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WO1999002585A1 - Film de resine conductrice, composition de resine conductrice, et procede d'obtention d'un film de resine conductrice - Google Patents

Film de resine conductrice, composition de resine conductrice, et procede d'obtention d'un film de resine conductrice Download PDF

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Publication number
WO1999002585A1
WO1999002585A1 PCT/JP1998/003073 JP9803073W WO9902585A1 WO 1999002585 A1 WO1999002585 A1 WO 1999002585A1 JP 9803073 W JP9803073 W JP 9803073W WO 9902585 A1 WO9902585 A1 WO 9902585A1
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WO
WIPO (PCT)
Prior art keywords
conductive
weight
conductive resin
parts
cyclic olefin
Prior art date
Application number
PCT/JP1998/003073
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English (en)
Japanese (ja)
Inventor
Shuichi Akita
Tsunehisa Ueda
Kenji Tsukakoshi
Kuniaki Goto
Original Assignee
Nippon Zeon Co., Ltd.
Asahi Kagaku Kogyo Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co., Ltd., Asahi Kagaku Kogyo Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1999002585A1 publication Critical patent/WO1999002585A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function

Definitions

  • the present invention relates to a conductive resin film useful as various conductive materials, electromagnetic wave shields, electrodes, and the like. More specifically, it is a conductive resin film having a small volume resistance value, and is particularly useful as a conductive partition wall material for electromagnetic wave shielding of electronic circuit components and a conductive partition wall for an electric double layer capacitor having a small internal resistance. About the film. Background art
  • Electronic circuits generate noise in their signal circuits due to electromagnetic waves radiated by them and external electromagnetic waves during operation, and may malfunction in extreme cases. For this reason, many electronic circuits are configured to cover predetermined circuit units or the entire device with a conductive shielding material to reduce the effects of electromagnetic waves.
  • a metal case or cover is used for electromagnetic wave shielding.
  • metal covers, etc. have to be formed with a certain amount of space between them and the space between components must be widened. There's a problem.
  • various electronic circuits are mounted adjacent to each other, so metal shielding materials cannot be attached. Instead, thin, flexible conductive film materials are used. Is required.
  • An electric double-layer capacitor (also referred to as an electric double-layer capacitor) is an electric element composed of a polarizable electrode and an electrolyte.
  • an electrolytic solution in which an electrolyte salt is dissolved is generally used (see Japanese Unexamined Patent Publication No. 9-6 8 2 5 4).
  • the electric double layer capacitor has a function of storing electric charge in the electric double layer formed between the electrolyte and the electrode due to the polarization of the electrode.
  • Electric double-layer capacitors are used as small power supplies for semiconductor memory backup, etc. Higher performance is required.
  • electric double layer capacitors are also expected to be used as auxiliary power sources for electric vehicles and fuel cell vehicles.
  • an aqueous electrolytic solution as an electrolytic solution, usually an aqueous solution of sulfuric acid having a concentration of about 25 to 50%
  • JP-A-63-213139, JP-A-2-174210, etc. and those using an organic solvent-based electrolyte (JP-A-49-16882) 54, JP-A-7-86696, etc.).
  • an organic solvent-based electrolyte has a drawback that the output voltage is high, but the ionic conductivity is low, so that the internal resistance of the electric double layer capacitor increases and the output current decreases.
  • an aqueous electrolyte has a low output voltage, but has a low internal resistance due to high ionic conductivity, and can provide a large output current. Furthermore, since those using an organic solvent-based electrolyte are flammable, the development of a large-output electric double-layer capacitor using an aqueous electrolyte is desired from the viewpoint of safety.
  • the internal resistance will be reduced and the output current will be reduced. Need to be larger.
  • the internal resistance is generated by the aqueous electrolyte, the carbon of the electrode, and the conductive partition.
  • the internal resistance of the electrolyte and the electrodes due to the carbon can be reduced by making the cell of the electric double layer capacitor thinner, but when the cell is made thinner, the capacity of each cell decreases. Therefore, it is very effective to reduce the volume resistance of the conductive partition.
  • a rubber film containing a conductive material is generally used (Japanese Patent Application Laid-Open No. 2-174210, Japanese Patent Application Laid-Open No. 412708/1994, Hei 5—29992296, etc.).
  • the conductive rubber film conventionally used has a large volume resistance of about 8 to 500 ⁇ cm in the direction perpendicular to the surface, and it is difficult to increase the output of the capacitor to a desired high level. is there.
  • these conductive rubber films have poor acid resistance, and may be eroded by an acidic aqueous electrolyte over a long period of use, resulting in reduced functions or liquid leakage.
  • Japanese Patent Application Laid-Open No. 7-126434 discloses a car having a wavelength of 0.01 to 100 nm.
  • a composition containing a hydrogenated resin of a norpollene-based ring-opening polymer obtained by mixing a pon fiber and a pon fiber of 1/2 to 100 times the length of the carbon fiber is used for a molded article.
  • the specific surface area of the carpon fiber was so small as to be less than 50 m 2 / g, the volume resistance was large, and the effect as a conductive film for the capacity was insufficient. Disclosure of the invention
  • An object of the present invention is to provide a conductive resin film having a low resistance value used for a conductive partition wall for electric and electronic parts and an antistatic material, and particularly for an electronic circuit part and a device.
  • An object of the present invention is to provide a conductive resin film suitable for an electromagnetic wave shield member and an electric double layer capacitor having a small internal resistance.
