサメチレンカーボネートジオール、ポリ(1,4-シクロヘキサンジメチレンカーボネート)ジオール、及びこれらのランダム/ブロック共重合体などを挙げることができる。
ポリウレタン樹脂(C-1)は、従来公知のポリウレタンの製造方法により製造することができる。具体的には、先ず、分子内に活性水素を含まない有機溶剤の存在下又は不存在下、カルボキシル基を含有するポリオール化合物(1)と、ポリオール(2)と、鎖伸長剤として必要に応じて用いられる短鎖ジオール化合物(3)と、必要に応じてポリアミン化合物(4)と、ポリイソシアネート(5)とからなる反応成分を反応させて反応物(例えばプレポリマー)を得る。反応成分は、一般的には末端イソシアネート基を有するプレポリマーが形成される配合組成とすればよい。また、ワンショット法又は多段法により、通常20~150℃、好ましくは60~110℃で、理論イソシアネート%となるまで反応させればよい。
本発明において使用することができるアクリル系樹脂(C-2)は、分子内にカルボキシル基を含有する樹脂であり、エポキシ樹脂と架橋反応を生じる。このアクリル系樹脂(C-2)は、カルボキシル基を有する重合性モノマー(6)と、その他重合性モノマー(7)とを、ラジカル重合、カチオン重合、及びアニオン重合などの通常の重合法で重合させて得られる。
アクリル系樹脂(C-2)は、カルボキシル基を有する重合性モノマー(6)と、その他重合性モノマー(7)とを、例えば、乳化重合、懸濁重合、溶液重合、又は塊状重合などの従来公知の重合方法によって重合することで得ることができる。例えば、溶液重合においては、重合開始剤の存在下、適当な溶剤中で重合成分を重合させればよい。
溶剤の使用量は、重合反応の条件によって適宜決定される。通常、重合成分に対して質量比で0.1~100倍程度、好ましくは0.2~20倍程度である。なお、これらの溶剤は、一種単独で又は二種以上を組み合わせて用いることができる。
本発明において、ビスフェノール型エポキシ樹脂(A)及びノボラック型エポキシ樹脂(B)の混合物と、ポリウレタン樹脂(C-1)及びアクリル系樹脂(C-2)との混合比は、70:30~30:70であることが好ましい。上記範囲内のものとすることで、成膜性の付与、耐熱性の調整が容易になるという点で好ましい。
本発明の導電性接着剤組成物は、上述した(A)、(B)及び(C)以外には、硬化反応に関与する成分を添加しないことが好ましい。すなわち、通常、エポキシ化合物と併用して使用されるエポキシ硬化剤は含有しないものとすることが好ましい。
本発明の導電性接着剤組成物は、導電性フィラー(D)を含有する。上記導電性フィラー(D)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。
また、特にフィラー同士の接触を得やすくするために、導電性フィラーの平均粒子径が3~50μmとすることが好ましい。また、導電性フィラーの形状としては、球状、フレーク状、樹枝状、繊維状などが挙げられる。
上記導電性フィラー(D)は、接続抵抗、コストの観点から、銀粉、銀コート銅粉、銅粉からなる群より選択される少なくとも1であることが好ましい。
上記導電性フィラー(D)は、導電性接着剤組成物の全量に対して40~90重量%の割合で含まれることが好ましい。
本発明の導電性接着剤組成物は、上述した各成分を反応させて導電性接着剤組成物を得た後、これを基材上に塗布して塗膜を形成することで、導電性接着剤として使用するものである。導電性接着剤組成物を基材上に塗布して塗膜を形成する際には、導電性接着剤組成物を溶媒中に溶解又は分散させた、これを基材上に塗布し、必要に応じて乾燥工程に供して塗膜を形成する製造方法等を採用することができる。
本発明の導電性接着フィルムは、離型フィルムに導電性接着剤をコーティングすることにより作製することができる。なお、コーティング方法は特に限られないが、ダイコート、リップコート、コンマコートに代表されるコーティング機器等の公知の機器を用いることができる。また、離型フィルムに導電性接着剤をコーティングした後、必要に応じて乾燥工程に供しても良い。この場合の乾燥条件は、生産性の観点で最適な条件を設定すれば良い。
次に、本発明の導電性接着フィルムの使用方法について説明する。この導電性接着フィルムは、その用途を特に限定するものではないが、例えば、回路基板に補強板を接着するのに使用される。特に、補強板が導電性のものであるとき、この金属製補強板を接着させるだけでなく、回路基板本体におけるグランド電極と、この金属製補強板とを電気的に導通させる目的で使用される。
なお、ここでいう電子部品としては、コネクタやICの他、抵抗器、コンデンサー等のチップ部品などを挙げることができる。
本発明の回路基板は、フレキシブル基板、導電性接着剤組成物及び導電性補強板をこの順に積層した部位を少なくとも一部に有する回路基板である。このような回路基板は、上述した接着方法によって接着されたものであってもよいし、その他の接着方法によって得られたものであってもよい。なお、このような回路基板の模式図を図4に示す。図4においては、回路基板と補強板が本発明の導電性接着剤組成物によって接着され、電気的にも接続されている。
