JP2010077235A - Conductive resin film and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive resin film having low volume resistivity, high mechanical strengths such as tear strength, and high resistance to electrolytes containing an organic solvent. <P>SOLUTION: This conductive resin film includes (1) 100 pts.mass of a resin component which contains (a) 90-100 mass% of a cyclic olefinic resin and (b) 10-0 mass% of a hydrogenated product of an aromatic vinyl-conjugated diene block copolymer, (2) 15-50 pts.mass of a conductive filler, and (3) 5-40 pts.mass of a glass fiber. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive resin film having a small volume resistivity, high mechanical strength such as tear strength, and high resistance to an electrolytic solution containing an organic solvent, and a method for producing the same.

As electric parts using an electrolytic solution containing an organic solvent, there are an electric double layer capacitor and a lithium ion battery. Electrolytic solutions for electric double layer capacitors are broadly classified into organic solvent-based electrolyte solutions and water-based electrolyte solutions. Generally, since the output voltage of an electric double layer capacitor using an organic solvent electrolyte is high, it is widely used.
The electric double layer capacitor has advantages such as a long cycle life and rapid charge / discharge, and is used as a backup power source for microcomputers, memory devices, timers and the like. An actual electric double layer capacitor has the following structure. An external lead wire is attached to an etched current collector having a thickness of 20 to 40 μm, and a polarizable electrode made of an electrode material containing activated carbon, a conductive agent, a binder, or the like is formed on the etched surface of the current collector. Has been. A collector having a polarizable electrode formed on the current collector is wound with a separator interposed therebetween to form a capacitor element. The capacitor element is immersed in the electrolytic solution, and the electrolytic solution is applied to the separator and the polarizable electrode. The impregnated material is inserted into the exterior material, and the opening of the exterior material is sealed by packing. The performance of the electric double layer capacitor is improved as the output per weight and the output per capacity are higher. Generally, a metal foil such as aluminum is used as a current collector, but the output per weight of an electric double layer capacitor in which a conductive resin film or a conductive elastomer film having a specific gravity smaller than that of a metal is used as a current collector is The output per unit weight of the electric double layer capacitor in which the metal is used as the current collector can be larger.
Further, like an electric double layer capacitor using an organic solvent electrolyte, a lithium ion battery also contains an organic solvent in the electrolyte. A lithium ion battery has the same structure as an electric double layer capacitor, and uses a metal foil such as copper or aluminum as a current collector. Therefore, it collects a conductive resin film or a conductive elastomer film having a specific gravity smaller than that of the metal. When used as a body, the output per unit weight can be larger than a lithium ion battery using a metal current collector.

Conventionally, a conductive elastomer film containing a vinyl aromatic hydrocarbon-conjugated diene block copolymer or a hydrogenated product thereof and a conductive filler has been studied as a current collector of an electric double layer capacitor using an aqueous electrolyte ( For example, see Patent Document 1). The strength of the conductive elastomer film is greatly reduced by an organic solvent such as diethyl carbonate contained in the organic solvent electrolyte. On the other hand, a conductive resin film containing a cyclic olefin resin and a conductive filler has been studied as a current collector of an electric double layer capacitor (see, for example, Patent Document 2). However, the tear strength of the conductive resin film was low.
International Publication No. 98/40435 Pamphlet International Publication No. 99/02585 Pamphlet

In a lithium ion battery, it is known that an active material expands and contracts during charging and discharging, and a conductive resin film or a conductive elastomer film is suitable as a current collector in terms of output per unit weight. However, until now, no conductive resin film or conductive elastomer film having high resistance to an organic solvent electrolyte has been found.
In addition, a conductive resin film or a conductive elastomer film having a small volume resistivity value, a high mechanical strength such as a tearing strength, and a high resistance to an electrolytic solution containing an organic solvent is used. Although it is calculated | required also as an electrical power collector of an electrical double layer capacitor, such a conductive resin film or a conductive elastomer film has not been found until now.

