WO2017014123A1 - フィルム - Google Patents
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- Publication number
- WO2017014123A1 WO2017014123A1 PCT/JP2016/070659 JP2016070659W WO2017014123A1 WO 2017014123 A1 WO2017014123 A1 WO 2017014123A1 JP 2016070659 W JP2016070659 W JP 2016070659W WO 2017014123 A1 WO2017014123 A1 WO 2017014123A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- mol
- copolymer
- dielectric constant
- khz
- Prior art date
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920002313 fluoropolymer Polymers 0.000 claims description 11
- 239000004811 fluoropolymer Substances 0.000 claims description 11
- 239000003990 capacitor Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000010408 film Substances 0.000 description 160
- 229920001577 copolymer Polymers 0.000 description 44
- 239000000178 monomer Substances 0.000 description 27
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000155 melt Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229920006367 Neoflon Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- 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
-
- 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
- H01G4/186—Organic dielectrics of synthetic material, e.g. derivatives of cellulose halogenated
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
- H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
Definitions
- the present invention relates to a film.
- Vinylidene fluoride homopolymer films and copolymer films made of vinylidene fluoride and other monomers are known to have a high dielectric constant.
- Patent Document 1 describes a film obtained from a vinylidene fluoride resin composition comprising 95 to 30% by weight of a vinylidene fluoride resin and 5 to 70% by weight of a polyether as a film exhibiting excellent dielectric properties. ing.
- Patent Document 2 describes a high dielectric film formed using a fluororesin containing a total of 95 mol% or more of vinylidene fluoride units and tetrafluoroethylene units.
- Patent Document 3 forms a film of a tetrafluoroethylene-based resin containing vinylidene fluoride units and tetrafluoroethylene units in the range of 0/100 to 49/51 in terms of vinylidene fluoride units / tetrafluoroethylene units (molar ratio).
- a film for a film capacitor contained as a resin is described.
- Patent Document 1 describes that the dielectric constant was measured at 80 ° C.
- Patent Document 3 describes that the dielectric constant was measured at 90 ° C. There is no mention of rates.
- the present inventors diligently examined a film that can be used at a high temperature. As a result, the conventional film has insufficient heat resistance and cannot maintain the shape of the film or has heat resistance. It has been found that there is a problem in that the dielectric constant of is significantly higher than the dielectric constant at low temperature. Films that have a large change in dielectric constant at low temperatures and high dielectric constants at high temperatures are difficult to use in equipment where the use temperature changes greatly. Power semiconductors using gallium nitride or silicon carbide are trump cards for realizing energy savings and operate at temperatures as high as 200 ° C or higher, so the electronic parts and materials used in the peripheral parts are also hotter than before. Therefore, there is a demand for the development of materials that have stable high-temperature characteristics of 150 ° C. or higher.
- An object of the present invention is to provide a film that has excellent heat resistance and has a small difference between a dielectric constant at a low temperature and a dielectric constant at a high temperature.
- the present invention has a relative permittivity of 8 or more at a frequency of 1 kHz and 30 ° C., and a relative permittivity A at a frequency of 1 kHz and 30 ° C. and a relative permittivity B at a frequency of 1 kHz and 150 ° C.
- the film of the present invention preferably has a relative dielectric constant of 8 to 12 at a frequency of 1 kHz and 30 ° C.
- the film of the present invention preferably contains a polymer.
- the film of the present invention preferably contains a fluoropolymer having a melting point of 180 ° C. or higher.
- the film of the present invention preferably contains a fluoropolymer containing vinylidene fluoride units.
- the film of the present invention preferably has a thickness of 1 to 100 ⁇ m.
- the film of the present invention can be suitably used as a high dielectric film or a piezoelectric film.
- the film of the present invention can be suitably used for a film capacitor, an electrowetting device, or a piezoelectric panel.
- the film of the present invention has the above-described configuration, it has excellent heat resistance, and the difference between the dielectric constant at low temperature and the dielectric constant at high temperature is small.
- the film of the present invention has a relative dielectric constant of 8 or more at a frequency of 1 kHz and 30 ° C.
- the relative dielectric constant is preferably 9 or more.
- the relative dielectric constant is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 12 or less.
- the film of the present invention has a rate of change of ⁇ 8 to + 8% calculated from the relative permittivity A at a frequency of 1 kHz and 30 ° C. and the relative permittivity B at a frequency of 1 kHz and 150 ° C. according to the following formula.
- the rate of change is preferably ⁇ 7 to + 7%, more preferably ⁇ 6 to + 6%.
- the rate of change may be -2.0% or less + 2.0% or more.
- Rate of change (%) (BA) / A ⁇ 100
- the film of the present invention preferably has a dielectric loss tangent of 7% or less at a frequency of 1 kHz and 150 ° C., more preferably 6% or less.