  • the present inventors have found that if a specific resin film containing a conductive filler is used as the conductive partition wall material, a conductive partition wall material having extremely low volume resistance and excellent film strength can be obtained. Was completed.
  • the present invention comprises (1) a cyclic olefin resin, and (2) 100 to 100 parts by weight of the cyclic olefin resin, and 5 to 100 parts by weight of a conductive filler.
  • a conductive resin film having a vertical volume resistance value of 0.01 to 5 ⁇ cm is provided.
  • a cyclic olefin resin (2) a conductive filler of 5 to 100 parts by weight with respect to 100 parts by weight of the cyclic olefin resin component, and (3) a cyclic olefin resin component.
  • a conductive resin composition comprising 100 to 100 parts by weight of a solvent for dissolving the cyclic olefin resin.
  • the conductive resin composition is coated on a release substrate, dried, and then the film thus obtained is peeled from the release substrate.
  • a method for producing a conductive resin film is provided.
  • the film of the present invention contains 100 parts by weight of the cyclic olefin resin, 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight of the conductive filler, and is perpendicular to the film surface.
  • the volume resistivity in the direction is 0.01 to 5 Qcm, preferably 0.01 to 3 ⁇ cm, more preferably 0.01 to 1 Qcm. If the amount of the conductive filler is too small, the volumetric resistance of the conductive resin film is too large, and if it is too large, the production of the conductive resin film becomes difficult.
  • the thickness of the conductive resin film of the present invention is appropriately determined depending on the application and shape, but is preferably 10 m or more, more preferably 20 // m or more, particularly preferably 30 m or more, and preferably Is at most 200 zm, more preferably at most 150 zm, particularly preferably at most 100 zm. If it is too thin, it is difficult to use because of insufficient strength, and if it is too thick, the resistance increases.
  • the method for producing the conductive resin film of the present invention is not particularly limited, but a method produced by a solvent casting method described below is preferable because the conductive filler is easily dispersed uniformly throughout the film. .
  • the conductive filler is not oriented in the plane direction, the volume resistance measured in the direction perpendicular to the plane is low.
  • a cyclic olefin resin is used.
  • This resin is a non-crystalline resin having an aliphatic hydrocarbon ring structure in the main chain or side chain of the polymer.
  • Examples of the resin include JP-A-63-264646 and JP-A-64-1705.
  • Patent Documents ring-opened polymers of monomers having a norpolpolene ring and hydrogenated products thereof disclosed in JP-A-11-168724, JP-A-1-168725 and the like, and JP-A-60-168708 and the like Polymer of a monomer having a norbornene ring and an ⁇ -olefin, an addition polymer of a cyclic olefin and a cyclic gen disclosed in JP-A-6-136057 and JP-A-7-258362, and the like. Hydrogenates and the like can be mentioned.
  • cyclic olefin resins are commercially available, for example, available under the trade names ⁇ from Zeon Corporation and APEL and AP ⁇ from Mitsui Petrochemical Industries, Ltd. It is.
  • ring-opened polymers of monomers having a norbornene ring and hydrogenated products thereof are preferred from the viewpoints of film forming properties, chemical resistance, etc., and particularly hydrogen-opened polymers of monomers having a norbornene ring are preferred. Additives are preferred.
  • Examples of the monomer having a norpolene ring include norpolene, a bicyclic olefin, which is an adduct of ethylene and cyclopentadiene, and tetracyclododecene, which is a tetracyclic olefin, to which cyclopentene is added.
  • Tricyclodecadiene also known as dicyclopentene
  • Tricyclodecene also known as dicyclopentene
  • Pentacyclopentadecadiene a pentacyclic pentamer of pentane
  • pentacyclic cyclopentadecene a pentacyclic olefin with some of the unsaturated bonds saturated by hydrogenation (2,3-dihydro Dicyclobenzene); and their substituted products.
  • substituents examples 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-norpolonene).
  • 1, 2, 3, 4, 4a, 5, 5a, 6, 9, 9a, 10, 10a Dodecahydro-2,3-cyclopentene tetracyclododecene derivatives such as dienoanthracene)
  • Substituents substituted by polar groups such as halogen, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, and silyl group (for example, 5-methoxy-carbonyl-2-norporene, 5-cyano- 2-norporene, 5-methyl-5-methoxy Carbonyl-1-norbornene).
  • olefins in a narrow sense such as ethylene, propylene, 1-butene and 4-methylpentene-11, and a part of these olefins is a polar group such as halogen.
  • olefins in a narrow sense such as ethylene, propylene, 1-butene and 4-methylpentene-11, and a part of these olefins is a polar group such as halogen.
  • Substituted oligomeric monomers can be mentioned.
  • Cyclic olefins include cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclohexene, cyclooctene, 1-methylcyclooctene, and 5-methylcyclopentene.
  • Monocyclic cycloolefins such as octene, cyclooctane, cyclododecene, etc., and the above-mentioned monomers having a norportene ring having one unsaturated bond can be exemplified.
  • Examples of the cyclic gen include monocyclic genes such as cyclopentene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene, and those having two unsaturated bonds among the above-mentioned monomers having a norportene ring. be able to.
  • the monomer having no polar group is preferably at least 50% by weight, more preferably at least 70% by weight, particularly preferably at least 90% by weight, based on the total amount of the monomers.