  Therefore, the problem to be solved by the present invention is to provide a conductive resin film having a small volume resistivity value, a high mechanical strength such as a tear strength, and a high resistance to an electrolytic solution containing an organic solvent.

  The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, (1) (a) a cyclic olefin resin and optionally contained (b) an aromatic vinyl-conjugated diene block copolymer. The present invention is completed by finding that a resin component comprising a hydrogenated product of (2), a conductive resin composition containing a conductive filler, and (3) a film obtained by solvent casting glass fiber solves the above-mentioned problems. It came to.

  The present invention comprises (1) (a) 90 to 100% by mass of a cyclic olefin resin and (b) 100 parts by mass of a resin component comprising 10 to 0% by mass of a hydrogenated aromatic vinyl-conjugated diene block copolymer. 2) Provide the conductive resin film containing 15-50 mass parts of conductive fillers, and (3) 5-40 mass parts of glass fiber.

  The (a) cyclic olefin resin is preferably a ring-opening polymer of a monomer having a norbornene ring or a hydrogenated product thereof. The hydrogenated product of the (b) aromatic vinyl-conjugated diene block copolymer is preferably a styrene-ethylene-butene-styrene block copolymer. The conductive filler is preferably carbon black. The conductive resin film preferably has a thickness of 10 to 200 μm.

  The present invention comprises (1) (a) 90 to 100% by mass of a cyclic olefin resin and (b) 100 parts by mass of a resin component comprising 10 to 0% by mass of a hydrogenated aromatic vinyl-conjugated diene block copolymer. 2) A conductive resin composition containing 15 to 50 parts by weight of a conductive filler, (3) 5 to 40 parts by weight of glass fiber, and (4) 100 to 1000 parts by weight of a solvent is coated on a substrate and then dried. The manufacturing method of the conductive resin film characterized by this is also provided.

  The conductive resin film of the present invention has a small volume resistivity, high mechanical strength such as tear strength, and high resistance to an electrolyte containing an organic solvent.

  The conductive resin film of the present invention contains a cyclic olefin resin. The cyclic olefin resin is an amorphous resin having an aliphatic hydrocarbon ring structure in the main chain or side chain of the polymer. Specific examples thereof include JP-A 63-264646 and JP-A 64-. No. 1705, JP-A-1-168724, JP-A-1-168725, etc., a ring-opening polymer of a monomer having a norbornene ring and its hydrogenated product, JP-A-60-168708, etc. Addition polymers of a monomer having a norbornene ring and α-olefins disclosed, addition polymers of cyclic olefins and cyclic dienes disclosed in JP-A Nos. 6-136057 and 7-258362, and the like, and Examples thereof include hydrogenated products. These cyclic olefin resins are commercially available. Specific examples of commercially available products are ZEONEX (registered trademark) manufactured by ZEON CORPORATION, APEL (registered trademark) manufactured by Mitsui Chemicals, Inc., APO (registered trademark), and Polyplastics Corporation. For example, TOPAS (registered trademark). Among these, a ring-opening polymer of a monomer having a norbornene ring and a hydrogenated product thereof are preferable from the viewpoint of film forming property, chemical resistance, etc., and a hydrogenated product of a ring-opening polymer of a monomer having a norbornene ring is particularly preferable. preferable.

