JPH11293133A - Resin composition - Google Patents

Abstract

[57] [Problem] A resin excellent in adhesiveness, heat resistance, moisture resistance, low water absorption, dielectric properties (low dielectric constant, low dielectric loss tangent), long-term reliability, and usable as an anisotropic conductive material Providing a composition. SOLUTION: The resin composition is obtained by dispersing a microcapsule type conductive filler in which the surface of conductive particles is coated with an insulating resin in a polymer having a ring structure, and dissolving or dispersing the resin composition in an organic solvent. And a sheet comprising the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a polymer having a ring structure and a microcapsule-type conductive filler, and more particularly to adhesiveness, heat resistance, moisture resistance, low water absorption, and dielectric properties. The present invention relates to a resin composition which has excellent characteristics (low dielectric constant, low dielectric loss tangent) and long-term reliability and can be used as an anisotropic conductive material. The resin composition of the present invention is suitable for use as an anisotropic conductive material in the form of a varnish or a sheet (including a film), for example, for mounting a bare chip on a wiring board, connecting a rigid board to a flexible board, and the like. Can be used for

[0002]

2. Description of the Related Art Conventionally, when mounting general electronic components and semiconductor elements such as resistors, capacitors, and coils on a wiring board such as a printed wiring board or a ceramic board, the electronic components are mounted on the wiring board and soldered. We attach and attach. In the soldering process, it is necessary to perform flow soldering following reflow soldering, so that the process is complicated and components without heat resistance cannot be mounted. Furthermore, in the bonding and joining of electronic components, the miniaturization of the joining portion is progressing, so that it is difficult to cope with solder joining.

Various surface mounting techniques have been developed to meet the demands for high-density mounting and miniaturization of electronic devices, improvement of electrical performance, reduction of manufacturing cost, automation of assembly, and the like. In recent years, as an electronic packaging technology, a connection method using an anisotropic conductive material has been attracting attention for bonding and joining electronic components and connecting between substrates. Adhesion of electronic parts
In the field of bonding technology, a technology for connecting an electrode on a wiring board and an electrode on a semiconductor integrated circuit element at a distance as short as possible has been developed. As a specific example, a bump (metal bump; Au bump, solder bump, or the like) is formed on a semiconductor integrated circuit element, an anisotropic conductive sheet is interposed in a gap between the conductive pattern on a wiring board, and pressed. ,
A method has been developed in which a bump and a conductor pattern on a wiring board are pressure-welded to form an electrical connection.

As a bonding technique between substrates, a method of connecting a flexible substrate and a rigid substrate via an anisotropic conductive film has been adopted. For example, a liquid crystal display (LC
D) In a module mounting mode, a method is used in which a tape carrier package (TCP) incorporating a semiconductor chip and an LCD panel are connected via an anisotropic conductive material.

The anisotropic conductive material is a material in which conductive fillers such as fine metal particles and resin balls (fine particles) having a conductive film provided on the surface thereof are dispersed in a binder resin. The mechanism of bonding using anisotropic conductive material is that the conductive filler dispersed in the anisotropic conductive material exists on the connection terminals with a certain probability, and by applying heat and pressure during bonding, The filler is crushed between the terminals from point contact to near surface contact, thereby obtaining conductivity,
In this method, the adherend is sufficiently bonded and stable bonding is performed. If the amount of the conductive filler is too large, leakage between terminals and a decrease in adhesive strength are caused. If the amount is too small, a problem occurs in connection resistance. That is, by adjusting the amount of dispersion of the conductive filler, the balance between the lateral insulation and the conductivity between the upper terminals is balanced, and further, the adhesive force is controlled.

Conventionally, as the binder resin for the anisotropic conductive material, a thermoplastic resin such as a polyethylene resin, a polypropylene resin, or an acrylic resin and a thermosetting resin such as an epoxy resin, a polyurethane resin, or a phenol resin have been used. Have been. Among these resins, epoxy resins are said to be superior in long-term reliability as compared with thermoplastic anisotropic conductive materials because the variation in connection resistance under high temperature conditions is small.

The anisotropic conductive material using a thermoplastic resin as a binder as described above has insufficient adhesion and heat resistance, and is inferior in long-term reliability particularly under high temperature and high humidity conditions. On the other hand, anisotropic conductive material using a thermosetting resin as a binder,
There has been a problem in repairability due to defective bonding generated in the assembly process. For example, when a bonding failure occurs in mounting 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, scrapping the whole due to a part of the defect causes a large loss in cost. Therefore, it is required to establish techniques such as wiring repair, semiconductor chip replacement, and reuse.

An anisotropic conductive material using a thermosetting resin such as an epoxy resin as a binder has good long-term reliability as compared with a material using a thermoplastic resin as a binder. When a severe stress is applied in a pressure cooker test (PCT), a temperature cycle test (TCT), or the like below, there is a problem that characteristics are changed and a connection resistance value is significantly increased. Furthermore, an anisotropic conductive material using a thermosetting resin as a binder has poor long-term storage properties. Therefore, it has been difficult for the conventional anisotropic conductive material to be widely used in a wide field in which strict use conditions are required to be satisfied.

On the other hand, as electronic components have become smaller and more densely packaged, the terminal spacing has been reduced, and it has been required to cope with finer pitches of electrodes and to ensure high reliability of connection portions. In order to cope with fine pitch, it is necessary to increase the number of conductive fillers per connection terminal by dispersing a large amount of conductive filler in resin. However, the conventional anisotropic conductive material cannot sufficiently cope with a fine pitch. In other words, 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 50 μm.
About 100 μm. When bumps are bonded to such a fine-pitch electronic component using a conventional anisotropic conductive material, it is difficult to ensure insulation between the bumps. Therefore, there is a need for a new resin material that is excellent in adhesiveness, heat resistance, moisture resistance, low water absorption, etc., has remarkably excellent dielectric properties, and can sufficiently cope with fine pitch.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide adhesiveness, heat resistance, moisture resistance, low water absorption, dielectric properties (low dielectric constant,
An object of the present invention is to provide a resin composition which is excellent in low dielectric loss tangent, long-term reliability, and can be used as an anisotropic conductive material. The present inventor has conducted intensive studies to solve the problems of the prior art, and as a result, dispersed a microcapsule-type conductive filler in which the surface of conductive particles is coated with an insulating resin, in a ring structure-containing polymer. It has been found that the resin composition obtained exhibits excellent properties as an anisotropic conductive material and can achieve the above object. While the ring structure-containing polymer exhibits excellent dielectric properties, the microcapsule-type conductive filler can increase the filling amount without impairing the insulating property, and thereby can cope with fine pitch. .

