WO2018034182A1 - ポリプロピレンフィルムロール - Google Patents
ポリプロピレンフィルムロール Download PDFInfo
- Publication number
- WO2018034182A1 WO2018034182A1 PCT/JP2017/028571 JP2017028571W WO2018034182A1 WO 2018034182 A1 WO2018034182 A1 WO 2018034182A1 JP 2017028571 W JP2017028571 W JP 2017028571W WO 2018034182 A1 WO2018034182 A1 WO 2018034182A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- roll
- polypropylene film
- polypropylene
- film roll
- Prior art date
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 146
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 145
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 145
- 238000004804 winding Methods 0.000 claims abstract description 47
- 239000003990 capacitor Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000003746 surface roughness Effects 0.000 claims description 7
- 230000014509 gene expression Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 40
- 239000011347 resin Substances 0.000 abstract description 40
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000012545 processing Methods 0.000 abstract description 11
- 238000001816 cooling Methods 0.000 description 48
- 238000007740 vapor deposition Methods 0.000 description 28
- 230000000704 physical effect Effects 0.000 description 22
- 230000037303 wrinkles Effects 0.000 description 20
- 238000005259 measurement Methods 0.000 description 19
- 230000005855 radiation Effects 0.000 description 19
- 239000011162 core material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005019 vapor deposition process Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive 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
- 238000004458 analytical method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent 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
-
- 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
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
Definitions
- the present invention relates to a polypropylene film roll, and more specifically, in capacitor applications, particularly when producing a vapor deposition capacitor, it is possible to prevent troubles in the vapor deposition process, and further excellent workability in manufacturing each capacitor. It relates to a polypropylene film roll.
- Polypropylene films are excellent in transparency, mechanical properties, electrical properties, etc., and are therefore used in various applications such as packaging applications, tape applications, cable wrapping and electrical applications including capacitors.
- the capacitor is particularly preferably used for high voltage capacitors because of its excellent withstand voltage characteristics and low loss characteristics, not limited to DC applications and AC applications.
- various types of electrical equipment are being converted to inverters, and accordingly, there is an increasing demand for miniaturization and large capacity of capacitors.
- the film is thinned while improving the voltage resistance of polypropylene film and maintaining productivity and processability. It has become an indispensable situation.
- Patent Document 1 and Patent Document 2 cannot solve the hardness difference in the film width direction in the capacitor manufacturing process and the vapor deposition process that require high-precision feeding in recent years, and solve problems such as film meandering and conveyance wrinkles. It did not reach.
- the vapor deposition film is formed with a number of vapor deposition lanes that are partitioned by a non-deposited portion called a margin, and in particular, the margin portion (non-deposition portion) has recently become narrower.
- margins are formed by partially blocking the vapor deposition with tape or oil (margin forming material), so that the film to be deposited and the margin forming material are not changed or formed in the evaporation process (in the vapor deposition apparatus). Without it, the finished margin will not fluctuate and will not be defectively formed.
- the object of the present invention is to solve the above-mentioned problems. That is, when producing a vapor deposition capacitor, it is possible to prevent troubles such as film roll winding deviation and vertical wrinkles in the vapor deposition process, meandering during conveyance, and the like, and a polypropylene film excellent in workability in manufacturing each capacitor. To provide a role.
- the polypropylene film roll of the present invention has the following configuration. That is, A polypropylene film in which a polypropylene film is wound around a core, the average hardness of the outermost layer of the roll being 84.0 to 94.0 °, and the hardness variation in the width direction of the outermost layer of the roll being within ⁇ 2.0 ° Roll.
- the polypropylene film roll of the present invention preferably has a maximum peak height SRp of 0.4 to 2.0 ⁇ m on at least one side of the polypropylene film.
- the polypropylene film roll of the present invention has a roll width at a distance of 0, L / 5, 2L / 5, 3L / 5, 4L / 5 from the outermost roll layer, where L is the distance in the diameter direction from the outermost roll layer to the core.
- L is the distance in the diameter direction from the outermost roll layer to the core.