  The monomer having a norbornene ring includes a bicyclic olefin norbornene which is an adduct of ethylene and cyclopentadiene, and a tetracyclic olefin tetracyclododecene and cyclopentadiene which are added by cyclopentadiene and a tricyclic ring. Tricyclodecadiene (also called dicyclopentadiene) which is a diene of formula, tricyclodecene which is a tricyclic olefin in which a part of its unsaturated bond is saturated by hydrogenation, and a pentamer of cyclopentadiene. Pentacyclopentadecadiene, which is a diene, pentacyclopentadecene (also called 2,3-dihydrodicyclopentadiene), which is a pentacyclic olefin in which a part of its unsaturated bond is saturated by hydrogenation; and substitution thereof Examples include bodies. Examples of the substituent include a derivative substituted with a group having no polar group such as an alkyl group, an alkylidene group or an aromatic group, a hydrogenated derivative, or a derivative obtained by dehydrogenation thereof (for example, 2-norbornene, 5 -Methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-hexyl-2-norbornene, 5 -Norbornene derivatives such as phenyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene, 5-ethylidene-2-norbornene, 1,4: 5,8-dimethano-1,2,3 4,4a, 5,8,8a-2,3-cyclopentadienooctahydronaphthalene, 6-methyl-1 4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4 4a, 5,5a, 6,9,9a, 10,10a-tetracyclododecene derivatives such as dodecahydro-2,3-cyclopentadienoanthracene); halogen, hydroxyl group, ester group, alkoxy group, cyano group, Substitutes substituted with polar groups such as amide group, imide group, silyl group (for example, 5-methoxy-carbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2- Norbornene, etc.);

  Specific examples of the α-olefin that is addition-copolymerized with a monomer having a norbornene ring include olefins in a narrow sense such as ethylene, propylene, 1-butene, 4-methylpentene-1, and a part of these α-olefins such as halogen. Examples include olefinic monomers substituted with polar groups.

  Cyclic olefins include cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclohexene, cyclooctene, 1-methylcyclooctene, 5-methylcyclo Examples include monocyclic cycloolefins such as octene, cyclooctatetraene, and cyclododecene, and monomers having one unsaturated bond among the above-described monomers having a norbornene ring.

  Examples of the cyclic diene include monocyclic dienes such as cyclopentadiene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene, and those having two unsaturated bonds among the monomers having the norbornene ring.

  Among these monomers, a monomer having no polar group is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more in all monomers, and the resulting conductivity is obtained. The resin film has excellent resistance to chemicals such as ethylene carbonate.

  Furthermore, in any of the above ring-opening polymerization and addition polymerization, various types of copolymerizable monomers may be mixed and copolymerized in each polymerization system. Examples of the copolymerizable monomer include linear or branched dienes such as butadiene and isoprene, in addition to the monomer having a norbornene ring, an α-olefin, a cyclic olefin, and a cyclic diene. The polymerization may be random, block type, or alternating type, and either 1,2-addition or 1,4-addition may be the main in addition polymerization. The ratio may be approximately the same.

  When the unsaturated bond remains in the polymer after polymerization, that is, in the case of a ring-opening polymer of a monomer having a norbornene ring or an addition polymer of a cyclic diene, the conductive resin film obtained by the residual unsaturated bond Therefore, it is preferable to saturate 80% or more, preferably 90% or more of the unsaturated bonds by hydrogenation for the purpose of improving the chemical resistance. Any known hydrogenation method and catalyst may be used.

  The molecular weight of the polymer is, for example, a number average molecular weight (Mn) in terms of polyisoprene measured by gel permeation chromatography using cyclohexane as a solvent, preferably 3,000 to 500,000, more preferably 8,000. The weight average molecular weight (Mw) is preferably 8,000 to 1,000,000.

  It is preferable to remove or reduce residues such as catalyst from the polymer solution after polymerization or after hydrogenation by a known method. The solvent is removed by filtration and then dried by heating or vacuum heating, or the resin solution from which metal contaminants have been removed by precipitation aggregation is directly heated or vacuum heated to remove the solvent. May be. When the solvent is a solvent suitable for producing the conductive resin film of the present invention, it can be used without removing the solvent or by removing a part thereof. Further, the solvent can be substituted with a solvent for film production without drying.

