JP2007297636A - Resin composition for anisotropic electric conduction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for anisotropic electric conduction, having excellent adhesiveness, heat resistance, moisture resistance, low-water absorption, dielectric characteristics (a low dielectric constant and a low dielectric loss tangent) and long-term reliability. <P>SOLUTION: The resin composition for the anisotropic electric conduction contains an alicyclic structure-containing polymer containing ≥30 wt.% repeating unit having a polar group and the alicyclic structure in the main chain, and an electroconductive filler. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an anisotropic conductive resin composition, and more specifically, a resin composition having excellent adhesion, heat resistance, moisture resistance, low water absorption, dielectric properties (low dielectric constant, low dielectric loss tangent), and long-term reliability. The present invention relates to an isotropic conductive resin composition. The anisotropic conductive resin composition of the present invention is used as a varnish or anisotropic conductive sheet (including a film) for, for example, mounting a bare chip on a wiring board, connecting a rigid board and a flexible board, and the like. Can be used.

  Conventionally, when mounting general electronic components such as resistors, capacitors, coils and semiconductor elements on wiring boards such as printed wiring boards and ceramic boards, electronic components are mounted on the wiring board and soldered and joined. Yes. In the soldering process, since it is necessary to perform the flow soldering after the reflow soldering, the process is complicated and it is not possible to mount a component having no heat resistance. Furthermore, in the bonding / joining of electronic components, the miniaturization of joints is progressing, making it difficult to cope with solder joints.

  Accordingly, various surface mounting technologies have been developed to meet demands for high-density mounting and miniaturization of electronic devices, improvement of electrical performance, reduction of manufacturing costs, and automation of assembly. In recent years, a connection method using an anisotropic conductive material has attracted attention as an electronic packaging technology for bonding / joining electronic components and connecting between substrates. In the field of electronic component bonding / bonding technology, a technology for connecting an electrode on the wiring board side and an electrode on the semiconductor integrated circuit element side at the shortest possible distance has been developed. As a specific example, bumps (metal protrusions; Au bumps, solder bumps, etc.) are formed on a semiconductor integrated circuit element, and an anisotropic conductive sheet is interposed between the conductive pattern on the wiring board and pressed down. Thus, a method of press-bonding the bump and the conductor pattern on the wiring board to form an electrical connection has been developed.

  In a bonding technique between substrates, a method of connecting a flexible substrate and a rigid substrate through an anisotropic conductive film is employed. For example, a liquid crystal display (LCD) module mounting form employs a system in which a tape carrier package (TCP) in which a semiconductor chip is incorporated and an LCD panel are connected via an anisotropic conductive material.

  The anisotropic conductive material is a material in which conductive fillers such as resin particles (fine particles) in which metal fine particles and a conductive film are provided on the surface are dispersed in a binder resin. The bonding mechanism using the anisotropic conductive material exists on the connection terminal with a probability that there is a conductive filler dispersed in the anisotropic conductive material. The filler is crushed from the point contact to the state close to the surface contact between the terminals, thereby obtaining conductivity, sufficiently adhering the adherend, and performing stable bonding. If the filling amount of the conductive filler is too large, leakage between terminals and a decrease in adhesive force are caused, and if it is too small, a problem occurs in connection resistance. That is, by adjusting the dispersion amount of the conductive filler, the balance between the insulation in the lateral direction and the conductivity between the upper and lower terminals is achieved, and the adhesive force is also controlled.

  Conventionally, thermoplastic resins such as polyethylene resins, polypropylene resins and acrylic resins and thermosetting resins such as epoxy resins, polyurethane resins and phenol resins have been used as binder resins for anisotropic conductive materials. . Among these resins, the epoxy resin is considered to be excellent in long-term reliability compared to the thermoplastic anisotropic conductive material because the variation of the connection resistance value under high temperature conditions is small.

  An anisotropic conductive material using a thermoplastic resin as a binder as described above is insufficient in adhesive strength and heat resistance, and is inferior in long-term reliability particularly under high temperature and high humidity conditions. On the other hand, an anisotropic conductive material using a thermosetting resin as a binder has a problem in repairability due to poor bonding generated in the assembly process. For example, when a bonding failure occurs in the mounting of the LCD module, it is difficult to remove the residue of the anisotropic conductive material after the TCP is peeled off. Further, in the case of a semiconductor device, scraping the whole due to some defects is a great cost loss. Therefore, establishment of techniques such as wiring repair, semiconductor chip replacement, and reuse is required.

  In addition, anisotropic conductive materials that use thermosetting resins such as epoxy resins as binders have better long-term reliability than those that use thermoplastic resins as binders. When severe stress is applied in a pressure cooker test (PCT), a temperature cycle test (TCT), etc., there is a problem that the characteristics change and the connection resistance value increases significantly. Furthermore, the anisotropic conductive material which uses a thermosetting resin as a binder is inferior in long-term storage stability. Therefore, it has been difficult to spread the conventional anisotropic conductive material in a wide field where it is required to satisfy strict usage conditions.

  On the other hand, as electronic components are miniaturized and high-density mounting progresses, the terminal spacing has been reduced, and it is required to cope with the fine pitch of the electrodes and to ensure the high reliability of the connection portion. However, conventional anisotropic conductive materials cannot sufficiently cope with fine pitch. As a method for coping with fine pitches, for example, a method is known in which a large amount of conductive filler that has been specially processed, such as an insulating film coating treatment on a metal film-coated resin ball, is dispersed in the resin. However, with the progress of fine pitch, for example, in the case of a beam lead type IC chip, the width of the beam lead is 50 to 100 μm and the lead interval is also about 50 to 100 μm. When such a fine pitch electronic component is bump-bonded using a conventional anisotropic conductive material, it is difficult to ensure insulation between the bumps. Therefore, an adhesive resin material having excellent dielectric characteristics is demanded.

