WO2016052303A1 - フィルムコンデンサ - Google Patents
フィルムコンデンサ Download PDFInfo
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- WO2016052303A1 WO2016052303A1 PCT/JP2015/076945 JP2015076945W WO2016052303A1 WO 2016052303 A1 WO2016052303 A1 WO 2016052303A1 JP 2015076945 W JP2015076945 W JP 2015076945W WO 2016052303 A1 WO2016052303 A1 WO 2016052303A1
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- WIPO (PCT)
- Prior art keywords
- film
- resin film
- group
- polymer
- stretching
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2045/00—Use of polymers of unsaturated cyclic compounds having no unsaturated aliphatic groups in a side-chain, e.g. coumarone-indene resins or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2386/00—Specific polymers obtained by polycondensation or polyaddition not provided for in a single one of index codes B32B2363/00 - B32B2383/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/16—Capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
- H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/32—Wound capacitors
Definitions
- the present invention relates to a film capacitor having, as a dielectric film, a resin film having excellent heat resistance, withstand voltage characteristics, and workability.
- a film capacitor has a structure in which dielectric films and metal layers are alternately arranged, and is an element capable of storing electric charges.
- film capacitors have become easier to generate heat during driving as a result of progress in miniaturization and increase in capacity. For this reason, a resin film used as a dielectric film of a film capacitor is required to be superior in heat resistance.
- a resin film used as a dielectric film of a film capacitor is required to be superior in heat resistance.
- it has been required to make the dielectric film thinner. However, if the dielectric film is made thinner, the dielectric strength characteristics (characteristic that the insulation state is maintained even under high voltage) ) And workability (property that a film capacitor can be manufactured stably even on an industrial production scale).
- Patent Document 1 describes a film capacitor that uses a film formed by molding a hydride of a norbornene-based ring-opening polymer or the like.
- a film made of a norbornene-based ring-opening polymer hydride is suitable as a dielectric film of a film capacitor.
- a film made of a norbornene-based ring-opening polymer hydride is suitable as a dielectric film of a film capacitor.
- the present invention has been made in view of the above-described prior art, and an object of the present invention is to provide a film capacitor having a resin film having excellent heat resistance, withstand voltage characteristics, and workability as a dielectric film.
- the present inventors have intensively studied a resin film used as a dielectric film of a film capacitor.
- an unstretched film formed using a crystalline dicyclopentadiene ring-opening polymer hydrogenated product is stretched and then heat-treated, and the softening point, thermal contraction rate, tan ⁇ ,
- the resin film which has a static friction coefficient in a specific range, respectively discovered that it was excellent in all of heat resistance, a withstand voltage characteristic, and workability
- a film capacitor comprising a resin film having a .0001 to 0.0010 and a static friction coefficient of 0.01 to 1.00.
- a film capacitor having, as a dielectric film, a resin film excellent in all of heat resistance, withstand voltage characteristics, and workability.
- the present invention is a film capacitor having a dielectric film and a metal layer.
- the dielectric film constituting the film capacitor of the present invention is a resin film obtained by subjecting an unstretched film made of a crystalline dicyclopentadiene ring-opening polymer hydrogenated product to a heat treatment after the stretching treatment.
- the resin film has a softening point of 250 to 320 ° C., a thermal shrinkage of 0.01 to 5.0%, a tan ⁇ of 0.0001 to 0.0010, and a static friction coefficient of 0.01 to 1.00. (Hereinafter sometimes referred to as “resin film (I)”).
- “Crystalline dicyclopentadiene ring-opened polymer hydrogenated product” used in the production of the resin film (I) is a dicyclopentadiene ring-opened polymer hydrogenated product, and the melting point is reduced by performing a stretching treatment or the like. A film-like molded product is obtained.
- the hydrogenated crystalline dicyclopentadiene ring-opening polymer include hydrogenated dicyclopentadiene ring-opening polymers having syndiotactic stereoregularity described in JP-A-2006-52333. Can be mentioned.
- polymer ( ⁇ ) ring-opened polymer of dicyclopentadiene having syndiotactic stereoregularity
- polymer ( ⁇ ) hydrophilic polymer
- polymer ( ⁇ ) hydrophilic polymer
- the polymer ( ⁇ ) can be obtained by ring-opening polymerization of dicyclopentadiene.
- the dicyclopentadiene to be used includes endo isomers and exo isomers, both of which can be used as monomers, and either isomer may be used alone or the endo isomer.
- An isomer mixture in which an exo isomer is present in an arbitrary ratio may be used.
- the ratio of one stereoisomer is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.
- the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic
- the polymer ( ⁇ ) may have a repeating unit other than the repeating unit derived from dicyclopentadiene as long as it gives a crystalline polymer ( ⁇ ).
- a polymer ( ⁇ ) can be produced by ring-opening copolymerization of dicyclopentadiene and a monomer other than dicyclopentadiene.
- monomers other than dicyclopentadiene polycyclic norbornene compounds other than dicyclopentadiene, bicyclic norbornene compounds having no ring structure condensed with norbornene skeleton, monocyclic olefins, and cyclic dienes, and these And derivatives thereof.
- the amount thereof is usually more than 0% by weight and 20% by weight or less, preferably more than 0% by weight and 10% by weight or less based on the total monomers.
- the catalyst used for producing the polymer ( ⁇ ) is not particularly limited as long as it can ring-open polymerize dicyclopentadiene to produce the polymer ( ⁇ ).
- a ring-opening polymerization catalyst containing a metal compound represented by the following formula (1) (hereinafter sometimes referred to as “metal compound (1)”) as a catalytically active component can be mentioned.
- M is a metal atom selected from group 6 transition metal atoms in the periodic table.
- R 1 may have a substituent at at least one of the 3, 4, and 5 positions.
- R 2 is a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent
- X is a halogen atom
- an alkyl group L is a group selected from an aryl group and an alkylsilyl group
- L is an electron-donating neutral ligand
- a is 0 or 1
- b is an integer of 0 to 2.
- the metal atom (M) constituting the metal compound (1) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Of these, molybdenum or tungsten is preferable, and tungsten is more preferable.
- the metal compound (1) comprises a metal imide bond.
- R 1 is a substituent on the nitrogen atom constituting the metal imide bond.
- substituent of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions of R 1 include an alkyl group such as a methyl group and an ethyl group; a fluorine atom, a chlorine atom, a bromine A halogen atom such as an atom; an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; and the like, and further, substituents present in at least two positions of the 3, 4, and 5 positions are bonded to each other. May be.
- phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include a phenyl group; a 4-methylphenyl group, a 4-chlorophenyl group, a 3-methoxyphenyl group, 4 -Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group; two groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group and 3,5-dimethoxyphenyl group; Substituted phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group, 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2- And 2-naphthyl group which may have a substituent such as naphthyl group.
- the carbon number of the alkyl group which may have a substituent of R 3 in the group represented by —CH 2 R 3 of R 1 is not particularly limited, but is usually 1 to 20, preferably 1 to 10 More preferably, it is 1 to 4.
- the alkyl group may be linear or branched.
- the substituent of the alkyl group is not particularly limited, and examples thereof include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group.
- Examples of the aryl group of R 3 which may have a substituent include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- the substituent of the aryl group is not particularly limited, and examples thereof include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; Can be mentioned.
- R 3 is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, or a decyl group. Is preferred.
- the metal compound (1) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. That is, in the formula (1), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In the metal compound (1), when there are two or more groups represented by X, these groups may be bonded to each other.
- Examples of the halogen atom for X include a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the alkyl group for X include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group.
- Examples of the aryl group for X include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- Examples of the alkylsilyl group of X include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.
- the metal compound (1) may have one metal alkoxide bond or one metal aryloxide bond.
- the substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R 2 in formula (1)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups.
- the alkyl group which may have a substituent of R 2 and the aryl group which may have a substituent include the alkyl group and substituent which may have a substituent of R 3 described above. The thing similar to what was shown as an aryl group which may have this is mentioned.