- the dielectric loss tangent is measured using an LCR meter.
- the film of the present invention preferably has a tensile elastic modulus at 25 ° C. in the longitudinal direction (MD) of 800 MPa or more, and more preferably 900 MPa or more.
- the tensile elastic modulus can be measured according to ASTM D1708.
- the film of the present invention preferably has a film thickness of 100 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 10 ⁇ m or less, and may be 1 ⁇ m or more.
- the film thickness can be measured using a digital length measuring instrument (MF-1001 manufactured by Sendai Nikon Corporation).
- the film of the present invention may have an elastic modulus at 25 ° C. in the longitudinal direction (MD) of 800 MPa or more and a film thickness of 100 ⁇ m or less.
- the elastic modulus is more preferably 900 MPa or more.
- the film thickness is more preferably 30 ⁇ m or less, further preferably 10 ⁇ m or less, and preferably 1 ⁇ m or more.
- the film of the present invention preferably has a crystallinity of 50% or more, and more preferably 55% or more.
- the upper limit is not particularly limited, but may be 90%.
- the crystallinity can be measured using an X-ray diffractometer (Ultima III, manufactured by Rigaku Corporation).
- the film of the present invention preferably contains a polymer, and more preferably contains a fluoropolymer.
- the film of the present invention may be an organic film.
- a fluoropolymer containing a vinylidene fluoride unit is preferable because it exhibits better heat resistance and the difference between the dielectric constant at low temperature and the dielectric constant at high temperature is further reduced.
- a tetrafluoroethylene copolymer is more preferable.
- the fluoropolymer preferably has a melting point of 180 ° C. or higher, and the upper limit may be 290 ° C. A more preferred lower limit is 190 ° C and an upper limit is 280 ° C.
- the fluoropolymer preferably contains vinylidene fluoride units in an amount of 10 to 49 mol%, more preferably 20 to 45 mol% of all copolymerized units.
- the copolymer exhibits superior heat resistance, and the difference between the dielectric constant at low temperature and the dielectric constant at high temperature is further reduced, so that the vinylidene fluoride unit / tetrafluoroethylene unit has a molar ratio of 10 / It is preferably 90 to 49/51, more preferably 20/80 or more, and more preferably 45/55 or less.
- the copolymer preferably further contains copolymer units of ethylenically unsaturated monomers (excluding tetrafluoroethylene and vinylidene fluoride).
- the ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with tetrafluoroethylene and vinylidene fluoride, but is ethylenic represented by the following formulas (1) and (2). It is preferably at least one selected from the group consisting of unsaturated monomers.
- CF 2 CF-ORf 1 (In the formula, Rf 1 represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.)
- the copolymer is 55.0-90.0 mol% tetrafluoroethylene, 5.0-44.9 mol% vinylidene fluoride, and 0.1-10.0 mol% of formula (1):
- CX 1 X 2 CX 3 (CF 2 ) n X 4 (1)
- X 1 , X 2 , X 3 and X 4 are the same or different and each represents H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride).
- the ethylenically unsaturated monomer represented by the formula (1) is CH 2 ⁇ CH—C 4 F 9 , CH 2 ⁇ CH—C. It is preferably at least one monomer selected from the group consisting of 6 F 13 and CH 2 ⁇ CF—C 3 F 6 H. More preferably, the ethylenically unsaturated monomer represented by formula (1) is CH 2 ⁇ CH—C 4 F 9 , CH 2 ⁇ CH—C 6 F 13 and CH 2 ⁇ CF—C 3 F 6 H.
- Tetrafluoroethylene having at least one monomer selected from the group consisting of 55.0 to 80.0 mol% of a copolymer, 19.5 to 44.9 mol% vinylidene fluoride, and 0.1 to 0.6 mol% of an ethylenically unsaturated monomer represented by the formula (1), It is a copolymer containing the copolymer unit of this.
- the copolymer is 58.0-85.0 mol% tetrafluoroethylene, 10.0-41.9 mol% vinylidene fluoride, and 0.1 to 5.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), A copolymer containing the copolymer unit may be used.
- the copolymer is 55.0-90.0 mol% tetrafluoroethylene, 9.2-44.2 mol% vinylidene fluoride, and 0.1 to 0.8 mol% of formula (2):
- CF 2 CF-ORf 1 (2)
- Rf 1 represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.
- Rf 1 represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms.
- the copolymer is 55.0-90.0 mol% tetrafluoroethylene, 5.0-44.8 mol% vinylidene fluoride, 0.1 to 10.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and 0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2), It is also preferable that it is a copolymer containing these copolymer units.
- the copolymer is 58.0-85.0 mol% tetrafluoroethylene, 9.5-39.8 mol% vinylidene fluoride, 0.1 to 5.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and 0.1 to 0.5 mol% of an ethylenically unsaturated monomer represented by the formula (2), A copolymer containing the copolymer unit may be used.