  An object of the present invention is to provide an anisotropic conductive resin composition excellent in adhesiveness, heat resistance, moisture resistance, low water absorption, dielectric properties (low dielectric constant, low dielectric loss tangent), and long-term reliability. is there.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have found that a resin composition containing an alicyclic structure-containing polymer having a polar group and a conductive filler is used for anisotropic conduction. It has been found that the resin composition exhibits excellent properties. This resin composition can be applied as a varnish to a wiring board or the like to form a coating film (anisotropic conductive film), and can also be used as an anisotropic conductive sheet (including a film). The anisotropic conductive resin composition of the present invention is particularly excellent in long-term reliability and excellent dielectric properties. The binder resin of the anisotropic conductive resin composition of the present invention can be used as a curable resin by blending a curing agent, but can also be used as a thermoplastic resin without blending a curing agent. . The anisotropic conductive resin composition of the present invention using this thermoplastic resin as a binder can be suitably applied to uses such as bonding of a flip chip to a wiring board that require repairability. The present invention has been completed based on these findings.

  Thus, according to the present invention, an alicyclic structure-containing polymer having a polar group and containing a repeating unit having an alicyclic structure in the main chain in a proportion of 30% by weight or more and a conductive filler are provided. An anisotropic conductive resin composition is provided.

  Further, according to the present invention, an alicyclic structure-containing polymer having a polar group and containing a repeating unit having an alicyclic structure in the main chain in a proportion of 30% by weight or more and a conductive filler are organic. An anisotropic conductive varnish is provided which is dissolved or dispersed in a solvent.

  Furthermore, according to the present invention, an alicyclic structure-containing polymer containing a polar group and having a repeating unit having an alicyclic structure in the main chain in a proportion of 30% by weight or more and a conductive filler An anisotropic conductive sheet comprising the resin composition to be contained is provided.

  According to the present invention, there is provided an anisotropic conductive resin composition excellent in adhesiveness, heat resistance, moisture resistance, low water absorption, dielectric properties (low dielectric constant, low dielectric loss tangent), and long-term reliability. The anisotropic conductive resin composition of the present invention can be used as a varnish or an anisotropic conductive sheet for, for example, mounting of a bare chip on a wiring board or connection between a rigid board and a flexible board. .

The alicyclic structure-containing polymer having a polar group The polar group of the alicyclic structure-containing polymer used in the present invention is not particularly limited, but is usually a hetero atom or an atomic group having a hetero atom. And so on. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. From the viewpoint of adhesion, an oxygen atom and a nitrogen atom are preferable, and an oxygen atom is particularly preferable. In the present invention, a polar group having active hydrogen is preferable because it is particularly excellent in adhesiveness. Specific examples of the polar group include an epoxy group, a carboxyl group, a hydroxyl group, an oxy group, an ester group, a carbonyloxycarbonyl group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group. Among these, a carboxyl group, a hydroxyl group, a silanol group, an amino group and the like are preferable, a carboxyl group and a hydroxyl group are more preferable, and a carboxyl group is particularly preferable.

  The polymer having an alicyclic structure having a polar group used in the present invention has an alicyclic structure in the main chain, and from the viewpoint of mechanical strength, heat resistance, etc., the alicyclic structure in the main chain. Containing. Examples of alicyclic structures include saturated cyclic hydrocarbon (cycloalkane) structures and unsaturated cyclic hydrocarbon (cycloalkene) structures. From the viewpoint of dielectric properties (low dielectric constant, low dielectric loss tangent) and heat resistance A cycloalkane structure is preferred. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The properties of heat resistance and moldability are highly balanced and suitable.

  The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably 50% by weight. % Or more, more preferably 70% by weight or more. If the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is too small, the dielectric properties, heat resistance, and long-term reliability are inferior. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is not particularly limited and is appropriately selected depending on the purpose of use.

  As the alicyclic structure-containing polymer having such a polar group, for example, an alicyclic structure-containing polymer obtained by introducing a polar group into the alicyclic structure-containing polymer by a modification reaction has a high molecular weight and a large number of polar groups. Contains, has high adhesiveness, and is suitably used.

  Specific examples of the alicyclic structure-containing polymer include, for example, (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) vinyl fat. And cyclic hydrocarbon polymers, and (5) hydrogenated products thereof. Among these, norbornene polymers and hydrogenated products thereof, cyclic conjugated diene polymers and hydrogenated products thereof are preferable, and norbornene polymers and hydrogenated products thereof are more preferable.

(1) Norbornene-based polymer The norbornene-based polymer is not particularly limited. For example, a norbornene-based monomer is produced by a method disclosed in JP-A-3-14882, JP-A-3-122137 or the like. A (co) polymerized one is used. Specific examples thereof include thermoplastic norbornene resins such as ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, and addition copolymers of norbornene monomers and vinyl compounds. Among these, in order to highly balance heat resistance and dielectric properties, a ring-opening polymer hydrogenated product of norbornene monomer, an addition polymer of norbornene monomer, a vinyl compound copolymerizable with norbornene monomer, and An addition copolymer or the like is preferable, and an open polymer hydrogenated product of a norbornene monomer is particularly preferable.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name “norbornene”), 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5 -Dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hepta-2 -Ene, 5-ethylidene-bicyclo [2.2.1] -hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2. 1] Hept-2-ene, 5-octadecyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [ 2.2.1] Hept-2-ene, 5-vinyl Bicyclo [2.2.1] hept-2-ene, 5-propenyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.12,5] deca-3,7- Diene (common name “dicyclopentadiene”), tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept 2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene (common name “tetracyclododecene”), 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] - dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -dodec-3-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] - dodeca-3-ene; tetracyclo ^{[7.4.0.1 10,13.} 0 ^2,7] trideca -2,4,6,11- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,8] tetradec -3,5,7,12- tetraene (1,4-methano -1,4,4a, also referred to as a 5,10,10a- hexahydrophthalic anthracene), pentacyclo [6.5.1 ^{3 ,} 6. 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] pentadeca-4,11-diene, cyclopentadiene tetramer or higher adduct, 5-phenylbicyclo [2.2.1] hept-2-ene, tetracyclo [6.5.0.1 ^2,5 . 0 ^8,13] trideca -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo [6.6.0.1 ^{2, 5.} 0 ^8,13] tetradeca -3,8,10,12- tetraene (1,4-methano -1,4,4a, 5,10,10a also called hexa hydro anthracene) norbornene having no polar groups, such as Based monomers.