- the metal compound (1) may have one or two electron-donating neutral ligands.
- this electron-donating neutral ligand (L in the formula (1)) for example, an electron-donating compound containing an atom of Group 14 or Group 15 of the Periodic Table can be mentioned.
- Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine. Among these, ethers are preferable.
- the metal compound (1) is preferably a tungsten compound having a phenylimide group (in the formula (1), M is a tungsten atom and R 1 is a phenyl group), and tetrachlorotungsten phenylimide (tetrahydrofuran). Is more preferable.
- the metal compound (1) includes a group 6 transition metal oxyhalide, a phenyl isocyanate which may have a substituent at at least one of the 3, 4, and 5 positions, or a monosubstituted methyl isocyanate. And an electron-donating neutral ligand (L) and, if necessary, an alcohol, a metal alkoxide, a metal aryloxide, etc. (for example, a method described in JP-A-5-345817) ) Can be synthesized.
- the synthesized metal compound (1) may be used for the ring-opening polymerization reaction after purification and isolation by crystallization or the like, or the obtained mixed solution may be used as a catalyst solution without purification. Good.
- the amount of the metal compound (1) used as the ring-opening polymerization catalyst is usually 1: 100 to 1: 2,000,000, preferably 1: 500, in a molar ratio of (metal compound (1): monomer).
- the amount is from 1 to 1,000,000, more preferably from 1: 1,000 to 1: 500,000. If the amount of the catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.
- the metal compound (1) When ring-opening polymerization is performed using the metal compound (1), the metal compound (1) may be used alone, or the metal compound (1) and an organometallic reducing agent may be used in combination. By using the metal compound (1) and the organometallic reducing agent in combination, the polymerization activity may be increased.
- the organometallic reducing agent include compounds of Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organolithium, organomagnesium, organozinc, organoaluminum, or organotin are preferably used, and organoaluminum or organotin are particularly preferably used.
- Examples of the organic lithium include methyl lithium, n-butyl lithium, and phenyl lithium.
- Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide and the like.
- Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc.
- organic aluminum examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Is mentioned.
- organic tin examples include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
- the amount of the organometallic reducing agent used is preferably 0.1 to 100 moles, more preferably 0.2 to 50 moles, and particularly preferably 0.5 to 20 moles, relative to the metal compound (1). If the amount of the organic metal reducing agent used is too small, the polymerization activity may not be improved. If the amount of the organic metal reducing agent used is too large, side reactions may easily occur.
- the ring-opening polymerization reaction is usually performed in an organic solvent.
- the organic solvent is not particularly limited as long as the target polymer ( ⁇ ) or polymer ( ⁇ ) can be dissolved or dispersed under predetermined conditions and does not inhibit the polymerization reaction or the hydrogenation reaction. .
- organic solvent examples include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane.
- aliphatic hydrocarbons such as pentane, hexane, and heptane
- cyclopentane cyclohexane
- methylcyclohexane dimethylcyclohexane
- trimethylcyclohexane ethylcyclohexane
- diethylcyclohexane diethylcyclohexane
- decahydronaphthalene bicycloheptane
- tricyclodecane examples include ali
- Alicyclic hydrocarbons such as hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Solvents.
- aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.
- the ring-opening polymerization reaction can be initiated by mixing the monomer, the metal compound (1), and, if necessary, the organometallic reducing agent.
- the order in which these components are added is not particularly limited.
- a mixture of the metal compound (1) and the organometallic reducing agent may be added to the monomer and mixed, or a mixture of the monomer and the metal compound (1) may be added to the organometallic reducing agent.
- the metal compound (1) may be added to and mixed with the mixture of the monomer and the organometallic reducing agent.
- the total amount of each component may be added at once, or may be added in multiple portions.
- the concentration of the monomer at the start of the ring-opening polymerization reaction is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. If the monomer concentration is too low, the productivity of the polymer ( ⁇ ) may decrease. If the monomer concentration is too high, the viscosity of the solution after polymerization is too high, and the subsequent hydrogenation reaction. May become difficult.
- An activity regulator may be added to the polymerization reaction system.
- the activity regulator is used for the purpose of stabilizing the ring-opening polymerization catalyst, adjusting the polymerization reaction rate and the molecular weight distribution of the polymer.
- the activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing organic compound, a nitrogen-containing organic compound, or a phosphorus-containing organic compound.
- ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Amines such as triisopropylamine, quinuclidine, N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as trimethyl phosphate and triphenyl phosphate; phosphine oxides such as triphenyl phosphine oxide; and the like.
- ketones such as acetone, benzophenone and cyclohexanone
- activity regulators can be used alone or in combination of two or more.
- the amount thereof is not particularly limited, but it may be usually selected within a range of 0.01 to 100 mol% with respect to the metal compound (1) used as the ring-opening polymerization catalyst.
- a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the polymer ( ⁇ ).
- molecular weight regulators include ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene, and the like; 1,3-buta
- the polymerization temperature is not particularly limited, but is usually in the range of ⁇ 78 ° C. to + 200 ° C., and preferably in the range of ⁇ 30 ° C. to + 180 ° C.
- the polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.
- the polymer ( ⁇ ) is made efficient by carrying out the ring-opening polymerization reaction of the monomer containing dicyclopentadiene under the conditions as described above. Can be manufactured well.
- the ratio of racemo dyad (degree of syndiotactic stereoregularity) in the polymer ( ⁇ ) is usually 60% or more, preferably 65% or more, more preferably 70 to 99%.
- the ratio of the racemo dyad in the polymer ( ⁇ ) can be adjusted by selecting the type of the ring-opening polymerization catalyst.
- the weight average molecular weight (Mw) of the polymer ( ⁇ ) is not particularly limited, but is usually 10,000 to 100,000, preferably 15,000 to 80,000.
- a polymer ( ⁇ ) obtained by hydrogenating a polymer ( ⁇ ) having a weight average molecular weight within this range is more excellent in moldability.
- molding this polymer ((beta)) is more excellent in heat resistance.
- the weight average molecular weight of a polymer ((alpha)) can be adjusted by adjusting the addition amount etc. of the molecular weight modifier used at the time of superposition
- the molecular weight distribution (Mw / Mn) of the polymer ( ⁇ ) is not particularly limited, but is usually 4.0 or less, preferably 3.5 or less.
- a polymer ( ⁇ ) obtained by hydrogenating a polymer ( ⁇ ) having a molecular weight distribution within this range is more excellent in moldability.
- the molecular weight distribution of the polymer ( ⁇ ) can be adjusted by the monomer addition method and the monomer concentration during the ring-opening polymerization reaction.
- the above weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are standard polystyrene equivalent values obtained by gel permeation chromatography using tetrahydrofuran as a solvent.
- the polymer ( ⁇ ) can be produced by carrying out a hydrogenation reaction (carbon-carbon unsaturated bond hydrogenation reaction) of the polymer ( ⁇ ).
- the hydrogenation reaction of the polymer ( ⁇ ) can be performed, for example, by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst.
- the hydrogenation catalyst is not particularly limited, and a homogeneous catalyst or a heterogeneous catalyst generally used for a hydrogenation reaction of an olefin compound can be appropriately used.
- Homogeneous catalysts include transition metal compounds such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium and alkali Catalyst system consisting of a combination of metal compounds, dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium And a noble metal complex catalyst.
- transition metal compounds such as cobalt acetate / triethylaluminum, nickel acety
- heterogeneous catalysts include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, nickel, palladium, platinum, rhodium, ruthenium, or these And a solid catalyst obtained by supporting the above metal on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide.
- the hydrogenation reaction is usually performed in an inert organic solvent.
- inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like.
- the inert organic solvent is usually the same as the solvent used for the polymerization reaction, and the hydrogenation reaction can be carried out using a polymerization reaction solution with the hydrogenation catalyst added as it is.