The 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), or used as an anisotropic conductive sheet (including a film). can do. The resin composition of the present invention has excellent long-term reliability as an anisotropic conductive material and excellent dielectric properties. The ring structure-containing polymer can be used as a curable resin by blending a curing agent,
It can also be used as a thermoplastic resin without blending a curing agent. A resin composition using a thermoplastic resin as a binder can be suitably used as an anisotropic conductive material, particularly for applications such as joining a flip chip to a wiring board, which requires repairability. The present invention has been completed based on these findings.

[0012]

Thus, according to the present invention, there is provided a resin composition comprising a ring structure-containing polymer and a microcapsule-type conductive filler in which the surface of conductive particles is coated with an insulating resin. Things are provided. Further, according to the present invention, there is provided a varnish obtained by dissolving or dispersing a ring structure-containing polymer and a microcapsule type conductive filler in which the surface of conductive particles is coated with an insulating resin in an organic solvent. You. Further, according to the present invention, there is provided a sheet comprising a resin composition obtained by dispersing a microcapsule type conductive filler in which the surface of conductive particles is coated with an insulating resin in a polymer having a ring structure.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer having a ring structure The polymer having a ring structure used in the present invention is a homopolymer or a copolymer having a ring structure in a main chain and / or a side chain, and has a mechanical strength. From the viewpoints of heat resistance and the like, those containing a ring structure in the main chain are preferable. Examples of the ring structure include an aromatic ring structure, a saturated cyclic hydrocarbon (cycloalkane structure), and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoints of mechanical strength and heat resistance, the cycloalkane structure is preferred. preferable. Further, examples of the ring structure include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a polycyclic ring obtained by combining these. The number of carbon atoms constituting the ring structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20.
When the number is in the range of 5 to 15, more preferably, the mechanical strength, heat resistance, and various properties of the moldability are highly balanced and suitable.

The proportion of the repeating unit having a ring structure in the polymer having a ring structure used in the present invention 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, it is 70% by weight, and the upper limit is 100% by weight. If the proportion of the repeating unit having a ring structure in the ring structure-containing polymer is excessively small,
Poor heat resistance is not preferred. The remainder other than the repeating unit having a ring structure in the ring structure-containing polymer is not particularly limited, and is appropriately selected depending on the purpose of use. That is, not only a homopolymer or a copolymer of a monomer having a ring structure but also a copolymer of an acyclic monomer copolymerizable therewith can be used. Further, the ring structure-containing polymer,
After the polymerization, a treatment such as hydrogenation or graft modification may be performed.

Specific examples of such a polymer having a ring structure include (1) a norbornene-based polymer, (2) a monocyclic cycloolefin-based polymer, (3) a cyclic conjugated diene-based polymer, 4) vinyl-based cyclic hydrocarbon polymer, (5)
Aromatic polymer having a repeating unit of an aromatic ring in the main chain,
And (6) hydrogenated products thereof. Among these, norbornene-based polymers and hydrogenated products thereof, cyclic conjugated diene-based polymers and hydrogenated products thereof are preferable, and norbornene-based polymers and hydrogenated products thereof are more preferable.

(1) Norbornene-based polymer The norbornene-based polymer is not particularly limited, and examples thereof include JP-A-3-14882 and JP-A-3-122.
A polymer obtained by polymerizing a norbornene-based monomer by a method disclosed in, for example, JP-A-137-137 is used. Specific examples include a ring-opened polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition-type polymer of a norbornene-based monomer, and an addition-type copolymer of a norbornene-based monomer and a vinyl compound. Among them, in order to highly balance heat resistance and dielectric constant, hydrogenated ring-opening polymer of norbornene-based monomer, addition-type polymer of norbornene-based monomer, addition of vinyl compound copolymerizable with norbornene-based monomer Type copolymers are preferred, and hydrogenated ring-opening polymers of norbornene monomers are particularly preferred.

The norbornene-based monomers are disclosed in the above publications, JP-A-2-227424 and JP-A-2-27684.
A known monomer disclosed in, for example, Japanese Patent Publication No. 2 (November 2), for example, a polycyclic hydrocarbon having a norbornene structure;
Substituted derivatives of alkyl, alkenyl, alkylidene, aromatic and the like; substituted derivatives of polar groups such as halogen, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group and silyl group; alkyl and alkenyl having these polar groups , Alkylidene, aromatic and other substituted derivatives; Among them, polycyclic hydrocarbons having a norbornene structure and substituted derivatives thereof such as alkyl, alkenyl, alkylidene, and aromatic are preferable because of their excellent chemical resistance and moisture resistance.