- the distance L in the diameter direction from the outermost roll layer to the core is preferably 20 to 300 mm.
- the 80 ° C. heat shrinkage rate of the polypropylene film is preferably 0.4 to 2.0% in the longitudinal direction and ⁇ 0.5 to 0.5% in the width direction.
- the polypropylene film roll of the present invention preferably has an air leakage index of 100 to 1,500 seconds when one surface and the opposite surface are overlapped.
- the polypropylene film roll of the present invention preferably has an air content of 0.1 to 8.0%.
- the polypropylene film roll of the present invention preferably has a surface roughness (central surface average roughness) SRa of at least one surface of the polypropylene film of 0.01 to 0.05 ⁇ m.
- the polypropylene film roll of the present invention preferably has a film thickness of 0.5 to 7.0 ⁇ m by a micrometer method.
- the film length of the polypropylene film roll of the present invention is preferably 20,000 m or more.
- the polypropylene film roll of the present invention preferably has a film width of 500 mm or more and 1,050 mm or less.
- the polypropylene film roll of the present invention is preferably for a capacitor.
- the polypropylene film roll of the present invention is used as a dielectric for a capacitor, it is not only excellent in workability but also excellent in withstand voltage in a vapor deposition process and a capacitor manufacturing process, and is suitably used as a dielectric for a capacitor. can do.
- the polypropylene film of the present invention preferably contains a polypropylene resin as a main component. Moreover, as a polypropylene resin, the copolymer and branched polypropylene which are mentioned later may be contained.
- the term “main component” means that the proportion of the specific component in all the components is 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, Especially preferably, it is 95 mass% or more.
- components other than the polypropylene resin include additives such as an antioxidant and an easy lubricant described later.
- a homopolymer of propylene may be mainly used, but a polypropylene copolymer copolymerized with other unsaturated hydrocarbons may be used as long as the object of the present invention is not impaired.
- a blend of the homopolymer of and other polymers may be used.
- Examples of the copolymer component of the polypropylene copolymer include ethylene, 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene, 4-methylpentene-1, 5- Ethylhexene-1,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicocene, vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene, 5 -Methyl-2-norbornene and the like.
- homopolymers of unsaturated hydrocarbons other than propylene and copolymers of unsaturated hydrocarbons containing propylene can be used.
- the copolymerization amount is preferably less than 1 mol%.
- the blend amount is preferably less than 20% by weight.
- the cold xylene-soluble part (hereinafter referred to as CXS) is preferably 5% by mass or less.
- CXS refers to a polypropylene component dissolved in xylene when the film is completely dissolved in xylene at 135 ° C. and then precipitated at 20 ° C., and has low stereoregularity and low molecular weight. This is considered to correspond to a component that is difficult to crystallize.
- the CXS of the polypropylene resin is more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less.
- the mesopentad fraction of the polypropylene resin constituting the polypropylene film of the present invention is preferably 95% or more, more preferably 97% or more from the viewpoint of heat shrinkage characteristics at high temperatures.
- the mesopentad fraction is an index indicating the stereoregularity of the crystal phase of the polypropylene resin measured by the nuclear magnetic resonance method (NMR method). The higher the value, the higher the crystallinity and the higher the melting point, especially at higher temperatures. From the viewpoint of vapor deposition workability in In order to obtain such a resin with high stereoregularity, there are a method of washing resin powder obtained with a solvent such as n-heptane, a method of appropriately selecting a catalyst and / or promoter, and a composition. Preferably employed. When the mesopentad fraction is in the above preferred range, the withstand voltage characteristics and dimensional stability are excellent.
- the melt flow rate (hereinafter referred to as MFR, unit: g / 10 minutes) of the polypropylene resin constituting the polypropylene film of the present invention is measured in accordance with the condition M (230 ° C., 2.16 kg) of JIS K 7210 (1995). In this case, it is preferably 1.0 to 10 g / 10 minutes, more preferably 1.5 to 8 g / 10 minutes, and further preferably 2.0 to 5 g / 10 minutes.