- the reaction temperature is usually ⁇ 20 ° C. to + 250 ° C., preferably ⁇ 10 ° C. to + 220 ° C., more preferably 0 ° C. to 200 ° C. If the reaction temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur.
- the hydrogen pressure is usually from 0.01 to 20 MPa, preferably from 0.05 to 15 MPa, more preferably from 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required.
- the reaction time is not particularly limited, but is usually 0.1 to 10 hours.
- the hydrogenation rate in the hydrogenation reaction is not particularly limited, but is preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more, and most preferably 99% or more. The higher the hydrogenation rate, the more the heat resistance of the polymer ( ⁇ ) is improved.
- the syndiotactic stereoregularity of the polymer ( ⁇ ) subjected to the hydrogenation reaction is usually maintained. Therefore, the polymer ( ⁇ ) has syndiotactic stereoregularity.
- the ratio of racemo dyad in the polymer ( ⁇ ) is not particularly limited as long as the polymer ( ⁇ ) has crystallinity, but is usually 60% or more, preferably 65% or more, more preferably 70 to 99%. .
- the ratio of the racemo dyad in the polymer ( ⁇ ) can be quantified based on the spectrum data obtained by measuring a 13 C-NMR spectrum.
- 13 C-NMR measurement was performed at 200 ° C. using a mixed solvent of 1,2,4-trichlorobenzene-d3 and orthodichlorobenzene-d4, and the 43.35 ppm signal derived from meso-dyad
- the ratio of racemo dyad can be determined from the intensity ratio of the 43.43 ppm signal derived from dyad.
- the polymer ( ⁇ ) has crystallinity (that is, a film-like molded body having a melting point is obtained).
- the temperature range of the melting point is not particularly limited, but is usually 260 to 275 ° C.
- the polymer ( ⁇ ) having such a melting point is excellent due to a balance between moldability and heat resistance.
- the melting point of the polymer ( ⁇ ) can be adjusted by adjusting the degree of syndiotactic stereoregularity (racemo dyad ratio) or selecting the type of monomer used. .
- Additives include: antioxidants such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants; light stabilizers such as hindered amine light stabilizers; petroleum waxes, Fischer-Tropsch waxes and polyalkylene waxes Waxes such as sorbitol compounds, metal salts of organic phosphoric acid, metal salts of organic carboxylic acids, nucleating agents such as kaolin and talc; diaminostilbene derivatives, coumarin derivatives, azole derivatives (for example, benzoxazole derivatives, benzotriazole derivatives) , Benzimidazole derivatives, and benzothiazole derivatives), carbazole derivatives, pyridine derivatives, naphthalic acid derivatives, and imidazolone derivatives, etc
- the amount of the additive used is not particularly limited as long as the effect of the present invention is not impaired, and can be appropriately determined according to the purpose.
- the content of these additives contained in the resin composition is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer ( ⁇ ).
- the manufacturing method of an unstretched film is not specifically limited, A well-known shaping
- the molding method include injection molding methods, extrusion molding methods, press molding methods, inflation molding methods, blow molding methods, calendar molding methods, cast molding methods, and compression molding methods.
- the extrusion molding method is preferable because the thickness of the unstretched film can be easily controlled.
- the cylinder temperature molten resin temperature
- the cast roll temperature is usually 45 to 160 ° C., preferably 45 to 130 ° C.
- the roll temperature is usually 25 to 150 ° C, preferably 45 to 120 ° C.
- the thickness of the unstretched film is not particularly limited, but is usually 1 ⁇ m to 1 mm, preferably 10 to 500 ⁇ m.
- the stretching method is not particularly limited, and a known method can be appropriately used. Stretching methods include uniaxial stretching in the longitudinal direction using the difference in peripheral speed on the roll side, uniaxial stretching in the lateral direction using a tenter stretching machine, and the like.
- Biaxial stretching method such as sequential biaxial stretching method that grips and stretches in the lateral direction using a tenter stretching machine; Feeding force, pulling force or pulling force at different speeds can be applied in the lateral or longitudinal direction And a method of continuously and obliquely stretching in a direction of an arbitrary angle ⁇ with respect to the width direction of the film using a tenter stretching machine.
- the stretching temperature is usually 95 to 135 ° C, preferably 100 to 130 ° C.
- the stretching temperature is 95 ° C. or higher, the problem that the film breaks during stretching or the productivity decreases due to the clip coming off becomes difficult to occur.
- the stretching temperature is 135 ° C. or lower, a resin film having a low thermal shrinkage rate can be efficiently produced.
- the draw ratio is usually 1.2 to 10 times, preferably 1.5 to 5 times.
- the draw ratio is 1.2 times or more, a resin film having a high softening point can be efficiently produced.
- the draw ratio is 10 times or less, a resin film having excellent toughness can be efficiently produced.
- the stretching ratio is defined by the product of the longitudinal and lateral stretching ratios.
- the stretching speed is usually 100 to 30,000 mm / min, preferably 1,000 to 20,000 mm / min.
- the stretching speed is 100 mm / min or more, the resin film (I) having a high softening point can be efficiently produced.
- the stretching speed is 30,000 mm / min or less, the problem that the film is broken during stretching or the productivity is lowered due to the clip coming off is less likely to occur.
- the heating method is not particularly limited, and a known method can be appropriately used.
- Examples of the heating method include a method in which a stretched film is fixed on a table and then heated using a heating apparatus such as a heat treatment oven or an infrared heater.
- the heating temperature is usually 150 to 240 ° C, preferably 160 to 210 ° C.
- the heating time is usually 0.1 to 600 minutes, preferably 3 to 300 minutes. Resin film (I) with a small heat shrinkage rate can be efficiently manufactured because heating time is 0.1 minutes or more.
- the heating time is 600 minutes or less, the resin film (I) having a small tan ⁇ can be efficiently produced.
- the thickness of the film obtained as described above is not particularly limited, but is usually 1 to 200 ⁇ m, preferably 2 to 150 ⁇ m.
- a film having a thickness within the above range is preferably used as a dielectric film of a film capacitor.
- the resin film (I) is obtained by subjecting an unstretched film formed using a crystalline dicyclopentadiene ring-opened polymer hydrogenated product to a heat treatment, followed by a heat treatment.
- the softening point is 250 to 320 ° C. and heating at 200 ° C. for 10 minutes
- the thermal shrinkage is 0.01 to 5.0%
- tan ⁇ is 0.0001 to 0.0010
- the static friction coefficient is 0.01 to 1.00. It is a resin film.
- the softening point of the resin film (I) is 250 to 320 ° C., preferably 250 to 300 ° C. If the softening point of the resin film (I) is too low, the static friction coefficient tends to be high, and the workability at the time of producing a film capacitor tends to be poor. On the other hand, the resin film (I) having a softening point exceeding 320 ° C. is usually difficult to obtain.
- the softening point of the resin film (I) can be increased by, for example, increasing the stretching ratio or increasing the stretching speed in the stretching process. Moreover, there exists a tendency for the resin film (I) of a higher softening point to be obtained by using the polymer ((beta)) with a high ratio of a racemo dyad and a hydrogenation rate.
- the heat shrinkage rate of the resin film (I) when heated at 200 ° C. for 10 minutes is 0.01 to 5.0%, preferably 0.1 to 4.9%.
- the resin film (I) having a too high heat shrinkage rate tends to be inferior in heat resistance.
- the resin film (I) having a thermal shrinkage rate of less than 0.01% is usually difficult to obtain.
- This heat shrinkage rate can be reduced by, for example, performing a stretching process at a stretching temperature that is not too high, or performing a heating process at an appropriate temperature over a certain period of time.
- the tan ⁇ of the resin film (I) is 0.0001 to 0.0010.
- the resin film (I) having tan ⁇ exceeding 0.0010 tends to be inferior in the withstand voltage characteristics.
- a resin film (I) having a tan ⁇ of less than 0.0001 is usually difficult to obtain.
- the tan ⁇ of the resin film (I) can be reduced by, for example, avoiding heating for a long time in the heat treatment.
