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 PDF

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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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conductive adhesive
resin
adhesive composition
conductive
epoxy resin
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PCT/JP2013/067776
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English (en)
French (fr)
Japanese (ja)
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岩井　靖
寺田恒彦
善治 柳
山本祥久
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タツタ電線株式会社
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Priority to JP2014522699A priority Critical patent/JP5886957B2/ja
Priority to CN201380033353.5A priority patent/CN104379696B/zh
Priority to KR1020147034441A priority patent/KR102055031B1/ko
Publication of WO2014003159A1 publication Critical patent/WO2014003159A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/04—Epoxynovolacs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • 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
    • 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
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2433/00—Presence of (meth)acrylic polymer
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    • C09J2463/00—Presence of epoxy resin

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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PCT/JP2013/067776 2012-06-29 2013-06-28 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 WO2014003159A1 (ja)

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CN201380033353.5A CN104379696B (zh) 2012-06-29 2013-06-28 导电胶组成物、导电胶膜、黏合方法及线路基板
KR1020147034441A KR102055031B1 (ko) 2012-06-29 2013-06-28 도전성 접착제 조성물, 도전성 접착필름, 접착방법 및 회로기판

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KR102055031B1 (ko) 2019-12-11
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