- MFR of the polypropylene resin is in the above preferred range, a polypropylene film can be obtained with excellent film forming properties and stability, and also withstand voltage characteristics.
- a method of controlling the average molecular weight or the molecular weight distribution is preferably employed.
- the polypropylene film roll of the present invention is a film roll formed by winding the above polypropylene film around a core.
- the core (cylindrical core) used for the film roll of the present invention is preferably made of plastic with little deformation, made of fiber reinforced plastics, and made of metal, and more preferably fiber reinforced plastics from the viewpoint of strength.
- the fiber reinforced plastic score include a resin-impregnated core obtained by winding a carbon fiber or a glass fiber into a cylindrical shape, impregnating it with a thermosetting resin such as an unsaturated polyester resin, and curing the core. .
- the average hardness of the outermost roll layer is 84.0 to 94.0 °.
- the angle is more preferably 86.0 to 92.0 °, and further preferably 88.0 to 90.0 °. If the average hardness of the outermost roll layer is less than 84.0 °, the roll is too soft, and roll-up may occur during transportation. When it exceeds 94.0 °, it is hardly wound, so that blocking occurs between the film layers at the time of unwinding, and film peeling at the time of unwinding may not be stable and may cause film breakage.
- the cooling drum condition during film formation and the stretching condition are specified conditions, and the film surface state is controlled. This can be achieved by setting the slit condition to a specific condition.
- the hardness of the roll outermost layer of the polypropylene film roll of the present invention is within ⁇ 2.0 °. More preferably, it is within ⁇ 1.5 °, and further preferably within ⁇ 1.0 °. If the hardness variation of the outermost roll layer exceeds ⁇ 2.0 °, air expands in the processing equipment during vapor deposition and widens the layer gap of the film, but the balance with the film winding tension becomes unstable in the width direction. A difference in the mechanical width direction occurs in the film, and the phenomenon of film meandering and wrinkling occurs, which may increase the defect rate.
- the cooling drum condition during film formation and the stretching condition are specified conditions, and the film surface This can be achieved by controlling the state and setting the slit condition as a specific condition.
- the polypropylene film roll of the present invention preferably has a maximum peak height SRp of 0.4 to 2.0 ⁇ m on at least one side of the polypropylene film. More preferably, it is 0.5 to 1.7 ⁇ m, and still more preferably 0.6 to 1.4 ⁇ m.
- SRp maximum peak height
- an appropriate air content can be maintained, and since it is not a smooth surface, blocking, winding deviation, and meandering are unlikely to occur.
- tightened by such pressure since there are no coarse protrusions, there is no possibility that fine irregularities are generated by transferring to the film in contact. Moreover, since the actual thickness is not reduced, the voltage resistance is not deteriorated.
- the maximum peak height SRp is within the above range on at least one side, an appropriate air content can be maintained and workability is improved.
- the slipperiness with the transport roll is also good, which results in excellent workability and is more preferable.
- the longitudinal stretching step and the lateral stretching step during film formation are performed under specific conditions. This can be achieved.
- the distance in the diameter direction from the outermost roll layer to the core is L, and the roll width direction at a distance of 0, L / 5, 2L / 5, 3L / 5, 4L / 5 from the outermost roll layer.
- the average hardness of each is H (0), H (L / 5), H (2L / 5), H (3L / 5), H (4L / 5), it is preferable to satisfy the following formula.
- the inner layer does not increase the tightening pressure from the outer layer, and the inner layer film is not crushed and deformed.
- the inner layer hardness is not high, and the inner layer is less likely to cause wrinkles and tarmi and has excellent workability. In order to make it into said range, it can achieve by making the slit process at the time of film forming into a specific condition as mentioned later using the polypropylene resin mentioned above.
- the hardness variation in the width direction at L / 5, 2L / 5, 3L / 5, 4L / 5 from the outermost roll layer is within ⁇ 2.0 °. More preferably, it is within ⁇ 1.5 °, and further preferably within ⁇ 1.0 °.