- the resin film (I) with smaller tan-delta can be manufactured by reducing the metal amount contained as an impurity in a polymer ((beta)).
- the static friction coefficient of the resin film (I) is 0.01 to 1.00, preferably 0.10 to 0.90.
- the resin film (I) having a static friction coefficient exceeding 1.00 and the resin film (I) having a static friction coefficient of less than 0.01 tend to be inferior in workability.
- the static friction coefficient of the resin film (I) can be determined by, for example, increasing the stretching ratio, increasing the stretching speed, or performing a heat treatment at an appropriate temperature over a certain amount of time in the stretching process. Can be small.
- the resin film (I) with a smaller static friction coefficient can be manufactured by using the polymer ((beta)) with a high ratio of a racemo dyad and a hydrogenation rate.
- the resin film (I) having the above characteristics is excellent in heat resistance, withstand voltage characteristics and workability. For example, even when the resin film (I) is heated at 220 ° C. for 10 minutes, the resin film (I) is less likely to shrink or soften and retain its shape. Moreover, when a dielectric breakdown test is performed on the resin film (I), the dielectric breakdown voltage is usually 400 kV / mm or more. In addition, since the resin film (I) has an appropriate coefficient of static friction, when winding the long resin film (I) into a roll shape or pulling out the resin film (I) from this roll, When manufacturing a film capacitor of a type, work can be performed efficiently.
- the resin film (I) is used as a dielectric film material for a film capacitor.
- the resin film (I) As the dielectric film made of the resin film (I), the resin film (I) is cut into a predetermined size, or the surface of the resin film (I) is subjected to surface treatment such as corona treatment or plasma treatment. Later, the thing cut
- Metal layer It does not specifically limit as a metal layer which comprises the film capacitor of this invention, The thing similar to the metal layer (it is also called an electrode layer) of the conventional film capacitor is mentioned.
- the metal which comprises a metal layer will not be specifically limited if it is an electroconductive metal, For example, aluminum, zinc, gold
- the metal layer can be formed by using a metal foil of these metals. Moreover, the vapor deposition metal film obtained by vapor-depositing a metal on the dielectric film [resin film (I)] surface can also be used as a metal layer.
- the thickness of the metal layer is not particularly limited, but is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 3 to 15 ⁇ m. It is a range.
- the thickness of the metal layer is not particularly limited, but is usually in the range of 10 to 200 nm, preferably 20 to 100 nm.
- a metal layer that is thin and excellent in adhesion to a dielectric film can be efficiently formed, and a film capacitor that is smaller and excellent in durability can be manufactured.
- a coating is preferred.
- the formation method of a vapor deposition metal film is not specifically limited, A vacuum evaporation method, sputtering method, an ion plating method, etc. can be utilized suitably.
- the deposited metal film may be a single layer or may be multilayered. Examples of the multilayered deposited metal film include a deposited metal film described in JP-A-2-250360.
- the film capacitor of the present invention has the dielectric film and a metal layer.
- the dielectric film is not particularly limited as long as the dielectric film is made of the resin film (I).
- the film capacitor of the present invention includes a laminated film capacitor in which dielectric films and metal layers are alternately laminated (Japanese Patent Laid-Open Nos. 63-181411, 3-18113, etc.); a tape-shaped dielectric And a wound film capacitor (Japanese Patent Laid-Open No. 60-262414, Japanese Patent Laid-Open No. 3-286514, etc.) including a body film and a metal layer.
- the manufacturing method of these film capacitors is not particularly limited, and a conventionally known method can be used.
- the film capacitor of the present invention has a resin film having excellent heat resistance, withstand voltage characteristics, and workability as a dielectric film. Therefore, even if the film capacitor of the present invention is small, it has excellent heat resistance and durability, and even when produced on an industrial scale, it is difficult for defective products to occur.
- Molecular weight of dicyclopentadiene ring-opened polymer (weight average molecular weight and number average molecular weight)
- the molecular weight of the dicyclopentadiene ring-opened polymer was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and obtained as a standard polystyrene equivalent value. Measurement was performed at 40 ° C. using System HLC-8320 (manufactured by Tosoh Corporation) as a measuring apparatus and an H type column (manufactured by Tosoh Corporation) as a column.
- Ratio of racemo dyad of hydrogenated dicyclopentadiene ring-opening polymer Using a mixed solvent of 1,2,4-trichlorobenzene-d3 and orthodichlorobenzene-d4, applying an inverse decoupling method, A 13 C-NMR measurement was performed at 200 ° C., and a signal of 43.35 ppm derived from meso dyad and 43.43 ppm signal derived from racemo dyad were obtained with a 127.5 ppm peak of orthodichlorobenzene-d4 as a reference shift. Based on the intensity ratio, the ratio of racemo dyad of the hydrogenated dicyclopentadiene ring-opening polymer was determined.
- the obtained resin film was cut into a circle having a diameter of 5 mm at an arbitrary position to obtain a measurement sample.
- the obtained measurement sample was heated using a thermomechanical analyzer (SS6100, manufactured by Hitachi High-Tech Science Co., Ltd.) under a temperature rising condition of 10 ° C./min, and the softening point of the resin film was measured.
- Thermal contraction rate of resin film The obtained resin film was cut into a square of 500 mm x 500 mm at an arbitrary site to obtain a measurement sample. At this time, each side of the square was made to coincide with the flow direction (MD direction) and the width direction (TD direction) during the production of the resin film. The obtained measurement sample was heated at 200 ° C. for 10 minutes using an oven, the amount of change in length in the MD direction and the TD direction before and after heating was examined, and the thermal contraction rate of the resin film was calculated. In addition, this thermal contraction rate is an average value of MD direction and TD direction.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the dicyclopentadiene ring-opened polymer in the obtained reaction solution are 8,750 and 28,100, respectively, and the molecular weight distribution (Mw / Mn) is 3.21.
- a hydrotalcite-like compound manufactured by Kyowa Chemical Industry Co., Ltd., Kyoward (registered trademark) 2000
- a filter aid Radiolite (registered trademark) # 1500, manufactured by Showa Chemical Industry Co., Ltd.
- a PP pleated cartridge filter manufactured by ADVANTEC Toyo Co., TCP-HX
- Example 1 After the unstretched film obtained in Production Example 3 was cut into a 90 mm ⁇ 90 mm square at an arbitrary site, this was placed in a small stretcher (EX10-B type, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the stretching temperature: The film was stretched under the conditions of 100 ° C., stretching ratio: 2.0 ⁇ 2.0 times, stretching speed: 10,000 mm / min. Next, the obtained stretched film was fixed to an iron plate, and this was subjected to a heat treatment at 200 ° C. for 20 minutes using an oven to obtain a resin film for a dielectric film. Various measurements were performed about the obtained resin film for dielectric films. The measurement results are shown in Table 1.
- Example 2 In Example 1, the stretching ratio was changed to 3.0 ⁇ 3.0 times, the stretching speed was changed to 300 mm / min, and the stretching process was performed. Further, the heating temperature was changed to 210 ° C., and the heating process was performed. Obtained the resin film for dielectric films like Example 1, and performed various measurements about the obtained resin film for dielectric films. The measurement results are shown in Table 1.
- Example 3 A resin film for a dielectric film was prepared in the same manner as in Example 1 except that in Example 1, the stretching process was performed by changing the stretching temperature to 130 ° C., and the heating process was further performed by changing the heating temperature to 150 ° C. Various measurements were performed on the obtained resin film for dielectric film. The measurement results are shown in Table 1.
- Example 4 In Example 1, except that the heating time was changed to 5 minutes and the heat treatment was performed, the resin film for dielectric film was obtained in the same manner as in Example 1, and the obtained resin film for dielectric film was variously obtained. Measurements were made. The measurement results are shown in Table 1.
- Example 5 In Example 1, the stretching ratio was changed to 1.5 ⁇ 1.5 times, the stretching process was performed, and the heating process was further performed by changing the heating temperature to 230 ° C. and the heating time to 100 minutes. In the same manner as in Example 1, a dielectric film resin film was obtained, and various measurements were performed on the obtained dielectric film resin film. The measurement results are shown in Table 1.