  • the resulting conductive resin film has excellent resistance to chemicals such as sulfuric acid.
  • copolymerization may be performed by mixing various copolymerizable monomers with the respective polymerization systems.
  • the copolymerizable monomer include, in addition to the above-mentioned monomer having a norpolene ring, ⁇ -olefin, cyclic olefin, and cyclic gen, linear or branched gens such as butadiene and isoprene. it can.
  • the polymerization may be random, block type or alternating type, and when addition polymerization has 1,2-addition and 1,4-addition, which may be the main one However, the ratios may be approximately the same.
  • the conductive resin obtained by the remaining unsaturated bonds This is because the chemical resistance of the film decreases. It is preferable to saturate 80% or more, preferably 90% or more of the unsaturated bonds by hydrogenation for the purpose of improving the hydrogen content.
  • a known method may be used for the method of hydrogenation and the catalyst.
  • the molecular weight of the polymer is, for example, preferably a number average molecular weight (Mn) in terms of polyisoprene measured by gel permeation 'chromatography using cyclohexane as a solvent, more preferably from 3,000 to 100,000, more preferably Is from 5,000 to 50,000, and the weight average molecular weight (Mw) is preferably from 8,000 to 200,000.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the number average molecular weight and the weight average molecular weight can be measured using a good solvent for the polymer such as toluene / tetrahydrofuran.
  • Solvent is removed by filtration and then removed by heating or vacuum heating, or by removing the solvent by directly heating or vacuum heating the resin solution from which metal contaminants have been removed by precipitation aggregation method. May be dried.
  • 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 partially removing it. Further, the solvent can be replaced with a solvent for film production without drying.
  • the glass transition temperature (hereinafter sometimes referred to as Tg) of cyclic olefin resin varies depending on the type of monomer, the proportion of comonomer in copolymerization, the molecular weight, the hydrogenation rate, etc., but the resin for conductive resin film When used as, it is preferably -150 to 300 ° C, more preferably one to 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 resin film are preferable because they are highly balanced.
  • Tg is a value measured by a differential scanning calorimeter (DSC).
  • the stabilizer include phenol-based antioxidants, phosphorus-based antioxidants, and zeolite-based antioxidants. Of these, phenol-based antioxidants are preferred, and alkyl-substituted phenol-based oxidation agents are preferred. Inhibitors are particularly preferred. These stabilizers are used alone or in combination of two or more. The amount of the stabilizer is appropriately selected according to the purpose of use, but is usually in the range of 0.001 to 10 parts by weight based on 100 parts by weight of the cyclic olefin polymer.
  • thermoplastic elastomer may be used in combination with the cyclic olefin resin.
  • the combined use of thermoplastic elastomers generally improves film strength.
  • the thermoplastic elastomer that can be used in combination may be any of those commonly known as thermoplastic elastomers.
  • the amount of the thermoplastic elastomer is usually 300% by weight or less, preferably 100 to 300% by weight, more preferably 20 to 200% by weight, based on 100% by weight of the cyclic olefin resin. More preferably, it is 30 to 100% by weight.
  • thermoplastic elastomer examples include polyolefin-based thermoplastic elastomers such as thermoplastic ethylene / propylene copolymers and thermoplastic ethylene / olefin copolymers; thermoplastic vinyl aromatic hydrocarbons / conjugated gen copolymers and the like. Block copolymers, thermoplastic ethylene / propylene / conjugated copolymers and other olefins / conjugated copolymers and their hydrogenated products; thermoplastic polyvinyl chloride polymers; butyl rubber with an iodine value of 30 or less, etc.
  • block copolymers of vinyl aromatic hydrocarbons and conjugated gens (a) blocks A mainly composed of at least two vinyl aromatic hydrocarbons and (b) mainly composed of at least one conjugated gen A block copolymer comprising the block B (hereinafter sometimes simply referred to as a vinyl aromatic block copolymer) is preferred, and particularly a hydrogenated vinyl aromatic obtained by hydrogenating the vinyl aromatic block copolymer.
  • Group block copolymers are particularly preferred.
  • Olefin which is a raw material of the above-mentioned thermoplastic elastomer
  • unsubstituted vinyl aromatic hydrocarbons such as styrene, and straight-chain or branched hydrocarbons having 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, 1-hexene and 1-octene. Refining is preferred, and styrene is particularly preferred.
  • olefins can be used alone or in combination of two or more.
  • conjugated diene examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentene, 1,3-hexadiene, and the like.
  • Butadiene and isoprene are exemplified. Particularly preferred.
  • the vinyl aromatic block copolymer which is a particularly preferred thermoplastic elastomer in the present invention, and its hydrogenated product may have either a linear structure or a branched structure, but preferably has at least two blocks A.
  • a block copolymer having a styrene phase at both terminal phases and a hydrogenated type olefin (specifically, a block obtained by hydrogenating a conjugated gen) as an intermediate phase is preferable from the viewpoint of breaking elongation and strength.
  • the structure of the copolymer having two or more blocks A is generally a linear structure such as A—B—A, A—B—A—B, A—B_A—B_A, and ( AnBm) M (where n and m are integers of 1 or more, p is an integer of 3 or more, and M is a residue of a polyfunctional coupling agent).