- the copolymer preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min, and more preferably 0.1 to 50 g / 10 min.
- MFR melt flow rate
- the above MFR conforms to ASTM D3307-01 and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at 297 ° C. under a load of 5 kg and the mass of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes. (G / 10 minutes).
- the copolymer preferably has a melting point of 180 ° C. or higher, and the upper limit may be 290 ° C. A more preferred lower limit is 190 ° C and an upper limit is 280 ° C.
- the melting point is measured using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) at a heating rate of 10 ° C./min in accordance with ASTM D-4591.
- the copolymer preferably has a thermal decomposition starting temperature (1% mass loss temperature) of 360 ° C. or higher. A more preferred lower limit is 370 ° C. If the said thermal decomposition start temperature is in the said range, an upper limit can be 410 degreeC, for example.
- the thermal decomposition starting temperature is a temperature at which 1% by mass of the copolymer subjected to the heating test is decomposed, and the temperature of the copolymer subjected to the heating test using a differential thermal / thermogravimetric measuring device [TG-DTA] is used. It is a value obtained by measuring the temperature when the mass is reduced by 1% by mass.
- the copolymer preferably has a storage elastic modulus (E ′) at 170 ° C. of 60 to 400 MPa as measured by dynamic viscoelasticity.
- the storage elastic modulus is a value measured at 170 ° C. by dynamic viscoelasticity measurement. More specifically, the storage elastic modulus is 30 mm in length, 5 mm in width, and 0. This is a value obtained by measuring a 25 mm sample under the conditions of a tensile mode, a grip width of 20 mm, a measurement temperature of 25 ° C. to 250 ° C., a temperature increase rate of 2 ° C./min, and a frequency of 1 Hz.
- a preferable storage elastic modulus (E ′) at 170 ° C. is 80 to 350 MPa, and a more preferable storage elastic modulus (E ′) is 100 to 350 MPa.
- the molding temperature is set to a temperature 50 to 100 ° C. higher than the melting point of the copolymer, and a film molded to a thickness of 0.25 mm at a pressure of 3 MPa is cut into a length of 30 mm and a width of 5 mm. Can be created.
- the copolymer may be a fluororesin.
- the film of the present invention contains the fluoropolymer or the copolymer, it may further contain another polymer.
- Other polymers include, for example, polycarbonate (PC), polyester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), silicone resin, polyether, polyvinyl acetate, polyethylene, polypropylene (PP) to increase flexibility.
- PVdF polyvinylidene fluoride
- VdF vinylidene fluoride
- HFP hexafluoropropylene copolymer
- poly (meth) acrylate epoxy resin, polyethylene oxide, polypropylene oxide , Polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polyamide (PA), polyimide (PI), polyamideimide (PAI), PC, polystyrene, polybenzimidazo Such as Le (PBI) and the like, also odd polyamide terms to supplement the high dielectric, cyano pullulan, such as copper phthalocyanine polymer.
- polymers to be combined with the above copolymer from the point of high affinity with the above copolymer, from the group consisting of PVdF, VdF / HFP copolymer, poly (meth) acrylate and polyvinyl acetate At least one polymer selected is preferred.
- PVdF and VdF / HFP copolymers are particularly preferable because they can improve the mechanical strength without impairing the dielectric constant.
- Poly (meth) acrylate and polyvinyl acetate are particularly preferable from the viewpoint of improving mechanical strength and insulation resistance.
- the mass ratio of the copolymer to the other polymer is preferably 50/50 to 99/1, and more preferably 75/25 to 99/1.
- the film of this invention can also contain a silica from the point which becomes possible to prevent blocking of a film, without impairing the mechanical strength of a film.
- the blending amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 parts by mass or more, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer. More preferably, it is 2 parts by mass or less.
- the film of the present invention may contain high dielectric inorganic particles, reinforcing fillers, affinity improvers and the like.
- high dielectric inorganic particles examples include barium titanate oxide particles and strontium titanate oxide particles.
- the high dielectric inorganic particles are preferably blended in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the polymer.
- the dielectric constant is improved, but an increase in dielectric loss and a decrease in withstand voltage are observed. Therefore, the upper limit of the content of the barium titanate-based oxide particles is about 200 parts by mass with respect to 100 parts by mass of the polymer. Further, the content of the barium titanate-based oxide particles is preferably 10 parts by mass or more from the viewpoint of the effect of improving the dielectric constant.
- strontium titanate-based oxide particles is preferable because an increase in dielectric constant and a decrease in dielectric loss are observed. On the other hand, since the withstand voltage is lowered, it is better not to blend when an improvement in withstand voltage is required.