  The norbornene monomer may have a polar group. Examples of the polar group include a hetero atom or an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. From the viewpoint of adhesiveness, an oxygen atom and a nitrogen atom are preferable. Specific examples of the polar group include an epoxy group, a carboxyl group, a hydroxyl group, an oxy group, an ester group, a carbonyloxycarbonyl group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

Specific examples of norbornene-based monomers having a polar group include, for example, 5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hepta-2. -Ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] Hept-2-ene, bicyclo [2.2.1] hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-methyloctanoate, bishi B [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept -2-ene; 5-cyanobicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic imide, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene and the like.

  These norbornene monomers can be used alone or in combination of two or more. The proportion of the norbornene-based monomer unit in the norbornene-based polymer is appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more. It is preferable that the dielectric properties, heat resistance, and long-term reliability are highly balanced.

  Examples of the copolymerizable vinyl compound include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1-pentene. 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1 -Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-echocene, etc., ethylene or α-olefin having 2 to 20 carbon atoms; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cycloo Cycloolefins such as ten, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4- Non-conjugated dienes such as hexadiene and 1,7-octadiene; and the like. These vinyl compounds can be used alone or in combination of two or more.

  The polymerization method of norbornene-based monomer or a vinyl compound copolymerizable with norbornene-based monomer and the hydrogenation method are not particularly limited and can be performed according to a known method.

A ring-opening polymer of a norbornene-based monomer comprises a norbornene-based monomer as a ring-opening polymerization catalyst, a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, a nitrate or an acetylacetone compound, and a reducing agent. Using a catalyst system or a catalyst system comprising a metal halide such as titanium, vanadium, zirconium, tungsten, molybdenum, or an acetylacetone compound and an organoaluminum compound, in a solvent or without a solvent, usually from −50 ° C. to It can be obtained by ring-opening (co) polymerization at a polymerization temperature of 100 ° C. and a polymerization pressure of 0 to 50 kg / cm ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, other Lewis acids A third component such as can be added to increase the polymerization activity and the selectivity of ring-opening polymerization.

An addition copolymer of a norbornene-based monomer and a vinyl compound is usually, for example, -50 ° C to 100 ° C in the presence of a catalyst component composed of a vanadium compound and an organoaluminum compound, in a solvent or without a solvent. It can be obtained by a method of copolymerization at a polymerization temperature of 0 ° C. and a polymerization pressure of 0 to 50 kg / cm ² . The hydrogenated norbornene-based polymer can be obtained by a method of hydrogenating a ring-opening polymer with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

(2) Monocyclic Cyclic Olefin Polymers Monocyclic cycloolefin polymers include, for example, monocyclic olefin polymers such as cyclohexene, cycloheptene, and cyclooctene disclosed in JP-A No. 64-66216. An addition polymer of a cyclic olefin monomer can be used.

(3) Cyclic conjugated diene-based polymer Examples of the cyclic conjugated diene-based polymer include cyclic conjugated dienes such as cyclopentadiene and cyclohexadiene disclosed in JP-A-6-136057 and JP-A-7-258318. A polymer obtained by 1,2- or 1,4-addition polymerization of a monomer and a hydrogenated product thereof can be used.

(4) Vinyl alicyclic hydrocarbon-based polymer Examples of vinyl alicyclic hydrocarbon-based polymers include vinyl alicyclic such as vinylcyclohexene and vinylcyclohexane disclosed in JP-A-51-59989. Polymers of hydrocarbon monomers and hydrogenated products thereof, vinyl aromatic units such as styrene and α-methylstyrene disclosed in JP-A-63-43910 and JP-A-64-1706 A hydrogenated product of an aromatic ring portion of a polymer of a monomer can be used.

  These alicyclic structure-containing polymers can be used alone or in combination of two or more.

  The modified alicyclic structure-containing polymer suitably used in the present invention is a polymer in which a polar group is introduced into these alicyclic structure-containing polymers by a modification reaction. The denaturing reaction is not particularly limited and can be performed according to a conventional method. Specific examples of the modified alicyclic structure-containing polymer include chlorinated products of alicyclic structure-containing polymers, chlorosulfonated products, graft-modified products of polar group-containing unsaturated compounds, preferably polar group-containing polymers. It is a graft modified product of a saturated compound.

  Examples of the polar group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl p-styrylcarboxylate, endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid, endo Cis-bicyclo [2,2,1] hept-5-ene-2-methyl-2,3-dicarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, m-allyl Unsaturated epoxy compounds such as glycidyl ether of phenol and glycidyl ether of p-allylphenol; acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylic acid, methyl- Unsaturated carboxylic acid compounds such as endo-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid; maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, anhydrous Unsaturated carboxylic anhydride compounds such as citraconic acid; unsaturated ester compounds such as monomethyl maleate, dimethyl maleate, glycidyl maleate; allyl alcohol, 2-allyl-6-methoxyphenol, 4-allyloxy-2-hydroxybenzophenone, Unsaturated alcohol compounds such as 3-allyloxy-1,2-propanediol, 2-allylsiphenol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol; chlorodimethylvinylsilane , Trimethylsilylacetylene, 5-trimethyl Silyl-1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol, trimethylsilyl methacrylate, 1-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-cyclopentene, 2-trimethylsilyloxyethyl methacrylate, 2-trimethylsilyl And unsaturated silane compounds such as loxyfuran, 2-trimethylsilyloxypropene, allyloxy-t-butyldimethylsilane, and allyloxytrimethylsilane. Among these, unsaturated epoxy compounds and unsaturated carboxylic acid anhydride compounds are suitable for increasing the modification rate.