  • the content of Bier aromatic hydrocarbon in the vinyl aromatic block copolymer and its hydrogenated product is usually 5 to 70% by weight, preferably 10 to 60% by weight. If the ratio of the vinyl aromatic hydrocarbon is too small, the strength of the film is insufficient, while if it is too large, the flexibility of the film becomes poor.
  • the amount of vinyl bond in the block B is not particularly limited, but is usually 90% or less, preferably 1 to 60%, more preferably 5 to 30%. Many vinyl bonds Too much is not preferred because the flexibility of the film is lost.
  • the molecular weight of the vinyl aromatic block copolymer and its hydrogenated product is not particularly limited, but the balance between elongation and flexibility when formed into a film is determined by gel permeation chromatography using toluene.
  • the measured polystyrene equivalent weight average molecular weight (Mw) is preferably in the range of 100, 000 to 1, 0000, 0000, and 20, 000 to 800, 000. Is more preferable, and the range of 50,000 to 500,000 is most preferable.
  • Such a vinyl aromatic block copolymer can be prepared by a known method, for example, in Japanese Patent Publication No. 36-192,86, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No.
  • an aromatic compound is used as an initiator in a hydrocarbon solvent using an organolithium compound as an initiator. It can be produced by polymerizing hydrogen and a conjugated diene.
  • a polar compound can be used for the purpose of adjusting the reactivity ratio between the vinyl aromatic hydrocarbon and the conjugated diene, changing the microstructure of the polymerized conjugated diene portion, and adjusting the polymerization rate.
  • hydrocarbon solvent used herein examples include aliphatic hydrocarbons such as butane, heptane, hexane, isopentane, heptane, octane, and isooctane; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • aliphatic hydrocarbons such as butane, heptane, hexane, isopentane, heptane, octane, and isooctane
  • cyclopentane methylcyclopentane
  • cyclohexane methylcyclohexane
  • ethylcyclohexane examples include alicyclic hydrocarbons such as xane; and aromatic hydrocarbons such as benzene, ethylbenzene, and xylene. These may be used alone or
  • polar compound examples include ethers such as tetrahydrofuran, getyl ether, anisol, dimethoxybenzene, ethylene glycol dimethyl ether; triethylamine, tetramethylenediamine, N-dimethylaniline, pyridine and the like. Amines; thioethers, phosphines, phosphoramides, alkylbenzene sulfonic acids, and alkoxides such as potassium sodium and the like can be mentioned, and can be selected according to required characteristics.
  • Use of polar compounds The dose can be appropriately determined depending on the kind of the compound and the like, but is usually in the range of 0.01 to 1 mol, preferably 0.01 to 0.5 mol, per 1 mol of the organolithium compound.
  • an organic lithium compound As the organic lithium compound as the initiator, an organic monolithium compound, an organic dilithium compound, or the like is used. Specific examples thereof include n_butyllithium, sec_butyllithium, tert_butyllithium, and n_hexyllithium. , Isohexyllithium, phenyllithium, naphthyllithium, hexamethylenedilithium, butadienyldilithium, isoprenyldilithium and the like. Generally, an organic monolithium compound is used. These are used alone or in combination of two or more.
  • the amount used is appropriately selected depending on the molecular weight of the target polymer and the type of the organolithium compound, but is usually 0.01 to 1 mol, preferably 0.01 to 0.1 mol, per mol of the monomer.
  • the range is 5 moles.
  • the polymerization reaction may be either an isothermal reaction or an adiabatic reaction, and is usually performed at a polymerization temperature range of 0 to 150 ° C, preferably 20 to 120 ° C.
  • a block copolymer produced by adding a coupling agent after the above polymerization reaction can also be used.
  • the coupling agent include tin tetrachloride, tin dichloride, tin tetrabromide, silicon tetrachloride, silicon tetrabromide, gay tetraiodide, germanium tetrachloride, lead dichloride, and methyltrichlorosilane.
  • Each of these coupling agents is used alone or in combination of two or more.
  • the amount of the coupling agent to be used is generally 0.25 to 2 equivalents, preferably 0.30, per organolithium compound. ⁇ : L.5 equivalents.
  • the coupling reaction is usually performed at 0 to 150 ° C. for 0.1 to 20 hours.
  • the block copolymer one produced using a modifying agent after the above polymerization reaction can be used.
  • the modifying agent include unsaturated carboxylic acids such as maleic anhydride disclosed in Japanese Patent Publication No. Sho 62-61615, and imino disclosed in Japanese Patent Publication No. Hei 41-87770. Compounds, cyanamide compounds, aziridinyl compounds, amide compounds and the like.
  • the copolymer thus obtained is subjected to a conventional method, for example, as described in Japanese Patent Application Laid-Open No. Hei 4-96905, Japanese Patent Application Laid-Open No. Hei 4-96904, No. 51, Japanese Patent Publication No. 63-5402, Japanese Patent Publication No. 48-35555, Japanese Patent Publication No. 45-2005, the method disclosed in Japanese Patent Publication No. Dissolves a vinyl aromatic block copolymer in an inert solvent such as cyclopentanone or tetrahydrofuran, and hydrogenates it in the presence of a hydrogenation catalyst to obtain a hydrogenated biel aromatic block copolymer be able to.
  • an inert solvent such as cyclopentanone or tetrahydrofuran
  • hydrogenation catalyst examples include nickel, platinum, palladium, rhodium, and other hydrogenation metal catalysts supported on carbon diatomaceous earth, Raney nickel, organic nickel compounds, organic cobalt compounds, and these compounds and other organic metal compounds. And a composite catalyst.