- Example 1 In Example 1, except that the stretching temperature was changed to 140 ° C. and the stretching process was performed, a resin film was obtained in the same manner as in Example 1, and various measurements were performed on the obtained resin film. The measurement results are shown in Table 1.
- Example 2 In Example 1, a resin film was obtained in the same manner as in Example 1 except that the stretching treatment was performed by changing the stretching ratio to 1.1 times x 1.1 times, and various measurements were performed on the obtained resin film. Went. The measurement results are shown in Table 1. This resin film was not sufficiently crystallized and the softening point was too low. For this reason, the heat shrinkage rate could not be measured.
- Example 3 In Example 1, a resin film was obtained in the same manner as in Example 1 except that the stretching process was performed while changing the stretching speed to 80 mm / min, and various measurements were performed on the obtained resin film. The measurement results are shown in Table 1. This resin film was not sufficiently crystallized and the softening point was too low. For this reason, the heat shrinkage rate could not be measured.
- Example 4 In Example 1, except that the heating temperature was changed to 250 ° C. and the heat treatment was performed, a resin film was obtained in the same manner as in Example 1, and various measurements were performed on the obtained resin film. The measurement results are shown in Table 1.
- Example 5 In Example 1, except that the heating temperature was changed to 140 ° C. and the heat treatment was performed, a resin film was obtained in the same manner as in Example 1, and various measurements were performed on the obtained resin film. The measurement results are shown in Table 1.
- Example 6 In Example 1, a resin film was obtained in the same manner as in Example 1 except that the heat treatment was performed while changing the heating time to 0.05 minutes, and various measurements were performed on the obtained resin film. The measurement results are shown in Table 1.
- Example 7 In Example 1, a resin film was obtained in the same manner as in Example 1 except that the heat treatment was performed with the heating time changed to 700 minutes, and various measurements were performed on the obtained resin film. The measurement results are shown in Table 1.
- the resin films obtained in Examples 1 to 5 are excellent in heat resistance, withstand voltage characteristics, and workability.
- the resin films obtained in Comparative Examples 1, 4 to 6 have a large heat shrinkage rate and are inferior in heat resistance.
- the resin films obtained in Comparative Examples 2 and 3 have a low softening point, and these resin films are also inferior in heat resistance.
- the resin films obtained in Comparative Examples 2, 3, 5, and 6 have a large coefficient of static friction and are inferior in workability.
- the resin film obtained in Comparative Example 7 has a large tan ⁇ and inferior withstand voltage characteristics.
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Abstract
Description
近年、フィルムコンデンサは、小型化や大容量化が進められた結果、駆動時に発熱し易くなってきている。このため、フィルムコンデンサの誘電体フィルムとして用いられる樹脂フィルムには、耐熱性により優れることが求められている。
また、フィルムコンデンサを小型化するために、誘電体フィルムをより薄くすることが求められてきているが、誘電体フィルムを薄くすると、耐電圧特性(高電圧下でも絶縁状態が維持されるという特性)や作業性(工業的生産規模でも安定してフィルムコンデンサを製造し得るという性質)に劣る傾向があった。
〔1〕誘電体フィルムと金属層とを有するフィルムコンデンサであって、前記誘電体フィルムが、結晶性のジシクロペンタジエン開環重合体水素添加物を用いてなる未延伸フィルムを延伸処理した後、加熱処理することにより得られる樹脂フィルムであり、前記樹脂フィルムは、軟化点が250~320℃、200℃で10分間加熱したときの熱収縮率が0.01~5.0%、tanδが0.0001~0.0010、静摩擦係数が0.01~1.00の樹脂フィルムからなるものであることを特徴とするフィルムコンデンサ。
〔2〕前記樹脂フィルムが、前記未延伸フィルムを、延伸温度が95~135℃、延伸倍率が1.2~10倍、延伸速度が100~30,000mm/分の条件で延伸処理した後、加熱温度が150~240℃、加熱時間が0.1~600分の条件で加熱処理することにより得られるものである、〔1〕に記載のフィルムコンデンサ。
本発明のフィルムコンデンサを構成する誘電体フィルムは、結晶性のジシクロペンタジエン開環重合体水素添加物を用いてなる未延伸フィルムを延伸処理した後、加熱処理することにより得られる樹脂フィルムであり、前記樹脂フィルムは、軟化点が250~320℃、熱収縮率が0.01~5.0%、tanδが0.0001~0.0010、静摩擦係数が0.01~1.00の樹脂フィルム(以下、「樹脂フィルム(I)」ということがある。)からなる。
結晶性のジシクロペンタジエン開環重合体水素添加物としては、例えば、特開2006-52333号公報に記載の、シンジオタクチック立体規則性を有するジシクロペンタジエンの開環重合体の水素添加物が挙げられる。
以下、「シンジオタクチック立体規則性を有するジシクロペンタジエンの開環重合体」を「重合体(α)」といい、「重合体(α)の水素添加物」を「重合体(β)」ということがある。
ジシクロペンタジエン以外の単量体としては、ジシクロペンタジエン以外の多環式ノルボルネン系化合物、ノルボルネン骨格に縮合した環構造を有しない2環のノルボルネン系化合物、モノ環状オレフィン、及び環状ジエン、並びにこれらの誘導体が挙げられる。