- Examples of the reinforcing filler include silicon carbide, silicon nitride, magnesium oxide, potassium titanate, glass, alumina, and boron compound particles or fibers.
- affinity improver examples include coupling agents, functional group-modified polyolefins, styrene-modified polyolefins, functional group-modified polystyrenes, polyacrylimides, cumylphenols, and the like within the range that does not impair the effects of the present invention. May be included. It is more preferable that these components are not included from the point of withstand voltage.
- the film of the present invention can be suitably produced by a production method described later.
- the present invention is also a production method for producing the above-described film, which includes a step of obtaining a film by melt extrusion molding a polymer, and a step of obtaining a stretched film by uniaxially stretching the film. It is also a manufacturing method characterized by this. Since the said manufacturing method has the said structure, it has the outstanding heat resistance, and can manufacture the film with a small difference of the dielectric constant in low temperature and the dielectric constant in high temperature. It is also possible to produce a thin film having a low dielectric loss tangent at a high temperature and a high tensile elastic modulus.
- the melt extrusion molding can be performed at 250 to 380 ° C.
- the melt extrusion molding can also be performed using a melt extrusion molding machine, and the cylinder temperature is preferably 250 to 350 ° C and the die temperature is preferably 300 to 380 ° C.
- the manufacturing method preferably includes a step of winding the film obtained by the extrusion molding with a roll.
- the temperature of the roll is preferably 120 to 180 ° C.
- the obtained film is uniaxially stretched to obtain a stretched film.
- the film is stretched in the same machine direction (MD) as the direction in which the polymer is extruded in extrusion molding.
- MD machine direction
- the draw ratio in the uniaxial stretching is preferably 2 to 6 times, more preferably 3 times or more, and even more preferably 5 times or less.
- the stretching temperature in the uniaxial stretching is preferably 100 to 250 ° C, more preferably 110 ° C or higher, and more preferably 200 ° C or lower.
- the stretching speed in the uniaxial stretching is preferably 100 to 500 mm / min, more preferably 200 mm / min or more, and more preferably 400 mm / min or less.
- the production method preferably further includes a step of obtaining a stretched film by biaxially stretching a stretched film obtained by uniaxial stretching.
- the film is stretched in the transverse direction (TD) perpendicular to the longitudinal direction (MD).
- the draw ratio in the biaxial stretching is preferably 2 to 6 times, more preferably 3 times or more, and more preferably 5 times or less.
- the stretching temperature in the biaxial stretching is preferably 100 to 250 ° C, more preferably 110 ° C or more, and more preferably 200 ° C or less.
- the stretching speed in the biaxial stretching is preferably 100 to 500 mm / min, more preferably 200 mm / min or more, and more preferably 400 mm / min or less.
- the manufacturing method preferably includes a step of heat-setting the obtained stretched film after the uniaxial stretching or biaxial stretching.
- the heat setting temperature is preferably 100 to 250 ° C., more preferably 150 ° C. or more, and more preferably 200 ° C. or less.
- the film of the present invention is suitable as a high dielectric film or a piezoelectric film.
- the film of the present invention is a piezoelectric film
- the film is preferably subjected to polarization treatment.
- the polarization treatment can be performed by corona discharge.
- the film is applied using a linear electrode; or the film is needle-shaped.
- the application can be performed by using an electrode.
- Heat treatment may be performed after the polarization treatment.
- the film of the present invention can also be suitably used for a film capacitor, an electrowetting device, or a piezoelectric panel.
- the film of the present invention can be suitably used as a high dielectric film for a film capacitor.
- the film capacitor may have the film of the present invention and an electrode layer provided on at least one surface of the film.
- the structure of the film capacitor for example, a laminated type in which electrode layers and high dielectric films are alternately laminated (Japanese Patent Laid-Open Nos. 63-181411, 3-18113, etc.) or a tape-like high dielectric Winding type in which a conductive film and an electrode layer are wound (disclosed in, for example, Japanese Patent Application Laid-Open No. 60-262414 in which electrodes are not continuously laminated on a high dielectric film, or electrodes on a high dielectric film And the like disclosed in Japanese Patent Laid-Open No. 3-286514, etc.) are continuously laminated.
- a wound film capacitor that has a simple structure and is relatively easy to manufacture, and in which a wound film capacitor is formed by continuously laminating electrode layers on a highly dielectric film, it is generally highly dielectric with electrodes laminated on one side. Two films are rolled up so that the electrodes do not come into contact with each other. If necessary, the film is rolled and fixed so as not to be loosened.
- an electrode layer is not specifically limited, Generally, it is a layer which consists of conductive metals, such as aluminum, zinc, gold
- the vapor-deposited metal film is not limited to a single layer, and for example, a method of forming a semiconductor aluminum oxide layer on an aluminum layer to provide moisture resistance to form an electrode layer (for example, JP-A-2-250306) If necessary, it may be multilayered.