- the variation in the width direction at the points L / 5, 2L / 5, 3L / 5, 4L / 5 from the outermost layer of the roll is within the above preferable range, the balance is not easily lost in the processing apparatus at the time of vapor deposition. Differences in the width direction are unlikely to occur, film meandering and wrinkles do not occur, and the defect rate does not increase.
- the above-described polypropylene resin is used, and as described later, the longitudinal stretching step, the lateral stretching step, and the slit conditions during film formation are specified conditions. Can be achieved.
- the distance L in the diameter direction from the outermost layer of the roll to the core satisfies 20 to 300 mm, from the viewpoint of capacitor demand and productivity. More preferably, it is 50 to 280 mm, and more preferably 90 to 240 mm.
- the polypropylene film of the present invention preferably has a thermal shrinkage rate of 0.4 to 2.0% in the longitudinal direction (the direction in which the film flows during film formation) at 80 ° C. for 15 minutes. More preferably, it is 0.5 to 1.5%.
- the heat shrinkage rate at 80 ° C. is related to the film shrinkage after winding, and when the heat shrinkage rate in the longitudinal direction is within the above-mentioned preferable range, the winding is not excessively tightened, so that wrinkles and tarmi are not easily generated, but the tightening is moderate.
- air escape between the film layers is good, it is difficult for the film to meander during vapor deposition.
- the thermal contraction rate in the width direction is ⁇ 0.5 to 0.5%. More preferably, it is -0.4 to 0.4%.
- the heat shrinkage rate in the width direction is in the above preferable range, unevenness in the film end surface in the width direction is less likely to occur after winding, and film breakage is less likely to occur during vapor deposition.
- transverse stretching during film formation This can be achieved by setting the process to specific conditions.
- the polypropylene film of the present invention preferably has an air leakage index of 100 to 1,500 seconds when the surface on one side and the opposite side are overlapped. More preferably, it is 200 to 900 seconds.
- the air leakage index of the film is within the above preferred range, the contact between the film layers is appropriate, and the protrusions and wrinkles are less likely to occur during winding, while the air trapped between the film layers can be eliminated, Sometimes winding misalignment hardly occurs.
- the above-described polypropylene resin is used, and the film surface state is controlled by setting the cooling drum condition and the stretching condition at the time of film formation as specific conditions. Can be achieved.
- the air content is preferably 0.1 to 8.0%, and more preferably 1.0 to 3.0%.
- the air content is in the above preferred range, the surface hardness of the film roll is moderate, blocking is not likely to occur between the film layers at the time of unwinding, and film peeling at the time of unwinding is stable, so that film breakage is unlikely to occur.
- the amount of air is moderate, and problems such as winding misalignment during vacuum deposition, meandering during running, wrinkles, and poor margin accuracy are unlikely to occur.
- the surface roughness SRa of the polypropylene film of the present invention is preferably 0.01 to 0.05 ⁇ m, more preferably 0.02 to 0.04 ⁇ m on at least one surface.
- the film surface roughness SRa is in the above-mentioned preferable range, the air content in the case of a film roll can be controlled appropriately, deterioration of vapor deposition workability such as winding deviation and meandering hardly occurs, and defects such as wrinkles at the time of device processing Is not generated, and the withstand voltage is not lowered.
- the unevenness of the film surface is moderate and the slipperiness is good, so that the conveyance wrinkle does not easily occur in the film forming process or the vapor deposition process, and the winding deviation hardly occurs.
- the film surface roughness SRa is satisfied on at least one surface, an appropriate air content can be maintained and workability is improved.
- the film surface roughness SRa satisfies the above range on both sides, it is more preferable because the slipping property with the transport roll is also good and the workability is excellent.
- the polypropylene film of the present invention preferably has a film thickness of 0.5 to 7.0 ⁇ m.
- the film thickness is more preferably 0.8 to 6.8 ⁇ m, and further preferably 1.2 to 6.5 ⁇ m.
- the mechanical strength and withstand voltage characteristics are excellent, and film breakage is unlikely to occur during film formation and processing.