  The glass transition temperature of the cyclic olefin resin (hereinafter sometimes referred to as Tg) varies depending on the type of monomer, the proportion of comonomer when copolymerized, the molecular weight, the hydrogenation rate, etc., but as a resin for conductive resin films When used, it is preferably −150 to + 300 ° C., more preferably −120 to + 200 ° C., and particularly preferably −100 to + 120 ° C. When it is in this range, the flexibility, strength, and heat resistance of the obtained conductive elastomer film are highly balanced and preferable. In the present invention, Tg is a value measured by a differential scanning calorimeter (DSC).

The conductive resin film of the present invention may contain a hydrogenated aromatic vinyl-conjugated diene block copolymer.
Specific examples of the aromatic vinyl compound constituting the aromatic vinyl-conjugated diene block copolymer are styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, divinyl. Examples thereof include benzene, N, N-dimethyl-p-aminoethylstyrene, 2,4-dimethylstyrene, N, N-diethyl-p-aminoethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene and the like. Of these, styrene and α-methylstyrene are particularly preferred aromatic vinyl compounds. One or more aromatic vinyl compounds are used.

  Specific examples of the conjugated diene compound constituting the aromatic vinyl-conjugated diene block copolymer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl. -1,3-pentadiene, 1,3-hexadiene, 4,5-dimethyl-1,3-octadiene, chloroprene and the like. Of these, 1,3-butadiene and isoprene are particularly preferred conjugated diene compounds. One or more conjugated diene compounds are used.

  The content of the aromatic vinyl compound unit in the aromatic vinyl-conjugated diene block copolymer is usually 5 to 80% by mass, preferably 10 to 70% by mass, and more preferably 20 to 60% by mass.

  Specific examples of the aromatic vinyl-conjugated diene copolymer include an aromatic vinyl compound polymer block (P) and a conjugated diene polymer block (Q), and the block structure is (PQ) nP or (P -Q) A block copolymer represented by m (where n is an integer of 1 or more, preferably an integer of 1 to 10, and m is an integer of 1 or more, preferably an integer of 2 to 10). Specific examples of the hydrogenated aromatic vinyl-conjugated diene copolymer include styrene-ethylene-butene-styrene block copolymer (SEBS); styrene-ethylene-propylene-styrene block copolymer (SEPS); , S: styrene, E: ethylene, B: butene, P: propylene). Of these, styrene-ethylene-butene-styrene block copolymer (SEBS) is particularly preferable.

The weight average molecular weight of the aromatic vinyl-conjugated diene block copolymer is preferably in the range of 5,000 to 1,000,000, more preferably 10,000 to 500,000.
The hydrogenated aromatic vinyl-conjugated diene copolymer is preferably 80 to 99.9 mol% of unsaturated double bonds in the polymer chain, more preferably 90 to 99.9 mol%, still more preferably. 95 to 99.9 mol% is hydrogenated. The hydrogenated aromatic vinyl-conjugated diene block copolymer is commercially available, and specific examples thereof include Clayton (registered trademark) G series such as Clayton (registered trademark) G1650M and Clayton (registered trademark) G1657M manufactured by Kraton Japan. Asahi Kasei Chemicals Corporation Tuftec (registered trademark) H1031, Tuftec (registered trademark) H1051 and other Tuftec (registered trademark) H series; Kuraray Co., Ltd. Septon (registered trademark) 2002, Septon (registered trademark) 2004 and other septon ( Registered trademark) series;

  The mass ratio of the aromatic vinyl-conjugated diene block copolymer in the resin component containing the cyclic olefin resin is 0% by mass to 10% by mass, preferably 1% by mass to 8% by mass. When the mass ratio of the aromatic vinyl-conjugated diene block copolymer is too high, the electrolytic solution resistance is poor. On the other hand, by blending an appropriate amount of the above-mentioned aromatic vinyl-conjugated diene block copolymer, the tensile strength and tensile elongation performance can be improved.

  The mass ratio of the said cyclic olefin resin in the resin component containing the said cyclic olefin resin is 90-100 mass%, Preferably it is 92 mass%-99 mass%. When the mass ratio of the cyclic olefin resin is too low, the electrolytic solution resistance is poor.