- the thickness of the vapor-deposited metal film is not particularly limited, but is preferably in the range of 100 to 2,000 angstrom, more preferably 200 to 1,000 angstrom. When the thickness of the deposited metal film is within this range, the capacity and strength of the capacitor are balanced, which is preferable.
- the method for forming the film is not particularly limited, and for example, a vacuum vapor deposition method, a sputtering method, an ion plating method or the like can be employed. Usually, a vacuum deposition method is used.
- Vacuum deposition methods include, for example, the batch method for molded products, the semi-continuous method used for long products, and the air-to-air method.
- the semi-continuous method is the mainstay. Has been done.
- the semi-continuous metal vapor deposition method is a method in which after vapor deposition and winding of a metal in a vacuum system, the vacuum system is returned to the atmospheric system, and the deposited film is taken out.
- the film surface can also be pretreated with a treatment for improving adhesion, such as corona treatment or plasma treatment.
- a treatment for improving adhesion such as corona treatment or plasma treatment.
- the thickness of the metal foil is not particularly limited, but is usually in the range of 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 3 to 15 ⁇ m.
- the fixing method is not particularly limited, and for example, fixing and protecting the structure may be performed simultaneously by sealing with resin or enclosing in an insulating case or the like.
- the method for connecting the lead wires is not limited, and examples thereof include welding, ultrasonic pressure welding, heat pressure welding, and fixing with an adhesive tape.
- a lead wire may be connected to the electrode before it is wound.
- the opening may be sealed with a thermosetting resin such as urethane resin or epoxy resin to prevent oxidative degradation.
- the film of the present invention can be suitably used as a high dielectric film of an electrowetting device.
- the electrowetting device includes a first electrode, a second electrode, a conductive liquid movably disposed between the first electrode and the second electrode, a first electrode, and the conductive liquid.
- the film of the present invention (high dielectric film) disposed so as to insulate the first electrode from the second electrode may be included.
- a water repellent layer may be provided on the film of the present invention.
- an insulating liquid is held between the first electrode and the second electrode, and the conductive liquid and the insulating liquid may constitute two layers.
- the electrowetting device includes an optical element, a display device (display), a variable focus lens, a light modulation device, an optical pickup device, an optical recording / reproducing device, a developing device, a droplet manipulation device, and an analytical instrument (eg, sample analysis). Therefore, it can be used for chemical, biochemical, and biological analytical instruments) in which a minute conductive liquid needs to be moved.
- the film of the present invention can be suitably used as a piezoelectric film for a piezoelectric panel.
- the piezoelectric panel may include a first electrode, a film of the present invention (piezoelectric film), and a second electrode in this order.
- the first electrode is arranged directly or indirectly on one main surface of the film
- the second electrode is arranged directly or indirectly on the other main surface of the film.
- the piezoelectric panel can be used for a touch panel.
- the touch panel can be used for an input device.
- the input device having the touch panel can input based on the touch position, the touch pressure, or both.
- the input device having the touch panel can include a position detection unit and a pressure detection unit.
- the input device can be used for electronic devices (eg, mobile phones (eg, smart phones), personal digital assistants (PDAs), tablet PCs, ATMs, automatic ticket vending machines, and car navigation systems).
- electronic devices eg, mobile phones (eg, smart phones), personal digital assistants (PDAs), tablet PCs, ATMs, automatic ticket vending machines, and car navigation systems.
- An electronic device including the input device can be operated and operated based on a touch position, a touch pressure, or both.
- ferroelectrics such as energy harvesting such as vibration power generation, touch sensors, touch panels, tactile sensors, dielectric bolometers, film speakers, tactile feedback (haptics), or electrostrictive actuators. it can.
- Fluoropolymer monomer composition Nuclear magnetic resonance apparatus AC300 (manufactured by Bruker-Biospin) was used, and 19 F-NMR measurement was carried out at a measurement temperature of (polymer melting point + 20) ° C. In some cases, the elemental analysis was appropriately combined.
- Melt flow rate [MFR] MFR is based on ASTM D3307-01 and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at 297 ° C. under a 5 kg load, the mass of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes ( g / 10 min) was defined as MFR.
- a film thickness digital length measuring instrument (MF-1001 manufactured by Sendai Nikon Corporation)
- the film placed on the substrate was measured at room temperature.
- Aluminum is vapor-deposited on both sides of the film in a dielectric loss tangent and dielectric constant vacuum to obtain a sample.
- the sample is measured for capacitance and dielectric loss tangent at 30 ° C. to 150 ° C. and a frequency of 1 kHz to 100 kHz with an LCR meter (NF circuit design block ZM2353).
- the relative dielectric constant was calculated from each obtained capacitance.