- it can be appropriately set by adjusting the discharge amount of the resin or adjusting the draft ratio when forming the sheet, but as the film thickness becomes thinner Since film breakage during film formation is likely to occur, using the above-described polypropylene resin, as described later, the casting process, the longitudinal stretching process, and the transverse stretching process can be stably performed under specific conditions. It becomes possible to form a film.
- the film roll width (the width of the polypropylene film) is preferably 500 mm or more and 1,050 mm or less. More preferably, they are 600 mm or more and 950 mm or less, More preferably, they are 620 mm or more and 820 mm or less, and capacitor productivity improves further.
- the productivity is good, while the deposition efficiency is good, and the productivity is good even when the difficulty of the winding technique is taken into consideration.
- the film length is 20,000 m or more, preferably 30,000 m or more. Considering the productivity viewpoint and the difficulty of the winding technique, it is more preferably 30,000 m or more and less than 80,000 m.
- the film length is in the above preferred range, the weight is appropriate, handling is easy, and the tightening is moderate, so that defects such as wrinkles and tarmi are less likely to occur during processing, while productivity deteriorates. Nor.
- the polypropylene film of the present invention may contain a branched polypropylene for the purpose of improving the film forming property.
- the branched polypropylene satisfies the relational expression that the melt tension (MS) and the melt flow rate (MFR) measured at 230 ° C. are log (MS)> ⁇ 0.56 log (MFR) +0.74.
- a branched polypropylene is preferred.
- the unit of melt tension (MS) is cN.
- To obtain a branched polypropylene satisfying the relational expression that the melt tension (MS) and the melt flow rate (MFR) measured at 230 ° C. are log (MS)> ⁇ 0.56 log (MFR) +0.74.
- a method or a method described in Japanese Patent No. 2869606 is preferably used.
- “PRO-FAX” (registered trademark) PF-814 manufactured by LyondellBasel, and “Daploy” (trademark) HMS-PP (WB130HMS, WB135HMS, etc.) manufactured by Borealis are exemplified.
- the resin obtained by the method is preferably used because the gel component in the resin is small.
- the branched polypropylene referred to here is a polypropylene having 5 or less internal trisubstituted olefins per 10,000 carbon atoms, and the presence of these internal trisubstituted olefins is shown in the 1 H-NMR spectrum. This can be confirmed by the proton ratio.
- the branched polypropylene can act as an ⁇ crystal nucleating agent, and can form a rough surface by a crystal form as long as the amount is within a certain range.
- the polypropylene spherulite size generated in the cooling process of the melt-extruded resin sheet can be controlled to be small, the generation of insulation defects generated in the stretching process can be suppressed, and a polypropylene film having excellent withstand voltage characteristics can be obtained.
- the content is preferably 0.05 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and The content is more preferably 3 to 1.5% by mass, and particularly preferably 0.5 to 1.0% by mass.
- the content of the branched polypropylene is within the above preferable range, an effect of improving the film forming property can be obtained.
- the stereoregularity as a polypropylene film is not deteriorated, so that the withstand voltage characteristics are excellent.
- various additives such as a crystal nucleating agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, and an antiblocking agent are used as long as the object of the present invention is not impaired. It is also preferable to include an agent, a filler, a viscosity modifier, an anti-coloring agent and the like.
- the type of antioxidant and the selection of the addition amount are important from the viewpoint of long-term heat resistance. That is, the antioxidant is a phenolic compound having steric hindrance, and at least one of them is preferably a high molecular weight type having a molecular weight of 500 or more.
- 2,6-di-t-butyl-p-cresol BHT: molecular weight 220.4
- 1,3,5-trimethyl-2,4,6-tris (3,5-di- -T-butyl-4-hydroxybenzyl) benzene
- Irganox registered trademark 1330 manufactured by BASF Corporation: molecular weight 775.2
- tetrakis [methylene-3 (3,5-di-t-butyl-4- Hydroxyphenyl) propionate] methane for example, “Irganox” (registered trademark) 1010: molecular weight 1177.7 manufactured by BASF
- Irganox registered trademark 1010: molecular weight 1177.7 manufactured by BASF
- the total content of these antioxidants is preferably 0.03 to 1.0% by mass, more preferably 0.1 to 0.9% by mass, based on the total amount of the polypropylene resin. While the antioxidant content in the polypropylene resin is excellent, the withstand voltage characteristics at high temperatures are excellent.