  In order to efficiently graft copolymerize the polar group-containing unsaturated compound, it is usually preferable to carry out the reaction in the presence of a radical initiator. As the radical initiator, for example, organic peroxides, organic peresters and the like are preferably used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne- 3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5- Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylberphenyl acetate, tert-butylperisobutylate, tert-butylper-sec-octate, tert-butylperpipa Over bets, it may be mentioned cumyl pin Pareto and tert- butyl hydroperoxide diethyl acetate. Further, in the present invention, an azo compound can be used as a radical initiator. Specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

  These radical initiators can be used alone or in combination of two or more. The use ratio of the radical initiator is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the unmodified alicyclic structure-containing polymer resin. The range is 2.5 parts by weight. The graft modification reaction is not particularly limited and can be performed according to a conventional method. The reaction temperature is usually 0 to 400 ° C., preferably 60 to 350 ° C., and the reaction time is usually 1 minute to 24 hours, preferably 30 minutes to 10 hours.

  The alicyclic structure-containing polymer having an active hydrogen-containing polar group suitably used in the present invention is, for example, after graft-modifying the unsaturated epoxy compound, unsaturated carboxylic anhydride compound, or unsaturated ester compound ( It can also be obtained by a) a method of reacting an active hydrogen-containing compound, (b) a method of reacting an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound and then hydrolyzing it.

  The active hydrogen-containing compound is not particularly limited as long as it is a substance capable of nucleophilic attack on electropositive carbon, but it contains at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, and a carboxyl group. The compound which has is used preferably. Specifically, water; ammonia; methanol, ethanol, 1-propanol, 2-propanol, allyl alcohol, 1-butanol, 2-butanol, 1-methyl-1-propanol, 2-methyl-2-propanol, methallyl Alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2 , 2-dimethyl-1-propanol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, cyclopentanol, 1-hexanol, cyclohexanol, geraniol, citronellol, benzyl alcohol , Furfuryl alcohol, ethylene glycol, propylene glycol, Alcohols such as serine; monomethylamine, monoethylamine, n-propylamine, i-propylamine, cyclopentylamine, cyclohexylamine, geranylamine, benzylamine, aniline, ethanolamine, diethylamine, diphenylamine, diisopropylamine, di-n- Amines such as butylamine, piperidine and pyrrolidine; methanethiol, ethanethiol, benzenethiol, thiophenol, mercaptoacetic acid, 2-mercaptonicotic acid, 2-mercaptobenzoic acid, 3-mercaptopropionic acid, 2 Thiols such as mercaptopropionic acid, mercaptosuccinic acid, N- (2-mercaptopropionyl) glycine; 2-amino-2-nor Lunan carboxylic acid, 2-amino-1-naphthalene sulfonic acid, 4-amino-1-naphthalene sulfonic acid, 5-amino-2-naphthalene sulfonic acid, 8-amino-2-naphthalene sulfonic acid, 4 -Amino-1,8-naphthalic anhydride, 3-amino-2-naphthoic acid, 3-amino-2,7-naphthalenedisulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid, 2-amino-a- (methoxyimino) -4-thiazoreacetic acid, 1-amino-1-cyclohexanecarboxylic acid, 1-amino-1-cyclopentanecarboxylic acid, 1-amino-1-cyclopropane Carboxylic acid, isonipecotic acid, Amino acids such as nicopetic acid, pipecolic acid acid, p-aminobenzoic acid; and the like.

  These active hydrogen-containing compounds can be used alone or in combination of two or more. The amount of the active hydrogen-containing compound used is appropriately selected depending on the reaction conditions, but is usually 0.1 with respect to the oxy group, epoxy group, oxycarbonyl group, carbonyloxy group or carbonyloxycarbonyl group introduced by the graft reaction. -100 equivalents, preferably 0.3-50 equivalents, more preferably 0.5-20 equivalents.

  The reaction of the active hydrogen-containing compound may be carried out in accordance with an ordinary method. After the grafting reaction, the graft-modified polymer may be isolated and reacted, or the active hydrogen-containing compound is added directly to the reaction solution after the grafting reaction. It can also be reacted. The reaction conditions are such that the reaction temperature is usually 0 to 250 ° C., preferably 50 to 200 ° C., and the reaction time is usually 10 minutes to 15 hours, preferably 30 minutes to 5 hours.

Examples of the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound include compounds such as lithium, sodium, potassium, and calcium salts of the active hydrogen-containing compound. The alkali metal salt or alkaline earth metal salt reaction of the active hydrogen-containing compound may be in accordance with a conventional method. After the grafting reaction is completed, the graft-modified polymer may be isolated and reacted, or the reaction solution after the grafting reaction is completed. It is also possible to react by directly adding an active hydrogen-containing compound. The reaction conditions are such that the reaction temperature is usually −50 to 200 ° C., preferably 0 to 100 ° C., and the reaction time is usually 10 minutes to 24 hours, preferably 30 minutes to 10 hours. The hydrolysis can be usually performed by adding a hydrolysis reagent to the reaction solution after the reaction with the alkali metal salt or alkaline earth metal salt of the active hydrogen-containing compound. It does not specifically limit as a hydrolysis reagent, For example, water, dilute hydrochloric acid, ammonium chloride saturated aqueous solution, and organic acids can be used. In the hydrolysis reaction, the reaction temperature is usually −50 ° C. to 100 ° C., preferably 0 to 50 ° C., and the reaction time is usually 1 minute to 24 hours, preferably 10 minutes to 10 hours.
In the present invention, an alicyclic structure-containing polymer obtained by (co) polymerizing the polar group-containing monomer may be used.