  The conductive resin film of the present invention contains a conductive filler. Specific examples of the conductive filler include carbon black, graphite, powder or fibrous metal or metal oxide.

Specific examples of the carbon black include furnace blacks such as conductive furnace black, super conductive furnace black, and extra conductive furnace black; conductive channel black; acetylene black and the like. Specific examples of commercially available conductive carbon black include Connexex CF (Conductive Furnace Black manufactured by Continental Carbon Co., Ltd.), Ketjen Black EC (Conductive Furnace Black manufactured by Ketchen Black International Co., Ltd.), and Vulcan C (Cabot Corporation). Such as Conductive Furnace Black), BLACK PEARLS 2000 (Conductive Furnace Black manufactured by Cabot), Denka Black (acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd.), and the like. DBP oil absorption of carbon black is 300 cm ^3/100 g or more, and a BET surface area is 500 meters ² / g or more.

Specific examples of graphite include scale-like natural graphite, artificial graphite, graphite fiber, and the like.
Specific examples of the metal are iron, copper, nickel, aluminum, titanium, tantalum, niobium, vanadium and any alloy containing two or more thereof.

  The said conductive filler can be used individually or in combination of at least 2 types. Content of an electroconductive filler is 5-50 mass parts with respect to 100 mass parts of resin components containing the said cyclic olefin resin, Preferably it is 10-40 mass parts. When there is too little content of an electroconductive filler, the resistance value of a film is too high and the electroconductivity of a film becomes low. On the other hand, when there is too much content of an electroconductive filler, a resin composition cannot be made into a film.

  The conductive resin film of the present invention contains glass fibers. The glass fiber may be a glass fiber that is commercially available for resin. Specific examples of the form of the glass fiber include a stable, a filament, a cord, a rope, and a canvas. The glass composition which comprises the said glass fiber is not limited to a specific composition. Specific examples of the glass composition include E-glass and high-strength glass. The filament diameter of the glass fiber is not limited to a specific range. The filament diameter is generally 5 to 13 μm. The fiber length of the glass fiber is not limited to a specific range.

  Content of glass fiber is 5-40 mass parts with respect to 100 mass parts of resin components containing the said cyclic olefin resin, Preferably it is 10-30 mass parts. If the glass fiber content is too small, the effects of the present invention cannot be obtained. On the other hand, when there is too much content of glass fiber, a resin composition cannot be made into a film.

The conductive resin film of the present invention may contain various compounding agents usually used in the resin industry field.
The conductive resin film of the present invention may contain a stabilizer. Specific examples of the stabilizer include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and the like. Among these, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants are particularly preferable. These stabilizers may be used alone or in combination of two or more. Although the compounding quantity of a stabilizer is suitably selected according to a use purpose, it is the range of 0.001-10 mass parts normally with respect to 100 mass parts of resin components.

  The method for producing a conductive resin film of the present invention comprises (1) (a) 90 to 100% by mass of a cyclic olefin resin and (b) 10 to 0% by mass of a hydrogenated aromatic vinyl-conjugated diene block copolymer. A conductive resin composition comprising 100 parts by mass of a resin component, (2) 15 to 50 parts by mass of a conductive filler, (3) 5 to 40 parts by mass of glass fiber, and (4) 100 to 1000 parts by mass of a solvent is formed on a substrate. It is characterized by coating and then drying. The thickness of the obtained conductive resin film of the present invention is 10 to 200 μm.

  The solvent is a solvent in which the cyclic olefin resin, an optionally used hydrogenated aromatic vinyl-conjugated diene block copolymer, and an optionally used thermoplastic resin are dissolved at room temperature or under heating, It is not limited to a specific solvent. Specific examples of the solvent include aromatic hydrocarbon compounds such as benzene, toluene and xylene; saturation of n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, nonane, decane, decalin, tetralin, dodecane, gasoline, industrial gasoline, etc. Aliphatic and alicyclic hydrocarbon compounds;

  If necessary, a compounding agent such as a softening agent such as paraffinic process oil or naphthenic process oil or an antioxidant may be added to the resin composition as long as the effects of the present invention are not impaired.