Examples of the norbornene-based monomer include 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene,
5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-
Methoxycarbonyl-2-norbornene, 5-cyano-
2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl-2-norbornene and the like;
Dicyclopentadiene, a substituted derivative thereof as described above,
For example, 2,3-dihydrodicyclopentadiene or the like; dimethanooctahydronaphthalene, a substituted derivative thereof as described above, for example, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5, 6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene- 1,4: 5,8-dimetano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimetano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-
1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-
1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5,8-
Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene and the like; adducts of cyclopentadiene with tetrahydroindene and the like, substituted derivatives thereof as described above, for example, 1,4-dimethano- 1,4,4a, 4b,
5,8,8a, 9a-octahydrofluorene, 5,8
-Methano-1,2,3,4,4a, 5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like;
Multimers of cyclopentadiene, substituted derivatives thereof as described above, for example, 4,9: 5,8-dimethano-3a, 4,4
4a, 5,8,8a, 9,9a-octahydro-1H-
Benzoindene, 4,11: 5,10: 6,9-trimethano-3a, 4,4a, 5,5a, 6,9,9a, 1
0,10a, 11,11a-dodecahydro-1H-cyclopentaanthracene and the like; 1,4-methano-1,4,4
a, 4b, 5,8,8a, 9a-octahydrofluorene, a substituted derivative thereof as described above; 1,4-methano-
1,4,4a, 9a-tetrahydrofluorene, a substituted derivative thereof as described above, for example, 1,4-methano-8-
Methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-chloro-1,4,4a, 9a
-Tetrahydrofluorene, 1,4-methano-8-bromo-1,4,4a, 9a-tetrahydrofluorene and the like;
1,4-methano-1,4,4a, 9a-tetrahydrobenzofuran, a substituted derivative thereof as described above; 1,4-methano-9-phenyl-1,4,4a, 9a-tetrahydrocarbazole, as described above Substituted derivatives of 1,4
-Methano-1,4,4a, 5,10,10a-hexahydroanthracene, substituted derivatives thereof as described above;
10-methano-6b, 7,10,10a-tetrahydrofluorancene, substituted derivatives thereof as described above; and the like.

These norbornene monomers can be used alone or in combination of two or more. The norbornene-based polymer may be a copolymer of a norbornene-based monomer and another monomer copolymerizable therewith. The proportion of the norbornene-based monomer in the norbornene-based polymer is appropriately selected depending on the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more.
It is preferred that the content is at least 70% by weight, more preferably at least 70% by weight, because the characteristics of dielectric constant, heat resistance and elongation are highly balanced.

Examples of the vinyl compound copolymerizable with the norbornene monomer include ethylene, propylene,
1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 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,
-Ethylene or α-olefin having 2 to 20 carbon atoms such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3 -Methylcyclohexene, 2
-(2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7
-Cycloolefins such as methano-1H-indene;
Non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination.
More than one species can be used in combination. A polymerization method and a hydrogenation method of a norbornene-based monomer or a vinyl compound copolymerizable with the norbornene-based monomer,
There is no particular limitation, and the reaction can be performed according to a known method.

The ring-opening (co) polymer of a norbornene-based monomer is prepared by converting a norbornene-based monomer into a ruthenium, rhodium, palladium, osmium,
Iridium, a metal halide such as platinum, a nitrate or acetylacetone compound and a catalyst system comprising a reducing agent, or titanium, vanadium, zirconium, tungsten, a metal halide such as molybdenum or an acetylacetone compound, and an organic aluminum compound Using a catalyst system consisting of: in a solvent or without solvent, usually at a polymerization temperature of -50 ° C to 100 ° C, 0 to 50 kg / c
It can be obtained by ring-opening (co) polymerization at a polymerization pressure of m ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound,
By adding a third component such as a halogen-containing compound, molecular iodine, and other Lewis acids, the polymerization activity and the selectivity of ring-opening polymerization can be increased.

The addition copolymer of a norbornene-based monomer and a vinyl compound can be prepared, for example, by adding a monomer component in a solvent or in the absence of a solvent in the presence of a catalyst system comprising a vanadium compound and an organoaluminum compound. 50 ° C ~
It can be obtained by copolymerization at a polymerization temperature of 100 ° C. and a polymerization pressure of 0 to 50 kg / cm ² . The hydrogenated norbornene-based polymer can be obtained by a method in which a ring-opened (co) polymer is hydrogenated with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. By hydrogenation, carbon-carbon unsaturated bonds present in the main chain or side chains are partially or completely hydrogenated to be saturated. In the case of a norbornene-based polymer containing an aromatic ring, the aromatic ring may be hydrogenated by hydrogenation, or only the non-aromatic carbon-carbon unsaturated bonds of the main chain and side chains are selectively hydrogenated. Is also good.

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cyclic olefin polymer include monocyclic cycloolefin polymers such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216. (Addition (co) polymer of a cyclic olefin monomer) can be used.

(3) Cyclic conjugated diene-based polymer As the cyclic conjugated diene-based polymer, for example, Japanese Unexamined Patent Publication No.
(Co) polymers obtained by 1,2- or 1,4-addition polymerization of cyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene disclosed in JP-B-136057 and JP-A-7-258318, and hydrogen thereof. Additives and the like can be used.

(4) Vinyl Cyclic Hydrocarbon Polymer Examples of the vinyl cyclic hydrocarbon polymer include vinyl cyclic hydrocarbons such as vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59989. Polymers of hydrocarbon monomers and hydrogenated products thereof, and vinyl cyclic hydrocarbon monomers such as styrene and α-methylstyrene disclosed in JP-A-63-43910 and JP-A-64-1706. The hydrogenated product of the aromatic ring portion of the (co) polymer can be used.

(5) Aromatic polymer having an aromatic ring in the main chain As the aromatic polymer having an aromatic ring in the main chain, for example, polyphenylene sulfide, polyphenylene ether, polyether sulfone, polysulfone and the like are used. be able to. In the present invention, the use of these ring structure-containing polymers as a curable resin is preferable because heat resistance can be further improved.
When using the ring structure-containing polymer as a curable resin,
For example, a resin composition in which a curing agent is blended with the above-mentioned ring-structure-containing polymer, more preferably a resin composition in which a curing agent is blended with a graft-modified product of the above-mentioned ring-structure-containing polymer, is used.
As the graft-modified product, a graft-modified product obtained by grafting a polar group-containing unsaturated compound to a polymer having a ring structure is usually used. Further, a graft-modified product obtained by grafting a polar group-containing unsaturated compound to a ring structure-containing polymer is excellent in adhesion to other materials, so that the resin composition of the present invention is used as an anisotropic conductive material, for example, a coating film Or when using in sheet form, it is particularly preferable. In this case, the resin may be cured or may be left uncured.