  • the elastomer When a film containing a thermoplastic elastomer is used as the conductive partition wall of the electric double layer capacitor, the elastomer does not react with a commonly used acidic electrolyte, so that the elastomer is a hydrogenated vinyl aromatic. Block copolymers are most desirable.
  • conductive filler contained in the conductive resin composition of the present invention include carbon, graphite, powdered or fibrous metal or metal oxide, and the like.
  • the specific surface area of the conductive filler is preferably 50 m 2 Zg or more, more preferably It is at least 200 m 2 Zg, particularly preferably at least 500 m 2 Zg.
  • the upper limit of the specific surface area is not particularly limited, but is usually 3,000 m 2 Zg or less. If the specific surface area is too small, the volume resistivity of the conductive resin film is undesirably large.
  • carbon examples include furnace black such as conductive furnace black, super conductive furnace black, and extra conductive furnace black, conductive channel black, and acetylene black.
  • conductive carbons include Continex CF (Continental Carbon, Conductive Furnace Black), Ketjen Black EC (Ketjen Black In Yuichi National, Conductive Furnace Black) , Vulcan C (Conductive Furnace Black, manufactured by Cabot), BLACK PEARLS 2000 (Conductive Furnace Black, manufactured by KYAPOT), Denka Acetylene Black (acetylene black, manufactured by Denki Kagaku Kogyo KK) and the like can be preferably used.
  • Continex CF Continuous Carbon, Conductive Furnace Black
  • Ketjen Black EC Ketjen Black In Yuichi National, Conductive Furnace Black
  • Vulcan C Conductive Furnace Black, manufactured by Cabot
  • BLACK PEARLS 2000 Conductive Furnace Black, manufactured by KYAPOT
  • Denka Acetylene Black ace
  • graphite examples include scaly natural graphite, artificial graphite, and graphite fiber.
  • the metal include iron, copper, nickel, aluminum, titanium, tantalum, niobium, vanadium, and alloys thereof.
  • titanium, tantalum, niob, vanadium and alloys thereof are preferable. It is also preferable that these metal fine particles are adhered to the surface of a carbon particle, and that these metals are coated on the surface of metal particles having low acid resistance such as iron and aluminum by plating or vapor deposition.
  • the conductive filter can be used alone or in combination of at least two kinds, for example, metal fine particles and carbon fiber.
  • the conductive resin composition of the present invention comprises 100 parts by weight of the above-described cyclic olefin resin, 5 to 100 parts by weight of the above-mentioned conductive filler, and 100 to 1,000 parts by weight of a solvent for dissolving the cyclic olefin resin. Is contained. Also need Various additives can be contained accordingly.
  • the solvent used in the present invention is not particularly limited as long as the above-mentioned cyclic olefin resin and optionally used other thermoplastic elastomer can be dissolved at room temperature or under heating.
  • Preferred solvents include hydrocarbon compounds. And chlorine-containing organic compounds.
  • the solvent include aromatic hydrocarbon compounds such as benzene, toluene, and xylene; n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, nonane, decane, decalin, and tetralin. , Dodecane, gasoline, industrial gasoline and other saturated aliphatic and alicyclic hydrocarbon compounds; Hydrogen compound;
  • a softening agent such as a paraffinic process oil or a naphthenic process oil or a compounding agent such as an antioxidant may be added to the cyclic olefin resin composition of the present invention as long as the effects of the present invention are not impaired. You may.
  • the resin used is preferably a resin that is not easily eroded by an acidic electrolytic solution, and examples thereof include olefin-based resins such as polyethylene and polypropylene, polystyrene, and polyvinyl chloride. Polyvinyl chloride, which is excellent in acid resistance, is preferable.
  • the mixing ratio of the resin component is preferably at least 0.1 part by weight, more preferably at least 5 parts by weight, preferably at most 50 parts by weight, more preferably at most 20 parts by weight, based on 100 parts by weight of the cyclic olefin resin. It is as follows. If the amount is too small, there is no reinforcing effect, and if the amount is too large, the flexibility of the film is insufficient.
  • a cyclic olefin resin component is blended with an organic peroxide such as hydroperoxide, a resin vulcanizing agent such as alkylphenol / formaldehyde resin, and a cross-linking agent such as an ultraviolet curing agent.
  • the cyclic olefin resin component, the conductive filler, and the conductive optional component, compounding agent, and resin added as necessary may be kneaded in advance. However, they may be dissolved or dispersed in a solvent when preparing a solution for casting.
  • the conductive cyclic olefin resin composition of the present invention comprises 100 parts by weight of an organic solvent, the above-described cyclic olefin resin component and a conductive filler, and optional conductive components and compounding agents added as necessary.
  • the total amount other than the organic solvent is usually at least 5 parts by weight, preferably at least 10 parts by weight, more preferably at least 15 parts by weight, usually at most 30 parts by weight, preferably at most 25 parts by weight, more preferably at most 2 parts by weight. It is prepared by dissolving or dispersing 0 parts by weight or less. If the concentration is too low, when the composition is formed into a conductive cyclic resin film, a sufficiently thick one cannot be obtained. Conversely, if the concentration is too high, the viscosity of the solution becomes too high, and the thickness of the film increases. Is not uniform.