  The method for producing the resin composition may be a method of kneading a cyclic olefin resin, a conductive filler, glass fiber and an optional component to be added as needed, or a method of dissolving or dispersing each component in a solvent. obtain.

  If the concentration of the component added to the solvent is too low, a conductive resin film having a sufficient thickness cannot be obtained. Conversely, if the concentration is too high, the viscosity of the resin composition becomes too high, and the conductive resin film The thickness is not uniform.

A method for producing a conductive resin film will be described in more detail. First, the lump and undispersed material in the resin composition are removed with a filter or the like as necessary. Specific examples of the filter to be used include a fiber-like fiber, a metal or the like woven in a mesh shape, or a fine fine hole drilled into a planar material.
Further, defoaming is performed as necessary to remove bubbles contained in the solution. Specific examples of the defoaming method include a vacuum method and an ultrasonic method.

  The prepared solution is formed on a substrate that is a smooth flat surface such as polyethylene terephthalate, Teflon (registered trademark), paper, metal, glass plate, polyester film, polyvinyl chloride film, bar coater, doctor knife, Meir bar, Using a roll coat, a die coat, or the like, or by spraying, brushing, rolling, spin coating, dipping, etc., the film is cast and coated so as to have a uniform thickness. When a desired film thickness cannot be obtained by a single coating, the coating can be repeated.

  Thereafter, it is usually dried at about 30 to 150 ° C. to remove the solvent, and if necessary, it is crosslinked at 130 to 180 ° C. for about 5 to 180 minutes to form a film. The film is usually peeled off from the substrate, but it is not necessary. Also, the film can be dried or annealed again after peeling.

  The residual solvent concentration is 5% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less by drying and removing the solvent. If the drying temperature is equal to or higher than the boiling point of the solvent or near the boiling point, foaming may occur and irregularities may be generated on the surface. The drying temperature is determined with reference to a temperature 5 ° C. or more, preferably 10 ° C. or more lower than the boiling point of the solvent, and the coating liquid is usually dried in the range of 30 to 100 ° C. in consideration of the boiling point.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following examples, “part” and “%” are based on mass unless otherwise specified. (1) Volume specific resistance value, (2) Tensile elongation and tensile strength, (3) Tear strength, (4) Electrolytic solution resistance of the conductive elastomer film are as follows.
(1) Volume resistivity value The volume resistivity value was calculated from the surface resistance value (Ω) and thickness (cm) of a 5 cm × 5 cm test piece.
(2) Tensile elongation and tensile strength Tensile elongation and tensile strength were measured according to JIS K 7127 under the conditions of specimen type 2, width 20 mm, 200 mm / min.
(3) Tear Strength Tear strength was measured by a trouser tear method according to JIS K 7128-1.
(4) Electrolytic solution resistance A concentration of 1 mol / l in a mixed solution obtained by mixing ethylene carbonate and diethyl carbonate at a mixing ratio of lithium hexafluorophosphate of ethylene carbonate: diethyl carbonate = 1: 1 (volume ratio). An electrolytic solution dissolved in was prepared. Next, the test piece was immersed in the electrolyte solution for 1 hour and folded in the electrolyte solution. When cracks and / or cuts did not occur, “O” was indicated, and when cracks and / or cuts occurred, “X” was indicated.
Example 1
The components shown in Table 1 were mixed in cyclohexane so that the solid content was 20%, and steel balls with a diameter of 5 mm having the same weight as the components were added to the obtained dispersion, and the steel The dispersion containing the spheres was treated with a paint shaker for 120 minutes to produce a uniform paint. The obtained paint was cast on a polyethylene terephthalate film using a doctor blade and dried at 100 ° C. for 1 hour to obtain a conductive resin film. A predetermined test piece was cut out from the film with a knife. The results are shown in Table 1.