More specifically, examples of the graft modified product of the ring structure-containing polymer include those obtained by subjecting a ring structure-containing polymer to a graft reaction with a polar group-containing olefin compound as a polar group-containing unsaturated compound. Can be Examples of the polar group include a hetero atom and 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, a halogen atom and the like, and from the viewpoint of adhesion and reactivity, 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,
Examples include a silanol group, a silyl group, an amino group, a nitrile group, a sulfone group, and an amide group. Among these,
Epoxy groups, hydroxyl groups, carboxyl groups, ester groups, silanol groups,
A carbonyloxycarbonyl group and the like are preferable, and an epoxy group, a hydroxyl group, and a carboxyl group are particularly preferable in terms of adhesion.

Specific examples of the polar group-containing olefin compound include, for example, 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-en-2-methyl-2,3
Epoxy group-containing olefin compounds such as dicarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl ether of o-allylphenol, glycidyl ether of m-allylphenol, and glycidylether of p-allylphenol; acrylic acid;
Methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, endo-cis-bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboxylic acid, methyl-endo-cis-bicyclo [2.2.1] hept-
Carboxyl group-containing olefin compounds such as 5-ene-2,3-dicarboxylic acid; carboxoxycarbonyl group-containing olefin compounds such as maleic anhydride, chloromaleic anhydride, butenylsuccinic anhydride, tetrahydrophthalic anhydride and citraconic anhydride; Ester group-containing olefin compounds such as monomethyl maleate, dimethyl maleate and glycidyl maleate; allyl alcohol, 2-allyl-6-methoxyphenol, 4-allyloxy-2-
Hydroxybenzophenone, 3-allyloxy-1,2-
Hydroxyl group-containing olefin compounds such as propanediol, 2-allylphenol, 3-buten-1-ol, 4-penten-1-ol and 5-hexen-1-ol; chlorodimethylvinylsilane, trimethylsilylacetylene, 5-trimethylsilyl- 1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol,
Trimethylsilyl methacrylate, 1-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-cyclopentene, 2-trimethylsilyloxyethyl methacrylate, 2-trimethylsilyloxyfuran, 2
-Silyl group-containing olefin compounds such as -trimethylsilyloxypropene, allyloxy-t-butyldimethylsilane, and allyloxytrimethylsilane.
Among these, an epoxy group-containing olefin compound and a carboxoxycarbonyl group-containing olefin compound are preferable for obtaining a graft-modified product having a high modification rate. Each of these polar group-containing olefin compounds, alone,
Alternatively, two or more kinds can be used in combination.

The graft reaction of the polar group-containing unsaturated compound onto the ring structure-containing polymer can be carried out by a conventionally known method, and is usually carried out in the presence of a radical initiator. The reaction is carried out by reacting with a contained unsaturated compound. 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 (peroxidebenzoate) hexyne- 3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butyl
Butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpiparate, cumyl perpiparate and tert-butyl perdiethyl acetate Can be mentioned. 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 usage ratio of the radical initiator is usually 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the unmodified ring structure-containing polymer. It is in the range of parts by weight. The graft modification reaction is not particularly limited, and can be performed according to a conventional method.
The reaction temperature is generally 0 to 400 ° C, preferably 60 to 35 ° C.
At 0 ° C., the reaction time is usually in the range of 1 minute to 24 hours, preferably 30 minutes to 10 hours.

The graft modification rate of the graft modified product of the ring structure-containing polymer resin used in the present invention is appropriately selected according to the purpose of use, but is usually 0 based on the total number of monomer units in the polymer. 0.1 to 100 mol%, preferably 1 to 100 mol%
It is in the range of 80 mol%, more preferably 5 to 50 mol%. When the rate of graft modification of the modified norbornene-based polymer is within this range, the dielectric constant and the peel strength (adhesion) between the metal layer and the metal layer are highly balanced, which is preferable. 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 modified groups in the polymer due to the grafted unsaturated compound Y: total number of monomer units of the polymer X is a graft monomer It can be referred to as the total number of moles of the denatured residue, and can be measured by ¹ H-NMR. Y
Is equal to the weight average molecular weight (Mw) of the polymer / molecular weight of the monomer. In the case of copolymerization, the molecular weight of the monomer is
The average molecular weight of the monomer.

The graft-modified product (for example, graft-modified norbornene-based polymer) of the present invention comprises a ring structure-containing polymer (for example, norbornene-based polymer) as a trunk polymer,
It is a graft-modified polymer in which a polar group-containing unsaturated compound is graft-bonded to this backbone polymer. The repeating unit of the graft portion is determined by the type of the graft monomer (polar group-containing unsaturated compound). In the present invention, a polymer having a ring structure having an active hydrogen-containing polar group such as a hydroxyl group or a carboxyl group is particularly preferable because of excellent adhesion to other materials. Such a ring structure-containing polymer having an active hydrogen-containing polar group can be obtained, for example, by graft-modifying an unsaturated epoxy compound, an unsaturated carboxylic anhydride compound, or an unsaturated ester compound, and then (a) converting the active hydrogen-containing compound to an unsaturated hydrogen compound. It can also be obtained by a method such as a method of reacting, or a method of reacting (b) an alkali metal salt or an alkaline earth metal salt of an active hydrogen-containing compound, followed by hydrolysis.