[合成例c1:カルボキシル基含有ポリウレタン(ウレタンウレア)]
攪拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、ジメチロールプロピオン酸(DMPA)6.0g、ポリヘキサメチレンカーボネートジオール(商品名「プラクセルCD220」、ダイセル株式会社製、末端官能基定量による数平均分子量2000)100g、及びジメチルホルムアミド(DMF)59.0gを仕込んだ。次いで、ヘキサメチレンジイソシアネート(HDI)31.9g(OH基に対してNCO基が2倍当量)を加え、樹脂のNCO基が理論値の4.0%となるまで90℃で反応を行ってウレタンプレポリマー溶液を得た。得られたウレタンプレポリマー溶液に、DMF298.5gを添加し、40℃に冷却した後、イソホロンジアミン(IPDA)16.1gを滴下して、ウレタンプレポリマーのNCO基と反応させた。赤外吸収スペクトル分析で測定される、遊離イソシアネート基による2,270cm-1の吸収が消失するまで攪拌して、酸価が16.4mgKOH/g、数平均分子量(Mn)が50,000、重量平均分子量(Mw)が105,000のポリウレタン樹脂(c1)のDMF溶液(固形分濃度30%)を得た。
攪拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、DMPA6.0g、1,4-ブタンジオール6.0g、プラクセルCD220 100g、及びDMF139.1gを仕込んだ。次いで、HDI27.1g(OH基に対してNCO基が当量)を加え、赤外吸収スペクトル分析で測定される、遊離イソシアネート基による2,270cm-1の吸収が消失するまで90℃で攪拌した後、DMF185.5gを添加し、酸価が18.1mgKOH/g、数平均分子量(Mn)が52,000、重量平均分子量(Mw)が112,000のポリウレタン樹脂(c2)のDMF溶液(固形分濃度30%)を得た。ポリウレタン樹脂(c2)が、ウレア結合を有しないことを赤外吸収スペクトルにて確認した。
攪拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、DMPA6.0g、プラクセルCD220 100g、DMF70.8gを仕込んだ。次いで、イソホロンジイソシアネート(IPDI)42.1g(OH基に対してNCO基が2倍当量)を加え、樹脂のNCO基が理論値の3.6%となるまで90℃で反応を行ってウレタンプレポリマー溶液を得た。得られたウレタンプレポリマー溶液に、DMF312.3gを添加し、40℃に冷却した後、IPDA16.1gを滴下して、ウレタンプレポリマーのNCO基と反応させた。赤外吸収スペクトル分析で測定される、遊離イソシアネート基による2,270cm-1の吸収が消失するまで攪拌して、酸価が15.3mgKOH/g、数平均分子量(Mn)が50,000、重量平均分子量(Mw)が102,000のポリウレタン樹脂(c3)のDMF溶液(固形分濃度30%)を得た。
攪拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、1,4-ブタンジオール4.0g、CD220 100g、及びDMF58.2gを仕込んだ。次いで、HDI31.7g(OH基に対してNCO基が2倍当量)を加え、樹脂のNCO基が理論値の4.1%となるまで90℃で反応を行ってウレタンプレポリマー溶液を得た。得られたウレタンプレポリマー溶液に、DMF295.8gを添加し、40℃に冷却した後、IPDA16.0gを滴下して、ウレタンプレポリマーのNCO基と反応させた。赤外吸収スペクトル分析で測定される、遊離イソシアネート基による2,270cm-1の吸収が消失するまで攪拌して、カルボキシル基を含有しない、数平均分子量(Mn)が52,000、重量平均分子量(Mw)が109,000のポリウレタン樹脂(c4)のDMF溶液(固形分濃度30%)を得た。
[合成例c5:カルボキシル基含有アクリル系樹脂]
攪拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン(MEK)100gを仕込み、窒素雰囲気下で80℃に加熱した。メタクリル酸メチル5g、メタクリル酸2-エチルヘキシル65g、メタクリル酸n-ラウリル25g、メタクリル酸5g、及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)2gの混合物を用意した。混合物の1/3を反応容器内に添加し、残りを滴下ロートで1時間かけて反応容器内に滴下した。滴下後、そのままの状態で6時間反応させて、酸価が32.5mgKOH/g、重量平均分子量(Mw)が29,000、数平均分子量(Mn)が10,000、及びTgの計算値が-18.5℃のアクリル系樹脂(c5)の溶液(固形分濃度50%)を得た。
攪拌機、還流冷却管、温度計、窒素吹き込み管、及びマンホールを備えた反応容器を用意した。反応容器の内部を窒素ガスで置換した後、メチルエチルケトン(MEK)100gを仕込み、窒素雰囲気下で80℃に加熱した。メタクリル酸メチル10g、メタクリル酸2-エチルヘキシル65g、メタクリル酸n-ラウリル25g、及び2,2’-アゾビス(2,4-ジメチルバレロニトリル)2gの混合物を用意した。混合物の1/3を反応容器内に添加し、残りを滴下ロートで1時間かけて反応容器内に滴下した。滴下後、そのままの状態で6時間反応させて、重量平均分子量(Mw)が35,000、数平均分子量(Mn)が14,000、及びTgの計算値が-19.1℃のアクリル系樹脂(c6)の溶液(固形分濃度50%)を得た。