  • the conductive cyclic resin film of the present invention is obtained by coating the above-mentioned cyclic resin composition of the present invention on a release substrate and drying the film, and then peeling the film from the release substrate. It can be produced by a method, that is, a solvent casting method or a solution casting method. A specific manufacturing method will be described below.
  • a lump or undispersed substance in the above-described conductive cyclic olefin resin composition of the present invention is removed by a filter or the like.
  • the filler used include a thread-like fiber, a metal woven in a mesh shape, or a fine hole pierced in a planar material, but is not necessarily limited to these. Absent.
  • degassing is performed to remove bubbles contained in the solution.
  • Examples of the defoaming method include a vacuum method and an ultrasonic method, but are not necessarily limited thereto.
  • the prepared solution is placed on a smooth, flat, mold-releasing substrate such as polyethylene terephthalate, Teflon, paper, metal, glass plate, polyester film, or polyvinyl chloride film, and is coated with a bar coater, doctor knife, and meir. 'Bar, Roll' Using a coat, die coat or the like, or by spraying, brushing, roll, spin coating, dipping, etc., so that the thickness becomes uniform and coating. If the desired film thickness cannot be obtained by one coating, the coating can be repeated. After that, it is usually dried at about 30 to 150 ° C to remove the solvent, and if necessary, crosslinked at 130 to 180 ° C for about 5 to 180 minutes to form a film. Then, the film is peeled from the release substrate. It is also possible to dry again after peeling off the film.
  • a smooth, flat, mold-releasing substrate such as polyethylene terephthalate, Teflon, paper, metal, glass plate, polyester film, or polyvinyl chloride film
  • the drying temperature is preferably determined according to the characteristics of the solvent. As described above, the temperature should preferably be set at a temperature lower by at least 10 ° C, and drying is usually performed in the range of 30 to 100 ° C in consideration of the boiling point.
  • a conductive elastomer film was produced in the same manner by using the composition containing the above-mentioned thermoplastic elastomer instead of the cyclic resin resin of the cyclic resin composition of the present invention. It can also be used as a two-layer film by laminating on the conductive cyclic resin film of the invention. At this time, a conductive elastomer film may be laminated on the conductive resin film of the present invention, or a conductive resin film may be laminated on the conductive elastomer film.
  • An example of a typical application of the above-described conductive cyclic resin film of the present invention is a conductive partition for an electric double layer capacitor.
  • the electric double-layer capacity is not only the basic cell, which is the minimum structural unit, but also the one in which a plurality of basic cells are connected in series to increase the output voltage, or the one in parallel to increase the output current. And may also include power sources that combine these.
  • the basic cell of an electric double-layer capacitor is composed of two electrodes placed through a separator, a conductive partition is placed so as to be in contact with the outside, an electrolyte is filled, and a conductive barrier
  • the wall was sealed with a gasket with at least a part of the outside exposed.
  • the separator is designed to prevent electrical shorts due to contact between the two electrodes, and is made of a material that is easy to pass through the electrolyte and has excellent liquid-trapping properties, such as glass fiber, fluoropolymer, A nonwoven fabric of polypropylene or polyethylene fibers, a porous film, or the like is used.
  • the electrode is a polarizable electrode that has a high conductivity and does not cause an electrochemical reaction with the electrolytic solution, and activated carbon is usually used as a material for the electrode. Activated carbon is preferably immobilized by a mechanical or physical method to maintain its shape.
  • the electrolytic solution is an acidic solution. As a specific example, an aqueous solution of sulfuric acid of about 25 to 50% is usually used since it has no volatility.
  • the gasket is not particularly limited as long as it has sulfuric acid resistance and can prevent electrolyte leakage, and is usually an elastomer having an iodine value of 30 or less, preferably 20 or less, such as butyl rubber. Is used. The gasket may also serve as the conductive partition wall material.
  • an electromagnetic wave shielding member for electronic circuit components and equipment for example, as an electromagnetic wave shielding film provided on a printed circuit board on which various electronic circuits provided in a housing of a portable electronic device are mounted to prevent coupling between circuits. Can be used.
  • the volume resistance of the film was measured in the direction perpendicular to the surface using a 320 low resistance meter manufactured by Hioki Electric.
  • DCP ring-opening polymer hydrogenated product obtained by hydrogenation of dicyclopentene ring-opening copolymer (hereinafter referred to as DCP ring-opening polymer) using a palladium one-pot hydrogenation catalyst under nitrogen atmosphere
  • Mn number average molecular weight measured by polyisoprene conversion in GPC using cyclohexane as a solvent
  • the hydrogenation rate is 99.8% or more, the Tg measured by a differential scanning calorimeter (DSC) is 97 ° C) 100 parts by weight, conductive carbon (Ketjen Black International Co., Ltd.) Made by Ketjen Black E C, specific surface area about 800 m 2 Zg) 50 parts by weight was added to decalin so as to have a solid concentration of 17% by weight, and a uniform slurry was obtained using a pole mill. This slurry was filtered through a 150-mesh wire net to remove lumps and undispersed matters, and then defoamed using a vacuum defoaming machine.
  • DSC differential scanning calorimeter
  • the slurry was cast on a release-treated polyethylene terephthalate film using an apriquet overnight, dried at 80 ° C for 15 hours, and peeled off to form a uniform 50 m-thick film. Obtained.
  • the volume resistivity in the thickness direction of the film was 0.40 ⁇ cm.