The active hydrogen-containing compound is not particularly limited as long as it is a substance capable of nucleophilic attack on electropositive carbon, and at least one compound selected from the group consisting of a hydroxyl group, an amino group, a mercapto group and a carboxyl group. Compounds having a functional group are preferably used. Specifically, water; ammonia; methanol, ethanol, 1-propanol, 2-propanol, allyl alcohol,
-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,
Alcohols such as -methyl-3-buten-1-ol, cyclopentanol, 1-hexanol, cyclohexanol, geraniol, citronellol, benzyl alcohol, furfuryl alcohol, ethylene glycol, propylene glycol, and glycerin; monomethylamine, monoethylamine , N-propylamine, i-propylamine, cyclopentylamine, cyclohexylamine, geranylamine, benzylamine, aniline, ethanolamine, diethylamine, diphenylamine,
Amines such as diisopropylamine, di-n-butylamine, piperidine and pyrrolidine; methanethiol, ethanethiol, benzenethiol, thiophenol, mercaptoacetic acid, 2-mercaptonicotic acid, 2-mercaptobenzoic acid, 3- Mercaptopropionic acid, 2-mercaptopropionic acid, mercaptosuccinic acid, N-
Thiols such as (2-mercaptopropionyl) glycine; 2-amino-2-norbornanecarboxylic acid, 2-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 5-amino-2 -Naphthalene sulphonic acid, 8-amino-2-naphthalene sulphonic 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-thiazoleacetic acid, 1-amino-1-cyclohexanecarboxylic acid, 1-amino-1-cyclopentanecarboxylic acid, 1-amino-1-cyclopropanecarboxylic Acid, isonipecotic acid,
Amino acids such as nicopetic acid, pipecolic acid, and 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 to 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, it is in the range of 0.5 to 20 equivalents. The reaction of the active hydrogen-containing compound may be performed according to a conventional method.After the completion of the graft reaction, the graft-modified polymer may be isolated and reacted, or the active hydrogen-containing compound may be directly added to the reaction solution after the completion of the graft reaction. It can also be reacted. The reaction conditions are such that the reaction temperature is usually 0 to 250 ° C., preferably 50 ° C.
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 of the above-mentioned active hydrogen-containing compound such as lithium, sodium, potassium and calcium salts. The alkali metal salt or alkaline earth metal salt reaction of the active hydrogen-containing compound may be performed according to a conventional method.After the completion of the grafting reaction, the graft-modified polymer may be isolated and reacted, or the reaction solution after the completion of the grafting reaction may be used. The reaction can also be carried out by directly adding an active hydrogen-containing compound. The reaction conditions are such that the reaction temperature is usually -5.
The reaction time is usually 0 minute 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 of the alkali metal salt or the alkaline earth metal salt of the active hydrogen-containing compound. The hydrolysis reagent is not particularly limited, and for example, water, diluted hydrochloric acid, a saturated aqueous solution of ammonium chloride, and organic acids can be used. In the hydrolysis reaction, the reaction temperature is usually -50C to 10C.
0 ° C., preferably 0 to 50 ° C., and the reaction time is usually 1 minute to 2 minutes.
4 hours, preferably 10 minutes to 10 hours.

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

The molecular weight of the polymer having a ring structure (including its graft-modified product) used in the present invention is appropriately selected according to the purpose of use, but it is determined by gel permeation chromatography (GPC) using toluene as a solvent. ) In terms of polystyrene-equivalent weight average molecular weight (Mw), which is usually 1,000 to 1,000,000, preferably 5,000.
0 to 500,000, more preferably 8,000 to 25
0000, most preferably 10,000-100,0
00 range. When the weight average molecular weight (Mw) of the ring structure-containing polymer is in this range, the balance between mechanical strength, long-term reliability, adhesiveness, and the like is obtained, which is preferable.

The molecular weight distribution of the polymer having a ring structure used in the present invention is appropriately selected according to the purpose of use. The weight average molecular weight (Mw) and number average molecular weight measured by GPC using toluene as a solvent are selected. Ratio with (Mn) (Mw / Mn)
And usually 5.0 or less, preferably 4.0 or less, and more preferably 3.0 or less. The above weight average molecular weight (M
The range of w) and the molecular weight distribution (Mw / Mn) and the measuring method are suitably adapted to the norbornene-based polymer, but are not limited thereto. In the case of a ring structure-containing polymer whose weight-average molecular weight or molecular weight distribution cannot be measured by the above method, a polymer having a melt viscosity and a degree of polymerization that can form a resin layer by a normal melt processing method is used. Can be.

Microcapsule type conductive filler The microcapsule type conductive filler used in the present invention is formed by forming an insulating resin layer on the surface of conductive particles. For example, nickel, aluminum, silver, copper ,
Metal particles such as tin, lead, gold, zinc, platinum, cobalt, and alloys thereof (eg, solder) coated with an insulating resin, or metal particles coated with resin such as Ni or Au Examples thereof include those in which an insulating resin is coated on the surface of coated resin particles, and those in which an insulating resin is coated on the surface of composite resin particles obtained by combining a resin and metal particles.

As the insulating resin, there are a thermoplastic resin and a thermosetting resin. The method for producing the microcapsule-type conductive filler is not particularly limited, and a known method can be employed. Specifically, a method in which a conductive intermediate layer is provided on a spherical core material resin and an insulating thermoplastic resin is coated thereon, or a method in which the surface of the spherical conductive fine particles is coated with an insulating thermoplastic resin (JP-A-62-176139, JP-A-62-76215, JP-A-63-47943, JP-A-63-5
No. 4,796, JP-A-2-103874, JP-A-2-103875), a method of forming an insulating film of a thermoplastic resin or a thermosetting resin on conductive particle surfaces by plasma polymerization or plasma CVD polymerization ( JP-A-2-103874 and JP-A-2-103875), the monomer is in situ on the surface of the conductive fine particles.
Method of polymerizing and polymerizing and coating (JP-A-4-96981, JP-A-5-320413, JP-A-6-88040, JP-A-8-29995)
Publication).

Examples of the insulating resin include thermoplastic resins such as acrylic resin, styrene resin, acrylic / styrene resin, polyamide resin, and polyurethane resin; epoxy / amine-based cured products, maleimide / amine-based cured products, and divinyl resins. There is a thermosetting resin such as a benzene polymer. It is preferable that these insulating resins have heat resistance enough to withstand the thermocompression bonding temperature between the chip and the substrate. The thickness of the coating layer made of an insulating resin is preferably 3 μm or less. The lower limit of the thickness of the insulating resin layer depends on the manufacturing method, but is usually about 0.05 μm. The shape of the microcapsule-type conductive filler used in the present invention is not particularly limited, but it is preferable that the shape is spherical, granular, or flat so that the surface contact effect between the terminals can be sufficiently obtained by heating and pressing. Is preferred. The average particle size of the microcapsule-type 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 in the range of 1 to 20 µm, more preferably 5 to 15 µm.