- the polypropylene film of the present invention preferably has a surface wetting tension of at least one side of 37 to 50 mN / m, more preferably 38 to 49 mN / m, still more preferably 39 to 48 mN / m, and 40 to 47 mN. / M is particularly preferable.
- a surface wetting tension is equal to or more than the above preferable lower limit, adhesion with the metal is sufficient when the metal is deposited.
- the preferred polypropylene resin described above is supplied to a uniaxial melt extruder, extruded from a slit-shaped die at a temperature of 230 to 260 ° C., and solidified on a cooling drum to obtain an unoriented sheet.
- a cooling drum in order to obtain the film of the present invention, it is preferable to appropriately control the temperature of the cooling drum for the purpose of appropriately generating ⁇ crystals.
- the resin temperature at which the ⁇ crystal generation efficiency is maximized for a predetermined time and the temperature is usually 115 to 135 ° C.
- the holding time is preferably 1.5 seconds or longer.
- the process can be determined as appropriate according to the resin temperature, the extrusion amount, the take-up speed, etc., but from the viewpoint of productivity, the diameter of the cooling drum greatly affects the holding time.
- the diameter of the drum is preferably at least 1 m.
- the cooling drum temperature to be selected is preferably 70 to 130 ° C., more preferably in the range of 90 to 110 ° C., although it includes a certain degree of freedom because other factors influence as described above. is there. If the cooling drum temperature is within the above preferred range, the film is not excessively crystallized, so that orientation in the subsequent process is easy, voids are not easily formed in the film, and the dielectric breakdown resistance does not deteriorate.
- Any method of electrostatic contact, contact using water surface tension, air knife method, press roll method, underwater cast method, etc. may be used as the method of close contact with the cooling drum,
- the air knife method is preferable because it is favorable and can control the heat shrink characteristics and surface roughness of the front and back surfaces.
- the obtained unstretched sheet is biaxially stretched to be biaxially oriented.
- the temperature control method includes a method using a temperature-controlled rotating roll and a method using a hot air oven.
- the non-oriented film is preheated through a roll kept at 100 to 150 ° C., and then the sheet is kept at a temperature of 110 ° C. to 150 ° C. In this case, the film is oriented 3 to 7 times as the stretching ratio in the longitudinal direction. Cool to room temperature through a chill roll at 10-40 ° C.
- the film surface structure is controlled by installing radiation heaters on both sides before entering the tenter type stretching machine and applying heat locally.
- the distance between the radiation heater and the film is preferably 5 to 10 mm, and more preferably 6 to 8 mm.
- the output of the radiation heater is preferably 6 to 10 kW, and more preferably 7 to 9 kW.
- the amount of heat required for film surface control can be sufficiently supplied, while the amount of heat is not excessive, the maximum peak height can be kept within an appropriate range, and the amount of heat is excessive.
- the film is not easily torn.
- the film end is held by a tenter type stretching machine and introduced.
- the temperature is preferably 147 to 160 ° C, more preferably 150 to 160 ° C.
- the heat treatment may be performed while relaxing in the longitudinal direction and / or the width direction of the film, and it is preferable that the relaxation rate in the width direction is 10 to 20%.
- the film is cooled in the cooling chamber.
- the cooling chamber temperature of the cooling chamber 1 is 110 to Hold the cooling chamber temperature at 130 ° C. for 0.5 seconds or longer, the cooling chamber temperature of the cooling chamber 2 at 80 to 100 ° C. for 0.5 seconds or longer, and the cooling chamber temperature of the cooling chamber 3 at 50 to 70 ° C. for 0.5 seconds or longer preferable.