  • Butyl rubber manufactured by Nippon Synthetic Rubber Co., Ltd., trade name "BUTYL 365" 100 parts by weight, conductive carbon (Ketjen Black in Yuichi National Co., Ltd., trade name “Ketjen Black EC”) 20 parts by weight, crosslinking agent Tamanol 53 1 (Arakawa Chemical Co., Ltd., alkyl phenol / formaldehyde resin) and tin dichloride / dihydrate are kneaded so that 2 parts by weight of each are not crosslinked, and the thickness is 220 m by a calendar method.
  • a conductive rubber film was manufactured. When the volume resistivity in the thickness direction of the film was measured, it was 5.5 ⁇ cm.
  • Polystyrene (manufactured by Mitsui Petrochemical Co., Ltd., TOPOLEX 550-51N-10) 100 parts by weight and 50 parts by weight of Ketjenblack EC are added to toluene so as to have a solid concentration of 17% by weight, and a pole mill is used. To obtain a uniform slurry. This slurry was filtered and defoamed in the same manner as in Example 1, and the polyethylene terephthalate filter was used. Cast on LUM. When the film was dried at room temperature for 24 hours and peeled off, the film was observed. As a result, many cracks were observed in the film, and a satisfactory film could not be obtained. Industrial applications
  • the conductive resin film of the present invention not only has a small volume resistance value, but also has excellent acid resistance, so that it does not easily deteriorate even in an acidic electrolytic solution and shows stable performance. Therefore, it is particularly useful as a conductive partition wall material of an electric double layer capacitor.
  • the basic cell of the obtained electric double-layer capacitor can be used for a long time, and the resistance of the basic cell decreases and the capacity increases, so connecting the basic cells in series or in parallel However, it is possible to manufacture a stable high-output battery.
  • Electromagnetic shielding materials and electrodes such as flooring materials, wall materials, and transport box materials for facilities, especially elastomer-composite electrodes with excellent flexibility, anode electrodes that can be used in electrolytic baths, soil electrodes, and electricity It can also be used as a connector, squeegee for screen printing, etc. (for screen printing) ⁇ sheet ion sensor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un film de résine conductrice comprenant: (1) 100 parties en poids d'une résine oléfinique cyclique et (2) de 5 à 10 parties en poids d'une charge conductrice, et dont la résistivité volumique perpendiculairement à la surface du film est comprise entre 0,01 et 5 Φcm. Ledit film est obtenu par moulage sur un matériau substrat permettant le démoulage d'une composition de résine conductrice comprenant (1) 100 parties en poids d'une résine oléfinique cyclique, (2) de 5 à 10 parties en poids d'une charge conductrice, et (3) de 100 à 1000 parties en poids d'un solvant de la résine oléfinique.
PCT/JP1998/003073 1997-07-09 1998-07-09 Film de resine conductrice, composition de resine conductrice, et procede d'obtention d'un film de resine conductrice WO1999002585A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/199354 1997-07-09
JP19935497 1997-07-09

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WO1999002585A1 true WO1999002585A1 (fr) 1999-01-21

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003133179A (ja) * 2001-10-29 2003-05-09 Nippon Zeon Co Ltd 集電用導電性フィルムおよび該フィルム製造用導電性塗料
US6717795B2 (en) 2001-11-01 2004-04-06 Nec Tokin Corporation Electric double-layer capacitor, and process for producing the same
US6741450B2 (en) 2001-12-20 2004-05-25 Nec Tokin Corporation Electric double-layer capacitor and method for preparing the same
US6751084B2 (en) 2001-10-19 2004-06-15 Nec Tokin Corporation Electric double layer capacitor and method for preparing the same
JP2006036945A (ja) * 2004-07-28 2006-02-09 Kinugawa Rubber Ind Co Ltd 導電性弾性体組成物
JP2010077235A (ja) * 2008-09-25 2010-04-08 Nippon Zeon Co Ltd 導電性樹脂フィルム及びその製造方法
JP2010138236A (ja) * 2008-12-10 2010-06-24 Nippon Zeon Co Ltd 導電性エラストマーフィルム及びその製造方法
JP2010222509A (ja) * 2009-03-25 2010-10-07 Nippon Zeon Co Ltd 導電性エラストマーフィルム及び積層フィルム
JP2010222508A (ja) * 2009-03-25 2010-10-07 Nippon Zeon Co Ltd 導電性エラストマーフィルム
JP2011008981A (ja) * 2009-06-24 2011-01-13 Nippon Zeon Co Ltd 導電性重合体フィルム、それを含んでなる集電体及びその製造方法
JP2011006534A (ja) * 2009-06-24 2011-01-13 Nippon Zeon Co Ltd 導電性重合体フィルム、それを含んでなる集電体及びその製造方法