これらの単量体を用いる場合、その量は、全単量体に対して、通常、0重量%超20重量%以下、好ましくは0重量%超10重量%以下である。
このような触媒としては、例えば、下記式(1)で表される金属化合物(以下、「金属化合物(1)」ということがある。)を触媒活性成分として含む開環重合触媒が挙げられる。
R1は、金属イミド結合を構成する窒素原子上の置換基である。
R1の、3,4,5位の少なくとも1つの位置に置換基を有していてもよいフェニル基の置換基としては、メチル基、エチル基等のアルキル基;フッ素原子、塩素原子、臭素原子等のハロゲン原子;メトキシ基、エトキシ基、イソプロポキシ基等のアルコキシ基;等が挙げられ、さらに、3,4,5位の少なくとも2つの位置に存在する置換基が互いに結合したものであってもよい。
R3としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t-ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基等の炭素数が1~20のアルキル基が好ましい。
この電子供与性の中性配位子(式(1)中のL)としては、例えば、周期律表第14族又は第15族の原子を含有する電子供与性化合物が挙げられる。
その具体例としては、トリメチルホスフィン、トリイソプロピルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン等のホスフィン類;ジエチルエーテル、ジブチルエーテル、1,2-ジメトキシエタン、テトラヒドロフラン等のエーテル類;トリメチルアミン、トリエチルアミン、ピリジン、ルチジン等のアミン類;が挙げられる。これらの中でも、エーテル類が好ましい。
有機金属還元剤としては、炭素数1~20の炭化水素基を有する周期律表第1、2、12、13、14族の化合物が挙げられる。なかでも、有機リチウム、有機マグネシウム、有機亜鉛、有機アルミニウム、又は有機スズが好ましく用いられ、有機アルミニウム又は有機スズが特に好ましく用いられる。
有機溶媒は、目的とする重合体(α)や重合体(β)を所定の条件で溶解もしくは分散させることが可能であり、重合反応や水素化反応を阻害しないものであれば、特に限定されない。
有機溶媒の具体例としては、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ビシクロヘプタン、トリシクロデカン、ヘキサヒドロインデン、シクロオクタン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;ジクロロメタン、クロロホルム、1,2-ジクロロエタン等のハロゲン系脂肪族炭化水素;クロロベンゼン、ジクロロベンゼン等のハロゲン系芳香族炭化水素;ニトロメタン、ニトロベンゼン、アセトニトリル等の含窒素炭化水素系溶媒;ジエチルエーテル、テトラヒドロフラン等のエーテル類;又はこれらの混合溶媒が挙げられる。これらの溶媒の中でも、芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素、エーテル類が好ましく用いられる。
各成分を混合するにあたっては、それぞれの成分の全量を一度に添加してもよいし、複数回に分けて添加してもよい。
活性調整剤は、官能基を有する有機化合物であれば、特に制限されないが、含酸素有機化合物、含窒素有機化合物、含リン有機化合物が好ましい。具体的には、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、アニソール、フラン、テトラヒドロフラン等のエーテル類;アセトン、ベンゾフェノン、シクロヘキサノン等のケトン類;エチルアセテート等のエステル類;アセトニトリルベンゾニトリル等のニトリル類;トリエチルアミン、トリイソプロピルアミン、キヌクリジン、N,N-ジエチルアニリン等のアミン類;ピリジン、2,4-ルチジン、2,6-ルチジン、2-t-ブチルピリジン等のピリジン類;トリフェニルホスフィン、トリシクロヘキシルホスフィン等のホスフィン類;トリメチルホスフェ-ト、トリフェニルホスフェ-ト等のホスフェート類;トリフェニルホスフィンオキシド等のホスフィンオキシド類;等が挙げられる。これらの活性調整剤は、1種を単独で、あるいは2種以上を混合して用いることができる。
活性調整剤を用いる場合、その量は、特に限定されないが、通常、開環重合触媒として用いる金属化合物(1)に対して0.01~100モル%の範囲で選択すればよい。
分子量調整剤としては、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン等のα-オレフィン類;スチレン、ビニルトルエン等の芳香族ビニル化合物;エチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル、酢酸アリル、アリルアルコール、グリシジルメタクリレート等の酸素含有ビニル化合物;アリルクロライド等のハロゲン含有ビニル化合物;アクリルアミド等の窒素含有ビニル化合物;1,4-ペンタジエン、1,4-ヘキサジエン、1,5-ヘキサジエン、1,6-ヘプタジエン、2-メチル-1,4-ペンタジエン、2,5-ジメチル-1,5-ヘキサジエン等の非共役ジエン;1,3-ブタジエン、2-メチル-1,3-ブタジエン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエン等の共役ジエン;等が挙げられる。
分子量調整剤を用いる場合、その量は目的とする分子量に応じて適宜決定すればよいが、通常、用いる単量体に対して、0.1~50モル%の範囲で選択すればよい。
重合体(α)の重量平均分子量は、重合時に用いる分子量調整剤の添加量等を調節することにより、調節することができる。
重合体(α)の分子量分布(Mw/Mn)は、特に限定されないが、通常4.0以下、好ましくは3.5以下である。分子量分布がこの範囲にある重合体(α)を水素添加して得られる重合体(β)は成形性により優れる。
重合体(α)の分子量分布は、開環重合反応時における単量体の添加方法や単量体の濃度により、調節することができる。
上記の重量平均分子量(Mw)、及び分子量分布(Mw/Mn)は、テトラヒドロフランを溶媒として用いた、ゲル・パーミエーション・クロマトグラフィーにより得られた標準ポリスチレン換算値である。
重合体(α)の水素添加反応は、例えば、水素化触媒の存在下で、反応系内に水素を供給することにより行うことができる。水素化触媒は、特に限定されず、オレフィン化合物の水素添加反応に一般に使用されている均一系触媒や不均一触媒を適宜使用することができる。
水素圧力は、通常0.01~20MPa、好ましくは0.05~15MPa、より好ましくは0.1~10MPaである。水素圧力が低すぎると水素化速度が遅くなりすぎる場合があり、高すぎると高耐圧反応装置が必要となる点において装置上の制約が生じる。反応時間は特に限定されないが、通常0.1~10時間である。
このような融点を有する重合体(β)は、成形性と耐熱性とのバランスにより優れる。重合体(β)の融点は、そのシンジオタクチック立体規則性の度合い(ラセモ・ダイアッドの割合)を調節したり、用いる単量体の種類を選択したりすること等により、調節することができる。
添加剤としては、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等の酸化防止剤;ヒンダードアミン系光安定剤等の光安定剤;石油系ワックスやフィッシャートロプシュワックスやポリアルキレンワックス等のワックス;ソルビトール系化合物、有機リン酸の金属塩、有機カルボン酸の金属塩、カオリン及びタルク等の核剤;ジアミノスチルベン誘導体、クマリン誘導体、アゾール系誘導体(例えば、ベンゾオキサゾール誘導体、ベンゾトリアゾール誘導体、ベンゾイミダゾール誘導体、及びベンゾチアソール誘導体)、カルバゾール誘導体、ピリジン誘導体、ナフタル酸誘導体、及びイミダゾロン誘導体等の蛍光増白剤;ベンゾフェノン系紫外線吸収剤、サリチル酸系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤等の紫外線吸収剤;タルク、シリカ、炭酸カルシウム、ガラス繊維等の無機充填材;着色剤;難燃剤;難燃助剤;帯電防止剤;可塑剤;近赤外線吸収剤;滑剤;フィラー、及び、軟質重合体等の重合体(β)以外の高分子材料;等が挙げられる。
成形方法としては、射出成形法、押出し成形法、プレス成形法、インフレーション成形法、ブロー成形法、カレンダー成形法、注型成形法、圧縮成形法等の方法が挙げられる。これらの中でも、未延伸フィルムの厚みを制御し易いことから、押出し成形法が好ましい。
押出し成形法において、シリンダー温度(溶融樹脂温度)は、通常250~330℃、好ましくは260~310℃であり、キャストロール温度は、通常45~160℃、好ましくは45~130℃であり、冷却ロール温度は、通常25~150℃、好ましくは45~120℃である。
未延伸フィルムを延伸処理する際、延伸方法は特に限定されず、公知の方法を適宜利用することができる。
延伸方法としては、ロール側の周速の差を利用して縦方向に一軸延伸する方法、テンター延伸機を用いて横方向に一軸延伸する方法等の一軸延伸法;固定するクリップの間隔を開いての縦方向の延伸と同時に、ガイドレールの広がり角度により横方向に延伸する同時二軸延伸法や、ロール間の周速の差を利用して縦方向に延伸した後、その両端部をクリップ把持してテンター延伸機を用いて横方向に延伸する逐次二軸延伸法等の二軸延伸法;横又は縦方向に左右異なる速度の送り力若しくは引張り力又は引取り力を付加できるようにしたテンター延伸機を用いてフィルムの幅方向に対して任意の角度θの方向に連続的に斜め延伸する方法;等が挙げられる。