  The proportion of the polar group in the polar group-containing alicyclic structure-containing polymer may be appropriately selected according to the purpose of use, but is usually 0.1 to 100 mol%, preferably 0, per all repeating units of the polymer. When the content is in the range of 2 to 50 mol%, more preferably 1 to 30 mol%, the properties of dielectric properties, adhesiveness, and long-term reliability are highly balanced and suitable. The content in the case where the polar group is an active hydrogen-containing polar group such as a carboxyl group or a hydroxyl group is usually 0.1 to 50 mol%, preferably 0.2 to 20 mol%, based on all repeating units of the polymer. More preferably, when it is in the range of 1 to 10 mol%, properties such as adhesion and long-term reliability are highly balanced and suitable.

The graft modification rate is represented by the following formula (1).
Graft modification rate (mol%) = (X / Y) × 100 (1)
X: total number of moles of modifying groups in the polymer by the grafted unsaturated compound Y: total number of monomer units in the polymer

X can be referred to as the total number of moles of the graft monomer-modified residue, and can be measured by ¹ H-NMR. Y is equal to the polymer weight average molecular weight (Mw) / monomer molecular weight. In the case of copolymerization, the molecular weight of the monomer is the average molecular weight of the monomer.

  The molecular weight of the alicyclic structure-containing polymer having a polar group used in the present invention is appropriately selected according to the purpose of use, but gel permeation of a cyclohexane solution (a toluene solution when the polymer does not dissolve). The number average molecular weight in terms of polystyrene measured by the chromatographic (GPC) method is 5,000 or more, preferably 5,000 to 500,000, more preferably 8,000 to 200,000, particularly preferably 10,000. It is in the range of ~ 100,000. If the number average molecular weight of the alicyclic structure-containing polymer having a polar group is excessively small, the adhesive strength and long-term reliability are inferior. On the other hand, when the number average molecular weight of the alicyclic structure-containing polymer having a polar group is excessively large, the dispersibility of the conductive filler and the adhesion to fine irregular surfaces are lowered.

  The glass transition temperature (Tg) of the alicyclic structure-containing polymer having a polar group used in the present invention may be appropriately selected according to the purpose of use, but the higher one from the usage environment of the bonded electronic component When it is usually 50 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or higher, it is excellent in long-term reliability and suitable.

Conductive filler As the conductive filler used in the present invention, those conventionally used can be used without any particular limitation. Specific examples of the conductive filler include (1) metal particles such as nickel, aluminum, silver, copper, tin, lead, gold, zinc, platinum, cobalt, and alloys thereof (for example, solder), and (2) aggregation. Metal particles, (3) molten metal particles, (4) conductive carbon black, (5) metal-coated resin particles obtained by subjecting resin particles to metal plating such as Ni or Au, and (6) a composite of resin and metal particles. Composite resin particles and the like.

  The shape of the conductive filler used in the present invention is not particularly limited, but is preferably spherical, granular, or flat to obtain a sufficient surface contact effect between terminals by heating and pressing. The average particle size of the conductive filler used in the present invention may be appropriately selected depending on the purpose of use, and is an average particle size of (major axis + minor axis) / 2, usually 0.1 to 30 μm, preferably It is 1-20 micrometers, More preferably, it is the range of 5-15 micrometers.

  These conductive fillers can be used alone or in combination of two or more. The blending ratio of the conductive filler is appropriately selected depending on the purpose of use, but is usually 0.1 to 50 parts by weight, preferably 0.3 to 100 parts by weight per 100 parts by weight of the alicyclic structure-containing polymer having a polar group. When it is in the range of 30 parts by weight, more preferably 1 to 25 parts by weight, dielectric properties, adhesiveness, and long-term reliability are highly balanced and suitable. When the blending ratio of the conductive filler is too small, the inter-terminal bonding becomes insufficient, and it becomes difficult to cope with the fine pitch. When the blending ratio of the conductive filler is excessive, there is a possibility that the adhesive strength is reduced or the lateral insulation is impaired.

Anisotropic conductive resin composition The anisotropic conductive resin composition of the present invention is a resin composition containing an alicyclic structure-containing polymer having a polar group and a conductive filler as essential components. If desired, other polymers such as elastomers and resins, and other compounding agents can be added to the resin composition.

  The elastomer is a polymer having a glass transition temperature of 40 ° C. or less, and includes a normal rubbery polymer and a thermoplastic elastomer. In addition, when the glass transition temperature is 2 points or more, such as a block copolymerized rubbery polymer, the rubbery polymer having a glass transition temperature of 40 ° C. or less according to the present invention is the lowest glass transition temperature of 40 ° C. or less. Can be used as