These microcapsule-type conductive fillers can be used alone or in combination of two or more. The mixing ratio of the microcapsule-type conductive filler is appropriately selected depending on the purpose of use,
Usually 0.1 to 60 parts by weight per 100 parts by weight of the ring structure-containing polymer.
When the amount is in the range of 0.3 parts by weight, preferably 0.3 parts by weight to 50 parts by weight, and more preferably 1 part by weight to 30 parts by weight, dielectric properties, adhesiveness, and long-term reliability are highly balanced and suitable. If the compounding ratio of the conductive filler is too small, bonding between terminals becomes insufficient, and it is particularly difficult to cope with fine pitch. If the compounding ratio of the conductive filler is too large, there is a possibility that the adhesive strength is reduced or the lateral insulation property is impaired.

Resin Composition The resin composition of the present invention is a resin composition containing a polymer having a ring structure and a microcapsule-type 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 lower, and includes a usual rubbery polymer and a thermoplastic elastomer. In the case where the glass transition temperature of the block copolymerized rubbery polymer or the like is 2 or more, if the lowest glass transition temperature is 40 ° C or lower, the rubbery polymer of the present invention having a glass transition temperature of 40 ° C or lower is used. Can be used as

Examples of the elastomer include isoprene.
Rubber, hydrogenated product thereof; chloroprene rubber, hydrogenated product thereof; ethylene / propylene copolymer, ethylene / α-
Saturated polyolefin rubber such as olefin copolymer, propylene / α-olefin copolymer; ethylene / propylene / diene copolymer, α-olefin / diene copolymer, diene copolymer, isobutylene / isoprene copolymer, isobutylene Diene copolymers such as diene copolymers, halides thereof, diene polymers or hydrogenated hydrogenated products thereof; acrylonitrile-butadiene copolymers, hydrogenated products thereof; vinylidene fluoride;
Fluoro rubbers such as ethylene trifluoride copolymer, vinylidene fluoride / propylene hexafluoride copolymer, vinylidene fluoride / propylene hexafluoride / ethylene tetrafluoride copolymer, and propylene / tetrafluoroethylene copolymer Special rubbers such as urethane rubber, silicone rubber, polyether rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, and ethylene acrylic rubber; copolymerization of norbornene monomer and ethylene or α-olefin Norbornene-based rubbers such as coalesced polymers, terpolymers of norbornene-based monomers and ethylene and α-olefins, ring-opened polymers of norbornene-based monomers, ring-opened polymers of norbornene-based monomers, and hydrogenated products Polymers; styrene-butadiene rubber, emulsion-polymerized or solution-polymerized, high-speed steel Random or block styrene / butadiene copolymers such as tylene rubber and hydrogenated products thereof; aromatics such as styrene / butadiene / styrene rubber, styrene / isoprene / styrene rubber, and styrene / ethylene / butadiene / styrene / rubber Random copolymers of vinyl monomers and conjugated dienes, hydrogenated products thereof; styrene / butadiene / styrene / rubber;
Styrene-based thermoplastic elastomers such as linear or radial block copolymers of aromatic vinyl monomers and conjugated dienes such as styrene, isoprene, styrene, rubber, styrene, ethylene, butadiene, styrene, rubber, etc., and their hydrogenated products , Urethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, 1,2-
Thermoplastic elastomers such as a polybutadiene-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, and a fluorine-based thermoplastic elastomer;

Among these, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer and a hydrogenated product thereof are preferable because of their 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, those in which a portion other than the aromatic ring is hydrogenated are more preferable. In particular,
Styrene / butadiene block copolymer, styrene / butadiene / styrene / block copolymer, styrene / isoprene / block copolymer, styrene / isoprene /
Styrene block copolymer, styrene butadiene
Examples thereof include random copolymers 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, ethylene- Polyolefins such as ethyl acrylate copolymer and ethylene-vinyl acetate copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate;
Polyamides such as nylon 6 and nylon 66; and other resins such as polycarbonate, polyimide and epoxy resin.

The other polymers can be used alone or in combination of two or more. The compounding ratio of the other polymers is as follows.
100 parts by weight or less, preferably 7 parts by weight,
0 parts by weight or less, more preferably 50 parts by weight or less.
Other compounding agents include, for example, curing agents, curing accelerators, curing assistants, flame retardants, heat stabilizers, weather stabilizers, leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants , Dyes, pigments, natural oils, synthetic oils, waxes, and the like, and the amount thereof is appropriately selected within a range that does not impair the purpose of the present invention. The resin composition of the present invention,
In applications such as flip chip bonding where repairability is required, it is used as a thermoplastic resin composition without blending a curing agent. On the other hand, in applications where high heat resistance and long-term reliability are required, a curable resin composition containing a curing agent, a curing accelerator if necessary, and a curing aid is used.