- the holding time of the cooling chambers 1, 2, and 3 is more preferably 1.0 seconds or more. When the holding time is equal to or more than the above preferable lower limit, it is difficult to cool rapidly, and thus thickness unevenness in the width direction can be suppressed, and thermal dimensional stability is good.
- a corona discharge treatment is applied at min / m 2 to provide adhesion of the deposited metal.
- the film roll is wound to the core with a predetermined width, and the slitting condition of the film is important together with the above-described control of the maximum peak height. It is preferably 8.0 kg / m.
- the tension at the time of winding is preferably 1.0 to 8.0 kg / m, more preferably 2.0 to 7.5 kg / m, and further preferably 3.0 to 7.0 kg / m.
- a film roll By adopting conditions such as a surface pressure of 5 to 60 kg / m at winding, a slit speed of 100 to 500 m / min, an oscillation speed of 75 to 125 mm / min, and an oscillation width of 10 to 400 mm, a film roll
- the air content is preferably 0.1 to 8%.
- the tension taper is preferably 60 to 80%, more preferably 65 to 75%.
- CXS Cold xylene soluble part
- A. Measurement conditions Apparatus: DRX-500 manufactured by Bruker Measurement nucleus: 13 C nucleus (resonance frequency: 125.8 MHz) Measurement concentration: 10 wt% Solvent: benzene / heavy orthodichlorobenzene mass ratio 1: 3 mixed solution Measurement temperature: 130 ° C. Spin rotation speed: 12Hz NMR sample tube: 5 mm tube Pulse width: 45 ° (4.5 ⁇ s) Pulse repetition time: 10 seconds Data point: 64K Conversion count: 10,000 times Measurement mode: complete decoupling B. Analysis condition LB (line broadening factor) was set to 1.0, and Fourier transform was performed to set the mmmm peak to 21.86 ppm.
- Peak splitting is performed using WINFIT software (manufactured by Bruker). At that time, the peak was divided from the peak on the high magnetic field side as follows, and the attached software was automatically fitted. After optimizing the peak division, the total of the mmmm peak fractions was determined. In addition, the said measurement was performed 5 times and the average value was made into the mesopentad fraction (mmmm) of this sample.
- melt flow rate It measured based on the conditions M (230 degreeC, 2.16 kg) of JISK7210 (1995). The unit of melt flow rate is g / 10 minutes.
- melt tension (MS) It measured according to the apparatus for MFR measurement shown by JISK7210 (1999). Using a melt tension tester manufactured by Toyo Seiki Co., Ltd., the resin sample was heated to 230 ° C., and the molten polymer was discharged at an extrusion speed of 15 mm / min to form a strand. The tension at the time of drawing this strand at a speed of 6.5 m / min was measured to determine the melt tension. The unit of melt tension is cN.
- SRa Arithmetic mean roughness
- SRp maximum peak height
- JIS B 0601 (1982) measurement was performed using a non-contact three-dimensional fine shape measuring instrument (ET-30HK) manufactured by Kosaka Laboratory Ltd. and a three-dimensional roughness analyzer (MODEL SPA-11). The measurement was performed at 10 arbitrary locations, and the arithmetic average roughness SRa, the maximum valley depth SRv, and the maximum peak height SRp were obtained as average values.
- Detailed conditions for one measurement were as follows.
- Measurement conditions Measurement surface treatment: Aluminum was vacuum-deposited on the measurement surface to obtain a non-contact method.
- Measurement direction Film width direction Width direction feed rate: 0.1 mm / second Measurement range (width direction ⁇ length direction): 1.0 mm ⁇ 0.249 mm Reference plane of height dimension: LOWER (lower side) Width direction sampling interval: 2 ⁇ m Sampling interval in length direction: 10 ⁇ m Number of samplings in the length direction: 25 Cutoff: 0.25 mm / second Magnification in the width direction: 200 times Magnification in the length direction: 20,000 times Waviness, roughness Cut: None.