- the volume resistivity ( ⁇ ⁇ cm) was measured at 90 ° C. in a dry air atmosphere at DC 300 V using a volume resistivity digital superinsulator / microammeter.
- a film in which a plurality of films having a degree of crystallinity of 40 ⁇ m or more are stacked is set in a sample holder and used as a measurement sample.
- the degree of crystallinity of the sample was calculated from the area ratio of the crystalline part to the amorphous part of the diffraction spectrum obtained in an X-ray diffractometer (Ultima III manufactured by Rigaku Corporation) in the range of 10 to 40 °.
- Example 1 A pellet resin was formed into a film with a melt extrusion molding machine at 290 to 340 ° C. to obtain a film with a film thickness of 15 ⁇ m.
- the 15 ⁇ m film was stretched 3.0 times at 160 ° C. by a uniaxial stretching machine to obtain a stretched film having a film thickness of 9 ⁇ m.
- Example 2 A pellet resin was formed into a film with a melt extrusion molding machine at 290 to 340 ° C. to obtain a film with a film thickness of 15 ⁇ m.
- the 15 ⁇ m film was stretched 4.0 times at 160 ° C. by a uniaxial stretching machine to obtain a stretched film having a film thickness of 7 ⁇ m.
- Example 3 The 7 ⁇ m film obtained in Example 2 was heat treated at 160 ° C. for 30 minutes after stretching to obtain a stretched film having a film thickness of 7 ⁇ m.
- Example 4 A pellet resin was formed into a film with a melt extrusion molding machine at 290 to 340 ° C. to obtain a film with a film thickness of 15 ⁇ m.
- the 15 ⁇ m film was stretched 4.5 times at 160 ° C. by a uniaxial stretching machine to obtain a stretched film having a film thickness of 6 ⁇ m.
- Example 5 A pellet resin was formed into a film with a melt extrusion molding machine at 290 to 340 ° C. to obtain a film with a film thickness of 15 ⁇ m.
- the 15 ⁇ m film was stretched 2.5 times at 160 ° C. by a uniaxial stretching machine to obtain a stretched film having a film thickness of 10 ⁇ m.
- Example 6 The pellet resin was formed into a film at a temperature of 290 to 340 ° C. using a melt extrusion molding machine to obtain a film having a film thickness of 50 ⁇ m.
- the 50 ⁇ m film was stretched 3.0 times at 160 ° C. by a uniaxial stretching machine to obtain a stretched film having a film thickness of 28 ⁇ m.
- Comparative Example 1 A pellet resin was formed into a film with a heat thickness at 250 ° C. to obtain a film having a film thickness of 100 ⁇ m.
- Comparative Example 2 Vinylidene fluoride homopolymer (Neoflon VP-825, manufactured by Daikin Industries, Ltd.) was formed into a film by a melt extrusion molding machine to obtain a film having a film thickness of 25 ⁇ m.
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Abstract