As the curing agent, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide,
1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide, dicumyl peroxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3,
Organic peroxides such as α, α′-bis (t-butylperoxy-m-isopropyl) benzene, octanoyl peroxide, isobutyryl peroxide, peroxydicarbonate; hexamethylenediamine, triethylenetetramine, diethylenetriamine, tetraethylenepentane Aliphatic polyamines such as min; diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2,6 ] decane; 1,3- (diaminomethyl) cyclohexane, Mensendiamine, isophoronediamine N-aminoethylpiperazine, bis (4-
Amino-3-methylcyclohexyl) methane, bis (4
Alicyclic polyamines such as -aminocyclohexyl) methane; 4,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenylmethane, α, α'-bis (4-aminophenyl) -1,3-diisopropylbenzene,
Aromatic polyamines such as α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 4,4'-diaminodiphenylsulfone, metaphenylenediamine, and metaxysilylenediamine; 4,4-bisazidobene Monkey (4-methyl) cyclohexanone, 4,4'-
Diazido chalcone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) -4-methyl-cyclohexanone, 4,4'-
Bisazides such as diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, 2,2'-diazidostilbene; phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, nadic 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 '-
Diols such as butanediol, hydroquinone dihydroxy diethyl ether, tricyclodecane dimethanol;
Triols such as 1,1,1-trimethylolpropane;
Polyphenols such as phenol novolak resin and cresol novolak resin; nylon-6, nylon-6
6, Nylon-610, Nylon-11, Nylon-6
12, polyamides such as nylon-12, nylon-46, methoxymethylated polyamide, polyhexamethylenediamine terephthalamide, and polyhexamethyleneisophthalamide; diisocyanates such as hexamethylene diisocyanate and toluylene diisocyanate; These curing agents can be used alone or in combination of two or more. The mixing 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, based on 100 parts by weight of the ring structure-containing polymer.

As the curing accelerator, for example, pyridine,
Examples include amines such as benzyldimethylamine, triethanolamine, triethylamine, tributylamine, tribenzylamine, dimethylformamide, and imidazole. These curing accelerators can be used alone or in combination of two or more. The compounding ratio of the curing accelerator is as follows.
It is usually in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 00 parts by weight.

The curing aid is not particularly limited, but may be any of those known in JP-A-62-34924, and examples thereof include quinone dioxime, benzoquinone dioxime and p-nitrosophenol. An oxime / nitroso curing aid; a maleimide curing aid such as N, Nm-phenylenebismaleimide; an allyl curing aid such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate; ethylene glycol dimethacrylate; Methacrylate-based curing aids such as trimethylolpropane trimethacrylate; vinyl-based curing aids such as vinyltoluene, ethylvinylbenzene, and divinylbenzene; and the like. These curing aids can be used alone or in combination of two or more. The mixing ratio of the curing aid is usually 1 to 1,000 parts by weight, preferably 10 to 5 parts by weight, per 100 parts by weight of the curing agent.
It is in the range of 00 parts by weight. The resin composition of the present invention can be used by mixing the above components according to a conventional method.

Form of Use The form of use of the resin composition of the present invention may be appropriately selected according to the purpose of use. When the resin composition is used for bonding fine uneven surfaces such as precision electronic parts, a varnish (anisotropic conductive material) is used. It is preferable to use it in the form of an adhesive) or a sheet (anisotropic conductive sheet). The varnish of the present invention is prepared by dissolving or dispersing the resin composition in an organic solvent. As an organic solvent,
There is no particular limitation as long as each component can be dissolved or dispersed. Examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; n-pentane, hexane,
Aliphatic hydrocarbons such as heptane; alicyclic hydrocarbons such as cyclohexane; chlorobenzene, dichlorobenzene,
Halogenated hydrocarbons such as trichlorobenzene; ketones such as methyl ethyl ketone, 2-pentanone and cyclohexanone; ethers; alcohols; These organic solvents may be used alone or
Used in combination of more than one species. The amount of organic solvent used is
The cyclic structure-containing polymer, the microcapsule-type conductive filler, and the other components contained as necessary may be in a quantity ratio sufficient to uniformly dissolve or disperse, but usually, the solid content concentration is 1 to 80. % By weight, preferably 5 to 60
%, More preferably 10 to 50% by weight.

The sheet (anisotropic conductive sheet) of the present invention comprises
It can be obtained by molding the resin composition. The method for forming the sheet may be a conventional method, for example, a method in which the varnish is applied to a smooth surface such as a mirror-finished metal plate or a resin carrier film, and then 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 in the range of 1 to 1,000 μm, preferably 5 to 500 μm, more preferably 10 to 100 μm. Reliability is highly balanced and preferred.

Form of Use The resin composition of the present invention is typically used as an anisotropic conductive material for bonding and joining electronic parts. As a method for bonding the adherends, for example, (1) after applying the varnish of the present invention to one adherend, drying the solvent to form a coating film (anisotropic conductive layer); And (2) laminating the sheet (anisotropic conductive sheet) of the present invention on one adherend, and applying the other adherend thereon. After installation, a method of heating and press-bonding may be used.

The heating and pressing conditions are such that the heating temperature is usually 150 to
The temperature is usually 250 ° C., the pressure is usually 20 to 40 kg / cm ² , and the heating and pressing time is usually about 10 to 60 seconds. A heater or a laser is used for heating. When heat and pressure are applied, pressure is applied to the conductive part, the insulating resin layer of the microcapsule-type conductive filler is broken, and the conductive part is conductive, and the microcapsule-type conductive filler remains as it is in other insulating parts. And stable insulation can be maintained. In FIG.
A lead 4 of a TCP (tape carrier package) 3;
The cross-sectional structure in the case where a coating film (anisotropic conductive film) made of resin 1 in which microcapsule-type conductive filler 2 is dispersed is used for bonding and bonding to electrode 6 of a liquid crystal panel (LCD panel). ing. When an anisotropic conductive film is formed on the surface of the TCP and heated and pressed against the LCD panel, pressure is applied to the conductive portion, the microcapsule type conductive filler is crushed, and the insulating resin layer is broken. Since the microcapsule-type conductive filler exists as it is in the conductive portion and in the other insulating portions, the lateral insulating property is maintained.

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

[0056]

The present invention will be more specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. [Parts] and [%] in these examples are, unless otherwise specified.
Based on weight. The measuring method is as follows. (1) The glass transition temperature was measured by the DSC method. However, in the case of a thermosetting resin, a film is used for TMA.
It was measured by the method. (2) Number average molecular weight (Mn) and weight average molecular weight (M
w) is a GP using toluene as a solvent unless otherwise specified.
It was measured as a polystyrene equivalent value by the C method. (3) Both the hydrogenation rate of the main chain and the modification rate of the polymer were measured by ¹ H-NMR. (4) The dielectric constant and dielectric loss tangent at 1 MHz are determined according to JIS.
It was measured according to 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, and the degree of increase in connection resistance was examined. <Initial> ：: 10 Ω or less, ：: 20 Ω or less, Δ: 30 Ω or less, ×: 50 Ω or more. <After PCT> ：: 10 Ω or less, ：: 20 Ω or less, Δ: 30 Ω or less, ×: 50 Ω or more.