各実施例、各参考例及び各比較例の導電性接着フィルムの製造方法について説明する。各材料を配合し、所定のペーストを作成する。これを、離型処理されたポリエチレンテレフタレートフィルム上に、ドクターブレイド(板状のヘラ)を用いてハンドコートし、100℃×3分の乾燥を行って導電性接着フィルムを作製した。なお、ドクターブレイドは、作製する導電性接着フィルムの厚みにより、1mil~5mil品を適切に選択する。なお、1mil=1/1000インチ=25.4μmである。なお、各実施例、各参考例及び各比較例においては、導電性接着フィルムの厚みが所定の厚みとなるように各導電性接着フィルムを作製した。なお、導電性接着フィルムの厚みは、マイクロメータによって測定したものである。
また、硬化剤は、3級アミン化合物(三菱化学製、商品名jER3010)を使用した。
導電性フィラーD-1:銀粉(平均粒径12μm、福田金属箔粉工業株式会社製)
導電性フィラーD-2:銀コート銅粉(平均粒径20μm、福田金属箔粉工業株式会社製)
導電性フィラーD-3:銀コート銅粉(平均粒径25μm、福田金属箔粉工業株式会社製)
プレス機(温度:120℃、時間:5秒、圧力:0.5MPa)で補強板と導電性接着フィルムを熱圧着で仮接着し、導電性接着フィルム上のセパレーターフィルムを剥離し、フレキシブル基板に上記仮接着方法で仮接着後、さらにプレス機(温度:170℃、時間:30分、圧力:3MPa)で熱圧着する。
評価に当たっては、上述した仮接着後1時間以内に熱圧着を行った場合と、仮接着後に一週間保管した後に熱圧着を行った場合について、ピール強度、接続抵抗値、耐リフロー性、レジンフロー、信頼性試験に関して以下の方法で評価を行った。ここで、長期間保管することを想定して、23℃、60%RHに調温調湿した室内に一週間保管した。
補強板との密着力を、90°ピール試験を用いて測定した。具体的には図1に示すように、ステンレス板(幅10mm、長さ100mm)と、ポリイミド層と薄膜状の銅層とを有する銅張積層板におけるポリイミド層の表面側と本実施例の導電性接着フィルムを介して、上記実施形態の導電性接着フィルムの使用方法で説明したようにプレス接合した後、銅張積層板を垂直方向に引っ張り剥した。10N/cm以上であれば問題なく使用できる。
上記の方法で作成した金属補強板付き回路基板について電気的評価を実施した。接続部の開口径が直径1.0mmのグランドを模擬したフレキシブルプリント基板に、導電性接着フィルムを補強板との間でプレス加工した際の金属補強板付き回路基板の接続抵抗(図2の電極間)を測定した。なお、1Ω以下であればシールド性能が確保される。
リフロー後の評価を行った。なお、リフローの温度条件としては、鉛フリーハンダを想定し、最高265℃の温度プロファイルを設定した。導電性接着フィルムを補強板との間でプレス加工した金属補強板付き回路基板の試験片を、IRリフローに5回通過させ、膨れの有無を観察した。
上記の方法で作成した金属補強板付き回路基板についてレジンフロー距離を測定した。作成した金属補強板付き回路基板を、補強板側から観察した際、補強板下からはみ出た導電性接着剤端と補強板端との距離を測定した。300μm以下であれば問題なく使用できる。
上記の方法で作成したピール試験用試験片と、接続抵抗測定用試験片とを高温高湿度環境下(85℃、85%)に1000時間放置した後、それぞれのピール強度と接続抵抗を測定した。
2.電極(Ni-Au無電解めっき処理)
3.レジンフロー
4.GND(Ni-Au無電解めっき処理)
5.導電性接着剤
6.カバーレイフィルム
7.銅箔層
8.銅張積層板
9.接続抵抗測定箇所
Claims (13)
- 1分子あたり2個以上のエポキシ基を有し、常温で固体であるビスフェノール型エポキシ樹脂(A)、
1分子あたり2個以上のエポキシ基を有し、常温で固体であるノボラック型エポキシ樹脂(B)、
カルボキシル基を有する樹脂(C)及び
導電性フィラー(D)を含有する導電性接着剤組成物において、
カルボキシル基を有する樹脂(C)が、カルボキシル基含有ポリウレタン樹脂(C-1)及びカルボキシル基含有ポリアクリル樹脂(C-2)からなる群から選択される少なくとも1つを含有することを特徴とする導電性接着剤組成物。 - ビスフェノール型エポキシ樹脂(A)とノボラック型エポキシ樹脂(B)との比率は、重量比85:15~99:1である請求項1記載の導電性接着剤組成物。
- ビスフェノール型エポキシ樹脂(A)は、エポキシ当量が800~10000である請求項1又は2に記載の導電性接着剤組成物。
- ノボラック型エポキシ樹脂(B)は、エポキシ当量が90~300である請求項1~3のいずれか1項に記載の導電性接着剤組成物。
- 導電性フィラー(D)は、銀粉、銀コート銅粉、銅粉からなる群より選択される少なくとも1つである請求項1~4のいずれか1項に記載の導電性接着剤組成物。