  Examples of elastomers include isoprene rubber, hydrogenated product thereof; chloroprene rubber, hydrogenated product thereof; saturated ethylene / propylene copolymer, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, etc. Polyolefin rubber: Diene copolymers such as ethylene / propylene / diene copolymers, α-olefin / diene copolymers, diene copolymers, isobutylene / isoprene copolymers, isobutylene / diene copolymers, and their halogens Hydrogenated product of dihydride, diene polymer or halide thereof; acrylonitrile / butadiene copolymer, hydrogenated product thereof; vinylidene fluoride / ethylene trifluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer , Vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer , Fluoro rubber such as propylene / tetrafluoroethylene copolymer; special rubber such as urethane rubber, silicone rubber, polyether rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, ethylene acrylic rubber Copolymer of norbornene monomer and ethylene or α-olefin, terpolymer of norbornene monomer and ethylene and α-olefin, ring-opening polymer of norbornene monomer, norbornene monomer Norbornene rubber polymers such as hydrogenated ring-opening polymers; random or block styrene / butadiene copolymers such as emulsion-polymerized or solution-polymerized styrene / butadiene / rubber, high-styrene rubber, etc. Additives: Styrene, butadiene, styrene, rubber, Random copolymers of aromatic vinyl monomers and conjugated dienes such as styrene, isoprene, styrene, rubber, styrene, ethylene, butadiene, styrene, rubber, and hydrogenated products thereof; styrene, butadiene, styrene, rubber, styrene, isoprene・ Styrene-rubber, aromatic vinyl monomers such as styrene / ethylene / butadiene / styrene / rubber, linear or radial block copolymers of conjugated dienes, and styrenic thermoplastic elastomers such as hydrogenated products, Examples of the thermoplastic elastomer include urethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, 1,2-polybutadiene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers.

  Among these, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer, and a hydrogenated product thereof are preferable because of good dispersibility with the alicyclic structure-containing thermoplastic resin. The copolymer of the aromatic vinyl monomer and the conjugated diene monomer may be a block copolymer or a random copolymer. From the viewpoint of heat resistance, it is more preferable to hydrogenate a portion other than the aromatic ring. Specifically, styrene / butadiene block copolymer, styrene / butadiene / styrene block copolymer, styrene / isoprene / block copolymer, styrene / isoprene / styrene / block copolymer, styrene / butadiene / random copolymer. Examples thereof include polymers and hydrogenated products thereof.

  Other polymers include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, polypentene, and ethylene-ethyl acrylate. Polymers, polyolefins such as ethylene-vinyl acetate copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6 and nylon 66; other resins such as polycarbonate, polyimide and epoxy resin;

  These other polymers can be used alone or in combination of two or more. The blending amount of the other polymer is usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the alicyclic structure-containing polymer having a polar group.

  Examples of other compounding agents include curing agents, curing accelerators, curing aids, flame retardants, heat stabilizers, weathering stabilizers, leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, and lubricants. , Dyes, pigments, natural oils, synthetic oils, waxes, and the like, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention.

  The resin composition of the present invention is used as a thermoplastic resin composition without blending a curing agent in applications such as flip chip bonding where repairability is required. On the other hand, in applications where high heat resistance and long-term reliability are required, a curable resin composition containing a curing agent and, if necessary, a curing accelerator and a curing aid is used.

Examples of the curing agent include methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, and t-butylhydro Peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, α, α'-bis (t -Butylperoxy-m-isopropyl) organic peroxides such as benzene, octanoyl peroxide, isobutyryl peroxide, peroxydicarbonate; aliphatic polyamines such as hexamethylenediamine, triethylenetetramine, diethylenetriamine, tetraethylenepentamine; Nocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2,6 ] decane; 1,3- (diaminomethyl) cyclohexane, mensendiamine, isophoronediamine N -Alicyclic polyamines such as aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane; 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, α , Α'-bis (4-aminophenyl) -1,3-diisopropylbenzene, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 4,4'-diaminodiphenylsulfone, metaphenylene Aromatic polyamines such as diamine and metaxylylenediamine; 4,4-bisazidoben Col (4-methyl) cyclohexanone, 4,4'-diazidochalcone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) -4-methyl-cyclohexanone, 4, Bisazides such as 4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, 2,2'-diazidostilbene; phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, nadic acid anhydride, Acid anhydrides such as 1,2-cyclohexanedicarboxylic acid and maleic anhydride-modified polypropylene; dicarboxylic acids such as fumaric acid, phthalic acid, maleic acid, trimellitic acid, and hymic acid; 1,3′-butanediol, 1,4 '-Butanediol, hydroquinone dihydroxydiethyl ether, tricyclodeca Diols such as dimethanol; Triols such as 1,1,1-trimethylolpropane; Polyhydric phenols such as phenol novolac resin and cresol novolac resin; Nylon-6, nylon-66, nylon-610, nylon-11, nylon- 612, nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, polyamide such as polyhexamethylene isophthalamide; diisocyanate such as hexamethylene diisocyanate, toluylene diisocyanate; and the like. These curing agents can be used alone or in combination of two or more. The blending ratio of the curing agent is usually 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the alicyclic structure-containing polymer having a polar group. Range.

  Examples of the curing accelerator include amines such as pyridine, benzyldimethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, dimethylformamide, and imidazole. These curing accelerators can be used alone or in combination of two or more. It is usually in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the alicyclic structure-containing polymer having a polar group and the blending ratio of the curing accelerator.

  The curing aid is not particularly limited, but may be one known in JP-A No. 62-34924, for example, oxime / nitroso such as quinone dioxime, benzoquinone dioxime, p-nitrosophenol. -Based curing aids; maleimide-based curing aids such as N, Nm-phenylenebismaleimide; allylic curing aids such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate; ethylene glycol dimethacrylate, trimethylolpropane Examples thereof include methacrylate-based curing aids such as trimethacrylate; vinyl-based curing aids such as vinyltoluene, ethylvinylbenzene, and divinylbenzene;

  These curing aids can be used alone or in combination of two or more. The blending ratio of the curing aid is usually 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the curing agent.

  The resin composition of the present invention is prepared by mixing an alicyclic structure-containing polymer having a polar group and a conductive filler as essential components and optionally adding other polymers and other compounding agents according to a conventional method. be able to.

Use form The use form of the anisotropic conductive resin composition of the present invention may be appropriately selected according to the purpose of use, but when used for bonding fine uneven surfaces such as precision electronic parts, varnish (anisotropic) In the form of a conductive conductive adhesive) or a sheet (an anisotropic conductive sheet).