WO2012161180A1 (fr) 2011-05-23 2012-11-29 株式会社カネカ Film conducteur multicouche, collecteur de courant utilisant celui-ci, batterie et batterie bipolaire
JP2018111218A (ja) * 2017-01-06 2018-07-19 国立大学法人長岡技術科学大学 感圧導電性エラストマーの製造方法
EP3216070A4 (fr) * 2014-11-05 2018-09-26 Yen, William Winchin Produit de type feuille microporeuse et procédés de fabrication et d'utilisation dudit produit
JPWO2018016442A1 (ja) * 2016-07-20 2019-05-09 日本ゼオン株式会社 導電性フィルム及びその製造方法
US10586965B2 (en) 2014-11-05 2020-03-10 William Winchin Yen Microporous sheet product and methods for making and using the same
US11021584B2 (en) 2014-08-21 2021-06-01 William Winchin Yen Microporous sheet product and methods for making and using the same
WO2024023578A1 (fr) 2022-07-28 2024-02-01 Institut Pasteur Hsc70-4 utilisé dans le silençage génique induit par l'hôte et induit par pulvérisation
EP4353269A1 (fr) 2022-10-14 2024-04-17 Röhm GmbH Procédé de stérilisation d'articles formés à partir de polymères thermoplastiques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132590A (ja) * 1991-04-05 1993-05-28 Idemitsu Kosan Co Ltd α−オレフイン系共重合体からなるシートまたはフイルム
JPH05148413A (ja) * 1991-08-05 1993-06-15 Japan Synthetic Rubber Co Ltd キヤストフイルム
JPH05206256A (ja) * 1991-11-29 1993-08-13 Nippon Zeon Co Ltd 電子部品処理用器材
JPH07126434A (ja) * 1993-10-29 1995-05-16 Nippon Zeon Co Ltd 帯電防止組成物、樹脂組成物、及びそれからなる成形品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132590A (ja) * 1991-04-05 1993-05-28 Idemitsu Kosan Co Ltd α−オレフイン系共重合体からなるシートまたはフイルム
JPH05148413A (ja) * 1991-08-05 1993-06-15 Japan Synthetic Rubber Co Ltd キヤストフイルム
JPH05206256A (ja) * 1991-11-29 1993-08-13 Nippon Zeon Co Ltd 電子部品処理用器材
JPH07126434A (ja) * 1993-10-29 1995-05-16 Nippon Zeon Co Ltd 帯電防止組成物、樹脂組成物、及びそれからなる成形品

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6751084B2 (en) 2001-10-19 2004-06-15 Nec Tokin Corporation Electric double layer capacitor and method for preparing the same
US6843810B2 (en) 2001-10-19 2005-01-18 Nec Tokin Corporation Electric double layer capacitor and method for preparing the same
JP2003133179A (ja) * 2001-10-29 2003-05-09 Nippon Zeon Co Ltd 集電用導電性フィルムおよび該フィルム製造用導電性塗料
US6717795B2 (en) 2001-11-01 2004-04-06 Nec Tokin Corporation Electric double-layer capacitor, and process for producing the same
US6741450B2 (en) 2001-12-20 2004-05-25 Nec Tokin Corporation Electric double-layer capacitor and method for preparing the same
JP2006036945A (ja) * 2004-07-28 2006-02-09 Kinugawa Rubber Ind Co Ltd 導電性弾性体組成物
JP2010077235A (ja) * 2008-09-25 2010-04-08 Nippon Zeon Co Ltd 導電性樹脂フィルム及びその製造方法
JP2010138236A (ja) * 2008-12-10 2010-06-24 Nippon Zeon Co Ltd 導電性エラストマーフィルム及びその製造方法
JP2010222509A (ja) * 2009-03-25 2010-10-07 Nippon Zeon Co Ltd 導電性エラストマーフィルム及び積層フィルム
JP2010222508A (ja) * 2009-03-25 2010-10-07 Nippon Zeon Co Ltd 導電性エラストマーフィルム
JP2011008981A (ja) * 2009-06-24 2011-01-13 Nippon Zeon Co Ltd 導電性重合体フィルム、それを含んでなる集電体及びその製造方法
JP2011006534A (ja) * 2009-06-24 2011-01-13 Nippon Zeon Co Ltd 導電性重合体フィルム、それを含んでなる集電体及びその製造方法
WO2012161180A1 (fr) 2011-05-23 2012-11-29 株式会社カネカ Film conducteur multicouche, collecteur de courant utilisant celui-ci, batterie et batterie bipolaire
KR20140023887A (ko) 2011-05-23 2014-02-27 가부시키가이샤 가네카 복층 도전성 필름, 이것을 사용한 집전체, 전지 및 쌍극형 전지
US9601780B2 (en) 2011-05-23 2017-03-21 Kaneka Corporation Multilayer conductive film, current collector using same, battery and bipolar battery
US11021584B2 (en) 2014-08-21 2021-06-01 William Winchin Yen Microporous sheet product and methods for making and using the same
EP3216070A4 (fr) * 2014-11-05 2018-09-26 Yen, William Winchin Produit de type feuille microporeuse et procédés de fabrication et d'utilisation dudit produit
US10586965B2 (en) 2014-11-05 2020-03-10 William Winchin Yen Microporous sheet product and methods for making and using the same
US10829600B2 (en) 2014-11-05 2020-11-10 William Winchin Yen Microporous sheet product and methods for making and using the same
JPWO2018016442A1 (ja) * 2016-07-20 2019-05-09 日本ゼオン株式会社 導電性フィルム及びその製造方法
JP2018111218A (ja) * 2017-01-06 2018-07-19 国立大学法人長岡技術科学大学 感圧導電性エラストマーの製造方法
WO2024023578A1 (fr) 2022-07-28 2024-02-01 Institut Pasteur Hsc70-4 utilisé dans le silençage génique induit par l'hôte et induit par pulvérisation
EP4353269A1 (fr) 2022-10-14 2024-04-17 Röhm GmbH Procédé de stérilisation d'articles formés à partir de polymères thermoplastiques

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