- 導電性フィラー(D)は、平均粒子径が3~50μmである請求項1~5のいずれか1項に記載の導電性接着剤組成物。
- ビスフェノール型エポキシ樹脂(A)及びノボラック型エポキシ樹脂(B)並びにカルボキシル基を有する樹脂(C)以外の硬化剤を含有しないことを特徴とする請求項1~6のいずれか1項に記載の導電性接着剤組成物。
- 請求項1~7のいずれか1項に記載の導電性接着剤組成物を用いた導電性接着剤層と、保護層を積層した導電性接着フィルム。
- 導電性接着剤層の厚みが15~100μmである請求項8に記載の導電性接着フィルム。
- プレス機で仮接着してから1週間経過後に熱圧着したときのピール強度が10N/cm以上であることを特徴とする請求項8または9に記載の導電性接着フィルム。
- 請求項8~10のいずれか1記載の導電性接着フィルムを導電性補強板又はフレキシブル基板である被接着基材(X)上に仮接着する工程(1)及び
工程(1)によって得られた導電性接着フィルムを有する被接着基材(X)にフレキシブル基板又は導電性補強板である被接着基材(Y)を重ね、熱プレスする工程(2)からなる接着方法。 - フレキシブル基板、導電性接着剤層及び導電性補強板をこの順に積層した部位を少なくとも一部に有する回路基板であって、導電性接着剤層は、請求項8~10のいずれか1項に記載の導電性接着フィルムによって形成されたものであることを特徴とする回路基板。
- フレキシブル基板表面における補強板以外の面が、電磁波シールドフィルムによって被覆されたものである請求項12記載の回路基板。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000017246A (ja) * | 1998-07-06 | 2000-01-18 | Lintec Corp | 粘接着剤組成物および粘接着シート |
JP2000086981A (ja) * | 1998-09-17 | 2000-03-28 | Nitto Denko Corp | シート状接着剤組成物およびその製法 |
JP2000129216A (ja) * | 1998-10-26 | 2000-05-09 | Nitto Denko Corp | シート状接着剤組成物およびそれを用いた電子部品装置ならびにそのリペアー方法 |
JP2000129217A (ja) * | 1998-10-26 | 2000-05-09 | Nitto Denko Corp | シート状接着剤組成物およびそれを用いた電子部品装置ならびにそのリペアー方法 |
JP2000345010A (ja) * | 1999-04-01 | 2000-12-12 | Mitsui Chemicals Inc | 異方導電性ペースト |
JP2001332124A (ja) * | 2000-05-22 | 2001-11-30 | Toshiba Chem Corp | 導電性ペーストおよび光半導体装置 |
JP2003082318A (ja) * | 2001-09-13 | 2003-03-19 | Three M Innovative Properties Co | カチオン重合性接着剤組成物及び異方導電性接着剤組成物 |
JP2005184022A (ja) * | 2000-12-14 | 2005-07-07 | Hitachi Chem Co Ltd | 接続用熱・電気伝導性フィルム及びその用途 |
WO2007125650A1 (ja) * | 2006-04-27 | 2007-11-08 | Sumitomo Bakelite Co., Ltd. | 接着テープ、半導体パッケージおよび電子機器 |
JP2008108625A (ja) * | 2006-10-26 | 2008-05-08 | Tatsuta System Electronics Kk | 導電性接着剤 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09263683A (ja) * | 1996-03-29 | 1997-10-07 | Sumitomo Kinzoku Electro Device:Kk | 導電性エポキシ樹脂組成物 |
JP2001115127A (ja) * | 1999-10-19 | 2001-04-24 | Hitachi Chem Co Ltd | 導電性接着剤とそれを用いた配線板 |
JP2005264095A (ja) * | 2004-03-22 | 2005-09-29 | Kyoto Elex Kk | 導電性樹脂組成物及び導電性ペースト |
JP4843979B2 (ja) | 2004-03-30 | 2011-12-21 | 住友ベークライト株式会社 | 回路基板 |
CN100584180C (zh) * | 2005-02-18 | 2010-01-20 | 东洋油墨制造株式会社 | 电磁波屏蔽性粘合薄膜、其制备方法以及被粘合物的电磁波屏蔽方法 |
TWI388584B (zh) * | 2005-03-04 | 2013-03-11 | Showa Denko Kk | The film is formed with a paste |