  The varnish of the present invention is prepared by dissolving or dispersing the resin composition in an organic solvent. The organic solvent is not particularly limited as long as each component can be dissolved or dispersed. For example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene; aliphatic carbonization such as n-pentane, hexane and heptane. Hydrogen; cycloaliphatic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; ketones such as methyl ethyl ketone, 2-pentanone and cyclohexanone; ethers; alcohols; These organic solvents are used alone or in combination of two or more. The amount of the organic solvent used may be an amount ratio sufficient to uniformly dissolve or disperse the alicyclic structure-containing polymer having a polar group, the conductive filler, and other components contained as necessary. Usually, the solid content concentration is 1 to 80% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

  The anisotropic conductive sheet of the present invention can be obtained by molding the resin composition. As a method for forming the sheet, a conventional method may be used. For example, after applying the varnish to a smooth surface such as a mirror-finished metal plate or a resin carrier film, the solvent is dried, or the resin composition A method of melt-extruding the product is selected. The thickness of the sheet of the present invention is appropriately selected according to the purpose of use, but is usually 1 to 1,000 μm, preferably 5 to 500 μm, and more preferably 10 to 100 μm. Sex is highly balanced and suitable.

As a method for bonding a bonding method adherends each other, for example, (1) after the varnish of the present invention was applied to one adherend, the solvent was dried to form an anisotropic conductive layer, and then, the (2) Laminating the anisotropic conductive sheet of the present invention on one adherend and placing the other adherend thereon Then, a method of thermocompression bonding is exemplified.

  Since the resin composition, varnish, and sheet of the present invention are excellent in long-term reliability, they can be suitably used as an anisotropic conductive material (anisotropic conductive adhesive). Specific applications include, for example, bonding / bonding of wiring boards such as printed wiring boards and ceramic boards to general electronic components and semiconductor elements, bump bonding of semiconductor chip electrodes and wiring board electrodes, and lead for integrated circuit components. Adhesion / bonding between a liquid crystal panel and a TCP transparent conductive film (ITO), adhesion to an electrode film of a crystal resonator, and the like.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples. In these examples, [part] and [%] are based on weight unless otherwise specified. Moreover, the measuring method is as follows.

(1) The glass transition temperature was measured by DSC method. However, in the case of a thermosetting resin, it measured by the TMA method using the film.

(2) The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured as polystyrene converted values by the GPC method using chloroform as a solvent unless otherwise specified.

(3) The hydrogenation rate of the main chain and the modification rate of the polymer were both measured by ¹ H-NMR.

(4) The dielectric constant and dielectric loss tangent at 1 MHz were measured according to JIS C6481.

(5) In the high-temperature and high-humidity test, the sample was left in an environment of 100% humidity and a temperature of 105 ° C. for 1,000 hours, the degree of increase in the connection resistance value was examined, and evaluated according to the following criteria.
<Initial>
A: 10Ω or less,
○: 20Ω or less,
Δ: 30Ω or less,
X: 50Ω or more.
<After PCT>
A: 10Ω or less,
○: 20Ω or less,
Δ: 30Ω or less,
X: 50Ω or more.

[Synthesis Example 1]
Using a polymerization catalyst system consisting of tungsten hexachloride, triisobutylaluminum, and isobutyl alcohol, 8-ethyltetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] -3-dodecene (hereinafter abbreviated as ETD), followed by a hydrogenation reaction by a known method using a hydrogenation catalyst system comprising nickel acetylacetonate and triisobutylaluminum, A combined hydrogenated product was obtained. To 100 parts of the resulting hydrogenated polymer, 2 parts of maleic anhydride, 1 part of dicumyl peroxide and 300 parts of tert-butylbenzene were mixed and reacted in an autoclave at 135 ° C. for 4 hours. The reaction solution was coagulated and dried in the same manner as above to obtain a maleic anhydride-modified polymer. To 100 parts of the resulting maleic anhydride-modified polymer, 3 parts of isopropyl alcohol was added and subjected to a decomposition reaction at 135 ° C. for 1 hour to obtain a maleic acid half ester-modified polymer (A). This was dissolved in xylene so that the resin component amount would be 30%. Using this solution, a 125-μm polyethylene terephthalate (PET) film was coated with a doctor blade to a thickness of 200-300 μm and dried in nitrogen at 160 ° C. for 1 hour to obtain a sheet with a thickness of 50-70 μm. It was. Table 1 shows the physical properties of the obtained sheet.

[Synthesis Example 2]
A sheet made of maleic anhydride-modified polymer (B) was obtained in the same manner as in Synthesis Example 1 except that 2 parts of maleic anhydride was changed to 8 parts and 1 part of dicumyl peroxide was changed to 4 parts. The physical properties are shown in Table 1.

[Synthesis Example 3]
An epoxy-modified polymer was obtained in the same manner as in Synthesis Example 2 except that maleic anhydride was replaced with allyl glycidyl ether. 3 parts of ammonia was added to 100 parts of the resulting epoxy-modified polymer, and a decomposition reaction was performed at 135 ° C. for 1 hour to obtain an alcohol-modified polymer (C). Using this alcohol-modified polymer (C), a sheet was prepared in the same manner as in Synthesis Example 1. The physical properties are shown in Table 1.

[Synthesis Example 4]
An epoxy resin varnish was prepared by adding 100 parts by weight of an epoxy resin (Epicoat 1009, manufactured by Yuka Shell Epoxy Co., Ltd.) and 170 parts by weight of HX3941HP (manufactured by Asahi Kasei Co., Ltd.) as a curing agent to 80 parts by weight of toluene. This was dried to obtain a sheet having a thickness of 25 μm. The physical properties of this sheet when hard baked at 180 ° C. for 2 hours are shown in Table 1.