加熱方法としては、延伸フィルムを台に固定した後、これを熱処理オーブン、赤外線ヒーター等の加熱装置を用いて加熱する方法が挙げられる。
加熱時間は、通常0.1~600分間、好ましくは3~300分間である。加熱時間が0.1分以上であることで、熱収縮率が小さい樹脂フィルム(I)を効率よく製造することができる。一方、加熱時間が600分以下であることで、tanδが小さい樹脂フィルム(I)を効率よく製造することができる。
厚みが上記範囲内であるフィルムは、フィルムコンデンサの誘電体フィルムとして好ましく用いられる。
樹脂フィルム(I)の軟化点が低すぎると、静摩擦係数が高くなる傾向があり、フィルムコンデンサを製造する際の作業性に劣り易くなる。一方、軟化点が320℃を超える樹脂フィルム(I)は、通常得られにくい。
樹脂フィルム(I)の軟化点は、例えば、延伸処理において、延伸倍率を高くしたり、延伸速度を速めたりすることで、高くすることができる。また、ラセモ・ダイアッドの割合や、水素添加率が高い重合体(β)を用いることで、より高い軟化点の樹脂フィルム(I)が得られる傾向がある。
この熱収縮率が大きすぎる樹脂フィルム(I)は、耐熱性に劣り易くなる。一方、この熱収縮率が0.01%未満の樹脂フィルム(I)は、通常得られにくい。
この熱収縮率は、例えば、高すぎない延伸温度で延伸処理を行ったり、適度な温度である程度の時間をかけて加熱処理を行ったりすることにより、小さくすることができる。
tanδが0.0010を超える樹脂フィルム(I)は、耐電圧特性に劣り易くなる。一方、tanδが0.0001未満の樹脂フィルム(I)は、通常得られにくい。
樹脂フィルム(I)のtanδは、例えば、加熱処理において長時間の加熱を避けることにより小さくすることができる。また、重合体(β)中に不純物として含まれる金属量を下げることで、tanδがより小さい樹脂フィルム(I)を製造することができる。
静摩擦係数が1.00を超える樹脂フィルム(I)や、0.01未満の樹脂フィルム(I)は、作業性に劣り易くなる。
樹脂フィルム(I)の静摩擦係数は、例えば、延伸処理において、延伸倍率を高くしたり、延伸速度を速めたりすることや、適度な温度である程度の時間をかけて加熱処理を行ったりすることで、小さくすることができる。また、ラセモ・ダイアッドの割合や、水素添加率が高い重合体(β)を用いることで、静摩擦係数がより小さい樹脂フィルム(I)を製造することができる。
例えば、樹脂フィルム(I)は、220℃で10分間加熱したときでも、収縮や軟化が生じにくく、その形状が保持される。
また、樹脂フィルム(I)について、絶縁破壊試験を行った場合、絶縁破壊電圧は、通常400kV/mm以上である。
また、樹脂フィルム(I)は、静摩擦係数が適度なものであるため、長尺の樹脂フィルム(I)をロール状に巻き取ったり、このロールから樹脂フィルム(I)を引き出す際や、巻回型のフィルムコンデンサを製造する際に、効率よく作業を行うことができる。
本発明のフィルムコンデンサを構成する金属層としては特に限定されず、従来のフィルムコンデンサの金属層(電極層ともいわれる)と同様のものが挙げられる。
金属層を構成する金属は、導電性金属であれば特に限定されず、例えば、アルミニウム、亜鉛、金、白金、銅等が挙げられる。
金属層が、金属箔を用いて形成されたものである場合、金属層の厚さは特に限定されないが、通常は、0.1~100μm、好ましくは1~50μm、より好ましくは3~15μmの範囲である。
金属層が、蒸着金属被膜である場合、金属層の厚さは特に限定されないが、通常は、10~200nm、好ましくは20~100nmの範囲である。
金属層として蒸着金属被膜を利用する場合、蒸着金属被膜の形成方法は特に限定されず、真空蒸着法、スパッタリング法、イオンプレーティング法等を適宜利用することができる。
蒸着金属被膜は一層であってもよいし、多層化されていてもよい。多層化された蒸着金属皮膜としては、例えば、特開平2-250360号公報に記載の蒸着金属皮膜が挙げられる。
本発明のフィルムコンデンサは、前記誘電体フィルムと金属層とを有するものである。
本発明のフィルムコンデンサは、誘電体フィルムが、前記樹脂フィルム(I)からなるものであればよく、その構造は特に限定されない。
これらのフィルムコンデンサの製造方法は特に限定されず、従来公知の方法を利用することができる。
したがって、本発明のフィルムコンデンサは、小さくても、耐熱性、耐久性に優れ、かつ、工業的規模で生産しても不良品が発生しにくいものである。
(1)ジシクロペンタジエン開環重合体の分子量(重量平均分子量及び数平均分子量)
ジシクロペンタジエン開環重合体の分子量は、テトラヒドロフランを溶媒とするゲル・パーミエーション・クロマトグラフィー(GPC)により測定し、標準ポリスチレン換算値として求めた。
測定装置として、システムHLC-8320(東ソー社製)を使用し、カラムとして、Hタイプカラム(東ソー社製)を用い、40℃で測定した。
1H-NMR測定を行い、ジシクロペンタジエン開環重合体水素添加物の水素添加率を求めた。
1,2,4-トリクロロベンゼン-d3とオルトジクロロベンゼン-d4の混合溶媒を用いて、inversegated decoupling法を適用して、200℃で13C-NMR測定を行い、オルトジクロロベンゼン-d4の127.5ppmのピークを基準シフトとして、メソ・ダイアッド由来の43.35ppmのシグナルと、ラセモ・ダイアッド由来の43.43ppmのシグナルの強度比に基づいて、ジシクロペンタジエン開環重合体水素添加物のラセモ・ダイアッドの割合を求めた。
得られた樹脂フィルムを任意の部位で、直径5mmの円形に切り出して測定サンプルを得た。得られた測定サンプルを、熱機械分析装置(日立ハイテクサイエンス社製、SS6100)を用いて、10℃/分の昇温条件で加熱し、樹脂フィルムの軟化点を測定した。
得られた樹脂フィルムを任意の部位で、500mm×500mmの正方形に切り出して測定サンプルを得た。このとき、正方形の各辺が、樹脂フィルム製造時の流れ方向(MD方向)と幅方向(TD方向)に一致するようにした。
得られた測定サンプルを、オーブンを用いて、200℃で10分間加熱し、加熱前後のMD方向及びTD方向の長さの変化量を調べ、樹脂フィルムの熱収縮率を算出した。なお、この熱収縮率は、MD方向とTD方向の平均値である。
得られた樹脂フィルムを任意の部位で、150mm×1mmの大きさに切り出して測定サンプルを得た。得られた測定サンプルについて、ネットワークアナライザ(アジレント社製、N5230A)を用いて、周波数1GHzにおけるtanδを測定した。
トライボギア表面性測定機(新東科学製、TYPE38)を用いて、ASTM D1894に準拠し、樹脂フィルムとボール圧子間の静摩擦係数を測定した。荷重は200g、速度は100mm/mmとした。
得られた樹脂フィルムを任意の場所で、500mm×500mmの正方形に切り出して測定サンプルを得た。
得られた測定サンプルを、オーブンを用いて、220℃で10分間加熱し、加熱後の測定サンプルの形状を目視観察し、以下の基準で樹脂フィルムの耐熱性を評価した。
○:加熱前後で測定サンプルの形状が保持されていた。
×:加熱後に、熱収縮や軟化による形状変化が観られた。
得られた樹脂フィルムについて、絶縁破壊電圧測定装置(ヤマヨ試験器社製、YST-243-100RHO)を用いて、絶縁破壊電圧を測定し、樹脂フィルムの耐電圧特性を調べた。
得られた樹脂フィルムを2枚重ね、この上に100gの重りを乗せた。樹脂フィルムの一方を10mm/秒の速さで水平に滑らせたときの様子を観察し、以下の基準で樹脂フィルムの作業性を評価した。
○:滑らせた樹脂フィルムのみが抵抗なく動いた。
×:抵抗を感じる、又は、2枚のフィルムが同時に動いた。
内部を窒素置換した金属製耐圧反応容器に、シクロヘキサン154.5部、ジシクロペンタジエン(エンド体含有率99%以上)のシクロヘキサン溶液(濃度70%)42.8部(ジシクロペンタジエンの量として30部)、1-ヘキセン1.9部を加え、全容を攪拌しながら、53℃に加熱した。
一方、テトラクロロタングステンフェニルイミド(テトラヒドロフラン)錯体0.014部を0.70部のトルエンに溶解させた溶液に、ジエチルアルミニウムエトキシド/n-ヘキサン溶液(濃度19%)0.061部を加えて10分間攪拌し、触媒溶液を調製した。
反応器の内容物を攪拌しながら、この触媒溶液を反応器内に加えて開環重合反応を開始させ、その後、全容を53℃に保ちながら4時間開環重合反応を行った。次いで、停止剤として、1,2-エタンジオール0.037部を反応器内に加えて、全容を60℃に加温し、1時間攪拌することで重合反応を停止させた。
得られた反応溶液中のジシクロペンタジエン開環重合体の数平均分子量(Mn)及び重量平均分子量(Mw)は、それぞれ、8,750及び28,100であり、分子量分布(Mw/Mn)は3.21であった。
濾過後のジシクロペンタジエン開環重合体溶液200部(重合体量30部)に、シクロヘキサン100部、クロロヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム0.0043部を添加し、水素圧6MPa、180℃で4時間水素添加反応を行なった。得られた水素添加反応液は、重合体が析出してスラリー液となっていた。
このスラリー液について、遠心分離処理を行って、ジシクロペンタジエン開環重合体水素添加物と溶液とを分離し、ジシクロペンタジエン開環重合体水素添加物を濾取した。次いで、これを60℃で24時間減圧乾燥することで、結晶性を有するジシクロペンタジエン開環重合体水素添加物28.5部を得た。
ジシクロペンタジエン開環重合体水素添加物の水素添加率は99%以上、融点(Tm)は262℃、ラセモ・ダイアッドの割合は89%であった。