JP4828151B2 (ja) * | 2005-04-15 | 2011-11-30 | タツタ電線株式会社 | 導電性接着シート及び回路基板 |
KR101307138B1 (ko) | 2005-09-16 | 2013-09-10 | 토요잉크Sc홀딩스주식회사 | 접착제 조성물, 이것을 사용한 접착제 시트, 및 이들의이용 |
KR100787727B1 (ko) * | 2006-10-31 | 2007-12-24 | 제일모직주식회사 | 스티렌-아크릴로니트릴 공중합체를 이용한 고신뢰성 이방전도성 필름용 조성물 |
JP5348867B2 (ja) * | 2007-09-28 | 2013-11-20 | 株式会社きもと | 粘接着剤および粘接着シート |
JP5487419B2 (ja) * | 2008-02-12 | 2014-05-07 | タツタ電線株式会社 | 導電性接着シート及びそれを備えた配線板、導電性接着シートの製造方法 |
JP2009290195A (ja) * | 2008-04-30 | 2009-12-10 | Toyo Ink Mfg Co Ltd | 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 |
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 |
JP5257125B2 (ja) * | 2009-02-20 | 2013-08-07 | 東洋インキScホールディングス株式会社 | 硬化性難燃性電磁波シールド接着フィルム |
JP2010229282A (ja) * | 2009-03-27 | 2010-10-14 | Toyo Ink Mfg Co Ltd | ポリウレタンポリウレア樹脂組成物、それを用いた硬化性電磁波シールド性接着性フィルム及びその製造方法 |
JP5742112B2 (ja) * | 2010-01-18 | 2015-07-01 | 東洋インキScホールディングス株式会社 | 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 |
JP5528857B2 (ja) * | 2010-03-11 | 2014-06-25 | タツタ電線株式会社 | 電磁波シールドフィルム、これを用いたフレキシブル基板及びその製造方法 |
KR101741292B1 (ko) * | 2010-07-23 | 2017-05-29 | 다츠다 덴센 가부시키가이샤 | 접착제 조성물 및 접착 필름 |
KR101886667B1 (ko) * | 2010-09-13 | 2018-08-09 | 가부시키가이샤 가네카 | 보강판 일체형 플렉서블 프린트 기판, 및 보강판 일체형 플렉서블 프린트 기판의 제조 방법 |
CN102443370A (zh) * | 2010-10-15 | 2012-05-09 | 深圳市道尔科技有限公司 | 一种低卤高导电性单组份银导电胶 |
JP5662104B2 (ja) * | 2010-10-26 | 2015-01-28 | 京セラケミカル株式会社 | 導電性樹脂組成物およびそれを用いた半導体装置 |
-
2013
- 2013-06-28 JP JP2014522699A patent/JP5886957B2/ja active Active
- 2013-06-28 CN CN201380033353.5A patent/CN104379696B/zh active Active
- 2013-06-28 TW TW105140589A patent/TW201708482A/zh unknown
- 2013-06-28 KR KR1020147034441A patent/KR102055031B1/ko active IP Right Grant
- 2013-06-28 CN CN201610849680.3A patent/CN106947409B/zh active Active
- 2013-06-28 TW TW102123328A patent/TWI583769B/zh not_active IP Right Cessation
- 2013-06-28 WO PCT/JP2013/067776 patent/WO2014003159A1/ja active Application Filing
-
2015
- 2015-08-12 JP JP2015159487A patent/JP2016040370A/ja active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000017246A (ja) * | 1998-07-06 | 2000-01-18 | Lintec Corp | 粘接着剤組成物および粘接着シート |
JP2000086981A (ja) * | 1998-09-17 | 2000-03-28 | Nitto Denko Corp | シート状接着剤組成物およびその製法 |