(footnote)
(1) ETD: 8-ethyltetracyclododecene (2) Allyl glycidyl ether ring opening: Alcohol modification by opening an epoxy group

[Example 1]
To 100 parts of the polymer (A) obtained in Synthesis Example 1, Ni particles (conductive filler a) having an average particle diameter of 7 μm were added at the blending ratio shown in Table 2, and the resin component amount was 30%. So that it was dissolved in xylene. Using this solution, a sheet having a thickness of 50 to 70 μm was prepared. The obtained sheet was placed on a glass epoxy substrate, and a semiconductor component (125 μm pitch, 360 pins) based on silicon was heated and pressure-bonded at 200 ° C. for 30 seconds and bonded thereto. This sample was subjected to a high temperature and high humidity test. The evaluation results are shown in Table 2, and excellent results were obtained for any of the samples.

[Examples 2 to 5]
A sheet was prepared in the same manner as in Example 1 except that the polymer and conductive filler shown in Table 2 were used in the blending ratio shown in Table 2, and a high temperature and high humidity test was performed. The evaluation results are shown in Table 2, and excellent results were obtained for any of the samples.

[Comparative Examples 1-3]
The epoxy resin varnish prepared in Synthesis Example 4 was mixed with the conductive filler shown in Table 2, and a semi-cured sheet was produced in the same manner as in Example 1. A semiconductor component was pressure-bonded onto a glass epoxy substrate in the same manner as in Example 1 using the sheet before hard baking thus produced. The evaluation results are shown in Table 2. In all cases, the connection resistance value after the high-temperature and high-humidity test was 50Ω or more, and conduction failure occurred.

(footnote)
Conductive filler a: Ni particle with an average particle size of 7 μm Conductive filler b: Particle with a Ni / Au plating on silica with an average particle size of 5 μm c: Benzoguanamine resin with an average particle size of 5 μm (manufactured by Nippon Chemical Co., Ltd., Bright 20GNRY 4.6EH) Ni / Au plated particles

  The anisotropic conductive resin composition of the present invention can be applied as a varnish to a wiring board or the like to form a coating film (anisotropic conductive film), and an anisotropic conductive sheet (including a film). Can be used as The anisotropic conductive resin composition of the present invention is particularly excellent in long-term reliability and excellent dielectric properties. The binder resin of the anisotropic conductive resin composition of the present invention can be used as a curable resin by blending a curing agent, but can also be used as a thermoplastic resin without blending a curing agent. . The anisotropic conductive resin composition of the present invention using this thermoplastic resin as a binder can be suitably applied to uses such as bonding of a flip chip to a wiring board that require repairability.

Claims (17)

  An anisotropic conductive resin containing an alicyclic structure-containing polymer having a polar group and a repeating unit having an alicyclic structure in the main chain in a proportion of 30% by weight or more and a conductive filler Composition.   2. The anisotropic conductive resin composition according to claim 1, wherein a ratio of the polar group in the alicyclic structure-containing polymer having a polar group is 0.2 to 50 mol% per all repeating units of the polymer.   The anisotropic conductive resin composition according to claim 1, wherein the polar group is a heteroatom or an atomic group having a heteroatom.   The anisotropic conductive resin composition according to any one of claims 1 to 3, wherein the polar group is a polar group having active hydrogen.   The polar group is an epoxy group, carboxyl group, hydroxyl group, oxy group, ester group, carbonyloxycarbonyl group, silanol group, silyl group, amino group, nitrile group, or sulfone group. Item 2. The anisotropic conductive resin composition according to item 1.   The anisotropic conductive resin composition according to any one of claims 1 to 5, wherein the alicyclic structure-containing polymer is a polymer containing a cycloalkane structure.   The resin composition for anisotropic conduction according to any one of claims 1 to 6, wherein the alicyclic structure has 4 to 30 carbon atoms.   The alicyclic structure-containing polymer is (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, (4) a vinyl alicyclic hydrocarbon heavy. The anisotropic conductive resin composition according to any one of claims 1 to 7, which is a coalescence or (5) a hydrogenated product thereof.   The anisotropic conductive resin composition according to any one of claims 1 to 8, wherein the alicyclic structure-containing polymer having a polar group has a number average molecular weight of 5,000 to 500,000.   The resin composition for anisotropic conduction according to any one of claims 1 to 9, wherein the alicyclic structure-containing polymer having a polar group has a glass transition temperature of 50 ° C or higher.   11. The anisotropic conductive material according to claim 1, wherein the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer having a polar group is 50% by weight or more. Resin composition.   The said resin composition contains a conductive filler in the ratio of 0.1-50 weight part with respect to 100 weight part of alicyclic structure containing polymers which have a polar group. The anisotropic conductive resin composition according to item 1.   The resin composition for anisotropic conduction according to any one of claims 1 to 12, wherein an average particle diameter of (major axis + minor axis) / 2 of the conductive filler is 0.1 to 30 µm.   The anisotropic conductive resin composition according to claim 1, wherein the conductive filler has a spherical shape, a granular shape, or a flat shape.   An alicyclic structure-containing polymer containing a polar group and having a repeating unit having an alicyclic structure in the main chain in a proportion of 30% by weight or more and a conductive filler are dissolved or dispersed in an organic solvent. Anisotropic conductive varnish.   A resin composition comprising a polymer containing an alicyclic structure containing a polar group and a repeating unit having an alicyclic structure in the main chain in a proportion of 30% by weight or more and a conductive filler. Isotropic conductive sheet.   The anisotropic conductive resin composition is placed between an electronic component and a wiring board or between each wiring board and heated and pressed to bond them together and to conduct electricity only between the terminals of both. The use method of the resin composition for anisotropic conduction of any one of Claims 1 thru | or 16 used for obtaining property and joining.