製造例1で得られたジシクロペンタジエン開環重合体水素添加物100部に、酸化防止剤として、テトラキス〔メチレン-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート〕メタン(BASFジャパン社製、イルガノックス(登録商標)1010)1.1部を混合し、原料組成物を得た。この原料組成物を、内径3mmのダイ穴を4つ備えた二軸押出し機(東芝機械社製、TEM-37B)に投入し、熱溶融押出し成形法により、ストランド状の成形体を得、これを冷却した後、ストランドカッターにて細断し、樹脂ペレットを得た。
・バレル設定温度:270~280℃
・ダイ設定温度:270℃
・スクリュー回転数:145rpm
・フィーダー回転数:50rpm
製造例2で得られた樹脂ペレットを用いて、Tダイを備える熱溶融押出しフィルム成形機(Optical Control Systems社製、Measuring Extruder Type Me-20/2800 V3)にて、厚み150μm、幅120mmのフィルム状に成形し、得られた未延伸フィルムを2m/分の速度でロール状に巻き取った。
・バレル温度設定:280~290℃
・ダイ温度:270℃
・スクリュー回転数:30rpm
製造例3で得られた未延伸フィルムを任意の部位で90mm×90mmの正方形に切り出した後、これを、小型延伸機(東洋精機製作所社製、EX10-Bタイプ)に設置し、延伸温度:100℃、延伸倍率:2.0倍×2.0倍、延伸速度:10000mm/分の条件で延伸処理した。
次いで、得られた延伸フィルムを鉄板に固定し、このものを、オーブンを用いて200℃で20分間、加熱処理を行うことにより、誘電体フィルム用樹脂フィルムを得た。
得られた誘電体フィルム用樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、延伸倍率を3.0倍×3.0倍、延伸速度を300mm/分の条件に変えて延伸処理を行い、さらに加熱温度を210℃に変えて加熱処理を行ったこと以外は、実施例1と同様にして誘電体フィルム用樹脂フィルムを得、得られた誘電体フィルム用樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、延伸温度を130℃に変えて延伸処理を行い、さらに加熱温度を150℃に変えて加熱処理を行ったこと以外は、実施例1と同様にして誘電体フィルム用樹脂フィルムを得、得られた誘電体フィルム用樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、加熱時間を5分に変えて加熱処理を行ったこと以外は、実施例1と同様にして誘電体フィルム用樹脂フィルムを得、得られた誘電体フィルム用樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、延伸倍率を1.5×1.5倍に変えて延伸処理を行い、さらに加熱温度を230℃、加熱時間を100分に変えて加熱処理を行ったこと以外は、実施例1と同様にして誘電体フィルム用樹脂フィルムを得、得られた誘電体フィルム用樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、延伸温度を140℃に変えて延伸処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、延伸倍率を1.1倍×1.1倍に変えて延伸処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
なお、この樹脂フィルムは、結晶化が十分には進行しておらず、軟化点が低すぎるものであった。このため、熱収縮率を測定することができなかった。
実施例1において、延伸速度を80mm/分に変えて延伸処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
なお、この樹脂フィルムは、結晶化が十分には進行しておらず、軟化点が低すぎるものであった。このため、熱収縮率を測定することができなかった。
実施例1において、加熱温度を250℃に変えて加熱処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、加熱温度を140℃に変えて加熱処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、加熱時間を0.05分に変えて加熱処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1において、加熱時間を700分に変えて加熱処理を行ったこと以外は、実施例1と同様にして樹脂フィルムを得、得られた樹脂フィルムについて、各種測定を行った。測定結果を第1表に示す。
実施例1~5で得られた樹脂フィルムは、耐熱性、耐電圧特性、及び作業性に優れている。
一方、比較例1、4~6で得られた樹脂フィルムは、熱収縮率が大きく、耐熱性に劣っている。
比較例2、3で得られた樹脂フィルムは、軟化点が低く、これらの樹脂フィルムも耐熱性に劣っている。
比較例2、3、5、6で得られた樹脂フィルムは、静摩擦係数が大きく、作業性に劣っている。
比較例7で得られた樹脂フィルムは、tanδが大きく、耐電圧特性に劣っている。
Claims (2)
- 誘電体フィルムと金属層とを有するフィルムコンデンサであって、
前記誘電体フィルムが、
結晶性のジシクロペンタジエン開環重合体水素添加物を用いてなる未延伸フィルムを延伸処理した後、加熱処理することにより得られる樹脂フィルムであり、
前記樹脂フィルムは、軟化点が250~320℃、200℃で10分間加熱したときの熱収縮率が0.01~5.0%、tanδが0.0001~0.0010、静摩擦係数が0.01~1.00の樹脂フィルム
からなるものであることを特徴とするフィルムコンデンサ。 - 前記樹脂フィルムが、前記未延伸フィルムを、延伸温度が95~135℃、延伸倍率が1.2~10倍、延伸速度が100~30,000mm/分の条件で延伸処理した後、加熱温度が150~240℃、加熱時間が0.1~600分の条件で加熱処理することにより得られるものである、請求項1に記載のフィルムコンデンサ。
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| EP15846890.0A EP3217411B1 (en) | 2014-09-30 | 2015-09-24 | Film capacitor |
| US15/512,920 US10529494B2 (en) | 2014-09-30 | 2015-09-24 | Dielectric film |
| JP2016551960A JP6631809B2 (ja) | 2014-09-30 | 2015-09-24 | フィルムコンデンサ |
| CN201580050179.4A CN107077969B (zh) | 2014-09-30 | 2015-09-24 | 膜电容器 |
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| WO2018174029A1 (ja) * | 2017-03-21 | 2018-09-27 | 日本ゼオン株式会社 | 成形材料、樹脂成形体、化粧料容器、半導体容器、及び半導体容器の製造方法 |
| WO2019167682A1 (ja) | 2018-02-28 | 2019-09-06 | 日本ゼオン株式会社 | コンデンサ用フィルムおよびその製造方法 |
| CN110447306A (zh) * | 2017-03-30 | 2019-11-12 | 日本瑞翁株式会社 | 有机电致发光显示装置用的多层膜以及包含其的偏振片、防反射膜和有机电致发光显示装置 |
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| US11309230B1 (en) | 2020-09-29 | 2022-04-19 | Toyota Motor Engineering & Manufacturing North America, Inc. | Power electronic modules including one or more layers including a polymer produced via a frontal ring-opening polymerization process |
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| JP7294314B2 (ja) | 2018-02-28 | 2023-06-20 | 日本ゼオン株式会社 | コンデンサ用フィルムおよびその製造方法 |
| US11891489B2 (en) | 2018-02-28 | 2024-02-06 | Zeon Corporation | Film for capacitor and method of producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| US10529494B2 (en) | 2020-01-07 |
| EP3217411A4 (en) | 2018-05-23 |
| EP3217411A1 (en) | 2017-09-13 |
| EP3217411B1 (en) | 2019-07-10 |
| CN107077969B (zh) | 2019-06-18 |
| US20170301473A1 (en) | 2017-10-19 |
| JPWO2016052303A1 (ja) | 2017-07-20 |
| CN107077969A (zh) | 2017-08-18 |
| JP6631809B2 (ja) | 2020-01-15 |
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