[0057] [Synthesis Example 1] tungsten hexachloride, triisobutylaluminum, and using a polymerization catalyst system comprising isobutyl alcohol, by methods known 8-ethyl-tetracyclo [4.4.1 ^{2,5. 17,10} . 0] -3-dodecene (hereinafter abbreviated as ETD), and then subjected to a hydrogenation reaction by a known method using a hydrogenation catalyst system comprising nickel acetylacetonate and triisobutylaluminum. A combined hydrogenated product was obtained. Maleic anhydride 2 was added to 100 parts of the obtained hydrogenated polymer.
Parts, 1 part of dicumyl peroxide and 300 parts of tert-butylbenzene, and 135 parts in an autoclave.
After reacting at 4 ° C. for 4 hours, the reaction solution was coagulated and dried in the same manner as above to obtain a maleic anhydride-modified polymer. For 100 parts of the obtained maleic anhydride-modified polymer,
3 parts of isopropyl alcohol was added, and a decomposition reaction was performed 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 was 30%. Using this solution, 125
200-300 μm in thickness on a polyethylene terephthalate (PET) film with a doctor blade
And dried in nitrogen at 160 ° C. for 1 hour to obtain a sheet having a thickness of 50 to 70 μm. Table 1 shows the physical properties of the obtained sheet.

[Synthesis Example 2] A maleic anhydride-modified polymer (B) was prepared 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. Was obtained. Table 1 shows the physical properties.

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 obtained 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. Table 1 shows the physical properties.

[Synthesis Example 4] To 80 parts by weight of toluene, 100 parts by weight of an epoxy resin (Epicoat 1009, manufactured by Yuka Shell Epoxy) and 170 parts by weight of HX3941HP (manufactured by Asahi Kasei Corporation) as a curing agent were added. Was prepared. This was dried to obtain a sheet having a thickness of 25 μm. Table 1 shows the physical properties when the sheet was hard baked at 180 ° C. for 2 hours.

[0061]

[Table 1] (Footnotes) (1) ETD: 8-ethyltetracyclododecene (2) Allyl glycidyl ether ring opening: Alcohol modification with epoxy group opening

[Synthesis Example 5] A hybridization system (manufactured by Nara Machine Co., Ltd.) in which an acrylic / styrene resin was mixed with Ni particles having an average particle diameter of 7 μm at a ratio of 5: 100.
The microcapsule-type conductive particles in which a coating having a thickness of 0.1 to 0.2 μm was formed on the Ni particles were obtained by treating the particles at 16200 rpm for 10 minutes using the above method.

Synthesis Example 6 N was added to silica having an average particle size of 5 μm.
Using i / Au-plated particles, microcapsule-type conductive particles having an acrylic / styrene resin film having a thickness of 0.1 to 0.2 μm were obtained in the same manner as in Synthesis Example 5.

[Synthesis Example 7] Benzoguanamine resin having an average particle size of 5 μm (Bright 20GNRY4.
6EH), microcapsule-type conductive particles having an acrylic / styrene resin film having a thickness of 0.1 to 0.2 μm were obtained in the same manner as in Synthesis Example 5 by using particles obtained by performing Ni / Au plating. .

Example 1 To 100 parts of the polymer (A) obtained in Synthesis Example 1, a microcapsule-type conductive filler was added at the compounding ratio shown in Table 2, and the resin component amount was reduced to 30%. % 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) having silicon as a base was heated and pressed at 200 ° C. for 30 seconds to bond the semiconductor component onto the glass epoxy substrate. 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.

[Examples 2 to 5] Sheets were prepared in the same manner as in Example 1 except that the polymers and the microcapsule type conductive fillers shown in Table 2 were used in the mixing ratio shown in Table 2, and a high-temperature sheet was prepared. A high humidity test was performed. The evaluation results are shown in Table 2, and all the samples showed excellent results.

[Comparative Examples 1 to 3] The epoxy resin varnish prepared in Synthesis Example 4 was mixed with the microcapsule-type conductive filler shown in Table 2, and a semi-cured sheet was produced in the same manner as in Example 1. . Using the sheet before hard baking produced in this manner, a semiconductor component was pressed on a glass epoxy substrate in the same manner as in Example 1. The evaluation results are shown in Table 2, and in all cases, the connection resistance after the high-temperature and high-humidity test was 50%.
Ω or more, resulting in poor conduction.

[0068]

[Table 2]

[0069]

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

[Brief description of the drawings]

FIG. 1 is an explanatory diagram relating to adhesion and bonding between a TCP and a liquid crystal panel using an anisotropic conductive film.

[Explanation of symbols]

 1. Resin 2. 2. Microcapsule type conductive filler TCP 4. Lead 5. Liquid crystal panel 6. electrode

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 71/12 C08L 71/12 81/00 81/00 101/02 101/02 C09D 5/24 C09D 5/24 C09J 7/00 C09J 7 / 00 145/00 145/00 // H05K 3/32 H05K 3/32 B 3/36 3/36 A

Claims (4)

[Claims] 1. A resin composition comprising a ring structure-containing polymer and a microcapsule-type conductive filler in which the surface of conductive particles is coated with an insulating resin is dispersed. 2. The resin composition according to claim 1, which is an anisotropic conductive material. 3. A varnish obtained by dissolving or dispersing, in an organic solvent, a ring structure-containing polymer and a microcapsule-type conductive filler in which the surface of conductive particles is coated with an insulating resin. 4. A sheet comprising a resin composition obtained by dispersing a microcapsule-type conductive filler in which conductive particles are coated with an insulating resin in a ring structure-containing polymer.