Description
変化率(%)=(B-A)/A×100
上記比誘電率は、LCRメーターを用いて容量(C)を測定し、容量、電極面積(S)フィルムの厚み(d)から、式C=ε×ε0×S/d(ε0は真空の誘電率)で算出した値である。
変化率(%)=(B-A)/A×100
変化率(%)=(F-E)/E×100
上記誘電正接は、LCRメーターを用いて測定する。
上記引張弾性率は、ASTM D1708に準拠して測定できる。
上記膜厚は、デジタル測長機(仙台ニコン社製MF-1001)を用いて測定できる。
上記結晶化度は、X線回折装置(リガク社製 Ultima III)を用いて測定できる。
上記フルオロポリマーは、ビニリデンフルオライド単位を全共重合単位の10~49モル%含むことが好ましく、20~45モル%含むことがより好ましい。
(式中、X1、X2、X3及びX4は、同一又は異なって、H、F又はClを表し、nは0~8の整数を表す。但し、テトラフルオロエチレン及びビニリデンフルオライドを除く。)
(式中、Rf1は炭素数1~3のアルキル基又は炭素数1~3のフルオロアルキル基を表す。)
CH2=CF-(CF2)nX4 (3)
(式中、X4及びnは上記と同じ。)、及び、下記式(4):
CH2=CH-(CF2)nX4 (4)
(式中、X4及びnは上記と同じ。)
からなる群より選択される少なくとも1種であることが好ましく、CF2=CFCl、CH2=CFCF3、CH2=CH-C4F9、CH2=CH-C6F13、CH2=CF-C3F6H及びCF2=CFCF3からなる群より選択される少なくとも1種であることがより好ましく、CF2=CFCl、CH2=CH-C6F13及びCH2=CFCF3から選択される少なくとも1種であることが更に好ましい。
55.0~90.0モル%のテトラフルオロエチレン、
5.0~44.9モル%のビニリデンフルオライド、及び、
0.1~10.0モル%の式(1):
CX1X2=CX3(CF2)nX4 (1)
(式中、X1、X2、X3及びX4は同一又は異なってH、F又はClを表し、nは0~8の整数を表す。但し、テトラフルオロエチレン及びビニリデンフルオライドを除く。)
で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体であることが好ましい。
55.0~85.0モル%のテトラフルオロエチレン、
10.0~44.9モル%のビニリデンフルオライド、及び、
0.1~5.0モル%の式(1)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体である。
55.0~85.0モル%のテトラフルオロエチレン、
13.0~44.9モル%のビニリデンフルオライド、及び、
0.1~2.0モル%の式(1)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体である。
55.0~80.0モル%のテトラフルオロエチレン、
19.5~44.9モル%のビニリデンフルオライド、及び、
0.1~0.6モル%の式(1)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体であることである。
58.0~85.0モル%のテトラフルオロエチレン、
10.0~41.9モル%のビニリデンフルオライド、及び、
0.1~5.0モル%の式(1)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体であってもよい。
55.0~90.0モル%のテトラフルオロエチレン、
9.2~44.2モル%のビニリデンフルオライド、及び、
0.1~0.8モル%の式(2):
CF2=CF-ORf1 (2)
(式中、Rf1は炭素数1~3のアルキル基又は炭素数1~3のフルオロアルキル基を表す。)
で表されるエチレン性不飽和単量体、の共重合単位を含む共重合体であることも好ましい。
58.0~85.0モル%のテトラフルオロエチレン、
14.5~39.9モル%のビニリデンフルオライド、及び、
0.1~0.5モル%の式(2)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体である。
55.0~90.0モル%のテトラフルオロエチレン、
5.0~44.8モル%のビニリデンフルオライド、
0.1~10.0モル%の式(1)で表されるエチレン性不飽和単量体、及び、
0.1~0.8モル%の式(2)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体であることも好ましい。
55.0~85.0モル%のテトラフルオロエチレン、
9.5~44.8モル%のビニリデンフルオライド、
0.1~5.0モル%の式(1)で表されるエチレン性不飽和単量体、及び、
0.1~0.5モル%の式(2)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体である。
55.0~80.0モル%のテトラフルオロエチレン、
19.8~44.8モル%のビニリデンフルオライド、
0.1~2.0モル%の式(1)で表されるエチレン性不飽和単量体、及び、
0.1~0.3モル%の式(2)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体である。上記共重合体がこの組成を有する場合、低透過性に特に優れる。
58.0~85.0モル%のテトラフルオロエチレン、
9.5~39.8モル%のビニリデンフルオライド、
0.1~5.0モル%の式(1)で表されるエチレン性不飽和単量体、及び、
0.1~0.5モル%の式(2)で表されるエチレン性不飽和単量体、
の共重合単位を含む共重合体であってもよい。
測定サンプルは、例えば、成形温度を共重合体の融点より50~100℃高い温度に設定し、3MPaの圧力で厚さ0.25mmに成形したフィルムを、長さ30mm、巾5mmにカットすることで作成することができる。
上記製造方法は、上記構成を有することから、優れた耐熱性を有しており、低温での誘電率と高温での誘電率との差が小さいフィルムを製造することができる。また、薄く、高温での誘電正接が低く、引張弾性率が高いフィルムを製造することも可能である。