JP2000129216A (ja) * | 1998-10-26 | 2000-05-09 | Nitto Denko Corp | シート状接着剤組成物およびそれを用いた電子部品装置ならびにそのリペアー方法 |
JP2000129217A (ja) * | 1998-10-26 | 2000-05-09 | Nitto Denko Corp | シート状接着剤組成物およびそれを用いた電子部品装置ならびにそのリペアー方法 |
JP2000345010A (ja) * | 1999-04-01 | 2000-12-12 | Mitsui Chemicals Inc | 異方導電性ペースト |
JP2001332124A (ja) * | 2000-05-22 | 2001-11-30 | Toshiba Chem Corp | 導電性ペーストおよび光半導体装置 |
JP2005184022A (ja) * | 2000-12-14 | 2005-07-07 | Hitachi Chem Co Ltd | 接続用熱・電気伝導性フィルム及びその用途 |
JP2003082318A (ja) * | 2001-09-13 | 2003-03-19 | Three M Innovative Properties Co | カチオン重合性接着剤組成物及び異方導電性接着剤組成物 |
WO2007125650A1 (ja) * | 2006-04-27 | 2007-11-08 | Sumitomo Bakelite Co., Ltd. | 接着テープ、半導体パッケージおよび電子機器 |
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US10266730B2 (en) | 2015-02-02 | 2019-04-23 | Tanaka Kikinzoku Kogyo K.K. | Thermally and electrically conductive adhesive composition |
WO2016125644A1 (ja) * | 2015-02-02 | 2016-08-11 | 田中貴金属工業株式会社 | 熱伝導性導電性接着剤組成物 |
CN107207935A (zh) * | 2015-02-02 | 2017-09-26 | 田中贵金属工业株式会社 | 导热性导电性粘接剂组合物 |
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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 |
JP2018067739A (ja) * | 2018-01-18 | 2018-04-26 | 藤森工業株式会社 | 接着性組成物及びfpc用導電性接着シート |
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JPWO2019198624A1 (ja) * | 2018-04-12 | 2021-04-15 | 東洋紡株式会社 | 導電性ペースト |
JP7331840B2 (ja) | 2018-04-12 | 2023-08-23 | 東洋紡エムシー株式会社 | 導電性ペースト |
JP2019165252A (ja) * | 2019-06-12 | 2019-09-26 | 藤森工業株式会社 | Fpc用導電性接着シート及びそれを用いたfpc |
WO2022023830A1 (en) * | 2020-07-29 | 2022-02-03 | 3M Innovative Properties Company | Electrically conductive adhesive film |
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Also Published As
Publication number | Publication date |
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CN104379696A (zh) | 2015-02-25 |
TW201708482A (en) | 2017-03-01 |
JPWO2014003159A1 (ja) | 2016-06-02 |
CN106947409B (zh) | 2018-12-11 |
JP5886957B2 (ja) | 2016-03-16 |
KR20150032527A (ko) | 2015-03-26 |
KR102055031B1 (ko) | 2019-12-11 |
TW201406920A (zh) | 2014-02-16 |
TWI583769B (zh) | 2017-05-21 |
CN104379696B (zh) | 2016-10-12 |
JP2016040370A (ja) | 2016-03-24 |
CN106947409A (zh) | 2017-07-14 |
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