Examples 2 to 4 and Comparative Examples 1 to 4
The same operation as in Example 1 was performed except that the blending ratio of the blending components was changed as shown in Table 1. The resin composition of Comparative Example 4 could not be made into a film. The results are shown in Table 1.

1) Clayton (registered trademark) G1657M (styrene content: 13% by mass) manufactured by Clayton Japan
2) ZEONOR (registered trademark) 1430R manufactured by Nippon Zeon Co., Ltd.
3) Ketchen Black International Co., Ltd. Ketchen black (registered trademark) EC-600JD (DBP oil absorption of 495cm ³ / 100g, BET surface area of 1270m ² / g)
4) CS JAFT 689 manufactured by Owens Corning Japan Co., Ltd. (diameter 10 μm, fiber length 3 mm)

  The volume specific resistance values of the films of Examples 1 to 4 which are conductive resin films of the present invention were small, the mechanical strength such as tear strength was high, and the resistance to the electrolytic solution containing an organic solvent was high. The tear strength of the films of Comparative Examples 1 and 2 obtained from the resin composition containing no glass fiber was small. The tensile elongation of the film of Comparative Example 1 was also small. The electrolyte solution resistance of the film of Comparative Example 3 obtained from the resin composition containing no cyclic olefin resin and glass fiber was low. The resin composition of Comparative Example 4 in which the glass fiber content was less than 5 parts by mass with respect to 100 parts by mass of the resin component could not be formed into a film.

  Since the conductive resin film of the present invention has a small volume specific resistance value and high resistance to electrolytic solution, it is hardly deteriorated by the electrolytic solution and exhibits stable performance. Therefore, an example of typical uses of the conductive resin film of the present invention is a current collector for an electric double layer capacitor and a current collector for a lithium ion battery using an organic electrolyte. In addition to the basic cell, which is the smallest structural unit, an electric double layer capacitor and a lithium ion battery in which a plurality of basic cells are connected in series to increase the output voltage, and an electric double layer capacitor in which the output current is increased by connecting in parallel In addition, a lithium ion battery and a power source combining these may be included in the electric double layer capacitor and the lithium ion battery. Since the electric double layer capacitor and the lithium ion battery using the conductive resin film of the present invention as a current collector can be lighter than those using a metal current collector, the output per unit weight should be increased. It is suitable for use in automobiles, railway vehicles and the like.

Claims (6)

(1) 100 parts by mass of a resin component comprising (a) 90 to 100% by mass of a cyclic olefin resin and (b) 10 to 0% by mass of a hydrogenated aromatic vinyl-conjugated diene block copolymer, and (2) conductivity. The conductive resin film containing 15-50 mass parts of fillers and (3) 5-40 mass parts of glass fiber. The conductive resin film according to claim 1, wherein the (a) cyclic olefin resin is a ring-opening polymer of a monomer having a norbornene ring or a hydrogenated product thereof. The conductive resin film according to claim 1 or 2, wherein the hydrogenated product of the aromatic vinyl-conjugated diene block copolymer (b) is a styrene-ethylene-butene-styrene block copolymer. The conductive resin film according to claim 1, wherein the (2) conductive filler is carbon black. The conductive resin film according to claim 1, wherein the thickness is 10 to 200 μm. (1) 100 parts by mass of a resin component comprising (a) 90 to 100% by mass of a cyclic olefin resin and (b) 10 to 0% by mass of a hydrogenated aromatic vinyl-conjugated diene block copolymer, and (2) conductivity. A conductive resin composition containing 15 to 50 parts by mass of filler, (3) 5 to 40 parts by mass of glass fiber, and (4) 100 to 1000 parts by mass of solvent is coated on a substrate and then dried. A method for producing a conductive resin film.