上記溶融押出成形は、また、溶融押出成形機を使用して行うことができ、シリンダー温度を250~350℃、ダイ温度を300~380℃とすることが好ましい。
上記一軸延伸における延伸倍率は、2~6倍であることが好ましく、3倍以上であることがより好ましく、5倍以下であることがより好ましい。
上記一軸延伸における延伸温度は、100~250℃であることが好ましく、110℃以上であることがより好ましく、200℃以下であることがより好ましい。
上記一軸延伸における延伸速度は、100~500mm/分であることが好ましく、200mm/分以上であることがより好ましく、400mm/分以下であることがより好ましい。
上記二軸延伸における延伸倍率は、2~6倍であることが好ましく、3倍以上であることがより好ましく、5倍以下であることがより好ましい。
上記二軸延伸における延伸温度は、100~250℃であることが好ましく、110℃以上であることがより好ましく、200℃以下であることがより好ましい。
上記二軸延伸における延伸速度は、100~500mm/分であることが好ましく、200mm/分以上であることがより好ましく、400mm/分以下であることがより好ましい。
上記熱固定の温度は、100~250℃であることが好ましく、150℃以上であることがより好ましく、200℃以下であることがより好ましい。
核磁気共鳴装置AC300(Bruker-Biospin社製)を用い、測定温度を(ポリマーの融点+20)℃として19F-NMR測定を行い、各ピークの積分値およびモノマーの種類によっては元素分析を適宜組み合わせて求めた。
示差走査熱量計RDC220(Seiko Instruments社製)を用い、ASTM D-4591に準拠して、昇温速度10℃/分にて熱測定を行い、得られた吸熱曲線のピークから融点を求めた。
MFRは、ASTM D3307-01に準拠し、メルトインデクサー(東洋精機社製)を用いて、297℃、5kg荷重下で内径2mm、長さ8mmのノズルから10分間あたりに流出するポリマーの質量(g/10分)をMFRとした。
デジタル測長機(仙台ニコン社製MF-1001)を用いて、基板に載せたフィルムを室温下にて測定した。
真空中でフィルムの両面にアルミニウムを蒸着しサンプルとする。このサンプルをLCRメーター(エヌエフ回路設計ブロック社製ZM2353)にて、30℃~150℃で、周波数1kHz~100kHzでの静電容量と誘電正接を測定する。得られた各静電容量から比誘電率を算出した。
デジタル超絶縁計/微小電流計にて、体積抵抗率(Ω・cm)を90℃、ドライエアー雰囲気下、DC300Vで測定した。
引張試験機(島津製作所社製 オートグラフAGS-Xシリーズ AGS-100NX)を使用して、500mm/分の条件下、短冊状のフィルムにて測定した。
複数のフィルムを40μm以上になるよう重ねあわせたものをサンプルホルダーにセットしこれを測定サンプルとする。サンプルをX線回折装置(リガク社製 Ultima III)にて10~40°の範囲で得られた回折スペクトルの結晶質部分と非晶質部分の面積比から結晶化度を算出した。
ペレット樹脂を290~340℃で溶融押出成形機にて製膜し、フィルム厚15μmのフィルムを得た。その15μmのフィルムを、一軸延伸機にて160℃で3.0倍延伸し、フィルム厚9μmの延伸フィルムを得た。
ペレット樹脂を290~340℃で溶融押出成形機にて製膜し、フィルム厚15μmのフィルムを得た。その15μmのフィルムを、一軸延伸機にて160℃で4.0倍延伸し、フィルム厚7μmの延伸フィルムを得た。
実施例2で得た7μmのフィルムを、延伸後160℃にて30分間熱処理を行うことで、フィルム厚7μmの延伸フィルムを得た。
ペレット樹脂を290~340℃で溶融押出成形機にて製膜し、フィルム厚15μmのフィルムを得た。その15μmのフィルムを、一軸延伸機にて160℃で4.5倍延伸し、フィルム厚6μmの延伸フィルムを得た。
ペレット樹脂を290~340℃で溶融押出成形機にて製膜し、フィルム厚15μmのフィルムを得た。その15μmのフィルムを、一軸延伸機にて160℃で2.5倍延伸し、フィルム厚10μmの延伸フィルムを得た。
ペレット樹脂を290~340℃で溶融押出成形機にて製膜し、フィルム厚50μmのフィルムを得た。その50μmのフィルムを、一軸延伸機にて160℃で3.0倍延伸し、フィルム厚28μmの延伸フィルムを得た。
ペレット樹脂を250℃でヒートプレスにて製膜し、フィルム厚100μmのフィルムを得た。
ビニリデンフルオライド単独重合体(ダイキン工業社製ネオフロンVP-825)を溶融押出成形機にて製膜し、フィルム厚25μmフィルムを得た。
Claims (8)
- 周波数1kHz、30℃での比誘電率が8以上であり、
周波数1kHz、30℃での比誘電率Aと、周波数1kHz、150℃での比誘電率Bとから、次式に従って算出される変化率が-8~+8%であることを特徴とするフィルム。
変化率(%)=(B-A)/A×100 - 周波数1kHz、30℃での比誘電率が8~12である請求項1記載のフィルム
- ポリマーを含む請求項1又は2記載のフィルム。
- 融点180℃以上のフルオロポリマーを含む請求項1、2又は3記載のフィルム。
- ビニリデンフルオライド単位を含むフルオロポリマーを含む請求項1、2、3又は4記載のフィルム。
- 厚みが1~100μmである請求項1、2、3、4又は5記載のフィルム。
- 高誘電性フィルム又は圧電フィルムである請求項1、2、3、4、5又は6記載のフィルム。
- フィルムコンデンサ、エレクトロウェッティングデバイス、又は、圧電パネルに使用される請求項1、2、3、4、5、6又は7記載のフィルム。
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JP2018135482A (ja) * | 2017-02-23 | 2018-08-30 | ダイキン工業株式会社 | フッ素樹脂フィルム |
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KR20220009489A (ko) * | 2017-01-31 | 2022-01-24 | 다이킨 고교 가부시키가이샤 | 불소 수지 필름 |
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