- the hardness variation is defined as a difference between the average hardness and the most distant hardness at each measurement point (the average hardness ⁇ the hardness of the measurement points farthest from the average hardness).
- the air leakage index was measured at 25 ° C. and 65% RH using a Toyo Seiki Digibeck smoothness tester.
- a film (5 cm ⁇ 5 cm, of which a hole having a diameter of 10 mm ⁇ is formed in the lower one) is set on a sample stage. At this time, the center of the hole is set at the center of the sample stage. In this state, a load of 0.2 kg / cm 2 is applied to set the degree of vacuum at 383 mmHg. After reaching 383 mmHg, the vacuum pump automatically stops, and then the air passes between the films and flows into the system, so that the degree of vacuum decreases. At this time, the time required to change from 382 mmHg to 381 mmHg was measured, and the average value measured five times was taken as the air leakage index.
- Air content (%) The outer peripheral length of the film roll is measured using a tape measure having a dimensional accuracy of 10 ⁇ m, and the roll diameter is obtained from the outer periphery. The outer circumference is measured over the entire width every 50 mm from a point 5 mm inside from either roll end, and the average value is used.
- the air content is a value represented by the following formula.
- the vapor-deposited film obtained as described above was slit into a tape shape with a width of 4.50 mm having a margin portion with a width of 0.50 mm on the left or right.
- the obtained left margin and right margin vapor-deposited polypropylene films were wound together to obtain a wound body. At this time, the two films were wound and wound so that the vapor deposition portion protruded by 0.5 mm in the width direction.
- KAW-4NHB manufactured by Minato Seisakusho was used for element winding.
- the core material was removed from the wound body, and pressed and wound at 150 ° C. and a temperature of 10 kg / cm 2 for 5 minutes to obtain a wound capacitor element.
- the capacitor end face displacement amount is a difference (mm) between the capacitor product width and the reel film width before winding.
- the film obtained in each of Examples and Comparative Examples described below is a vacuum manufactured by ULVAC, Inc.
- a vapor deposition pattern having a so-called T-shaped margin pattern in which a margin portion was provided in a direction perpendicular to the longitudinal direction with a film resistance of 9 ⁇ / ⁇ was applied to aluminum with a vapor deposition machine to obtain a vapor deposition reel having a width of 60 mm.
- the capacitor element was wound up with an element winding machine (KAW-4NHB) manufactured by Minato Seisakusho Co., Ltd., metallized, and then subjected to heat treatment at 105 ° C. for 10 hours under reduced pressure. Wires were attached to finish the capacitor element.
- the capacitance of the capacitor element at this time was 5 ⁇ F.
- a voltage of 100 VDC is applied to the capacitor element at a high temperature of 100 ° C., and the applied voltage is gradually increased in steps of 50 VDC / 1 minute after 10 minutes at that voltage.
- a so-called step-up test was repeated.
- the capacitance change at this time is measured and plotted on a graph, and the value obtained by dividing the voltage at which the capacitance becomes 70% of the initial value by the micrometer film thickness (described above) is the withstand voltage (V / ⁇ m) and was evaluated according to the following criteria. Excellent and good can be used without problems, but if possible, it can be used depending on conditions. A defect causes a practical problem.
- Example 1 100 mass% of polypropylene resin (manufactured by Prime Polymer Co., Ltd., melting point: 166 ° C., MFR: 2.5 g / 10 min, mmmm: 0.991) is supplied to a single-screw melt extruder, and melt extrusion is performed at 250 ° C. Foreign matter was removed with a sintered filter of 25 ⁇ m cut. The molten sheet discharged from the T-die was brought into intimate contact with a cooling drum whose surface temperature was controlled at 95 ° C., and indirectly passed through the cooling drum for 1.5 seconds to obtain an unstretched sheet. An air knife was used to bring the molten sheet into close contact with the cooling drum.
- polypropylene resin manufactured by Prime Polymer Co., Ltd., melting point: 166 ° C., MFR: 2.5 g / 10 min, mmmm: 0.991
- preheating was performed using a ceramic roll heated to 130 ° C., and the film was stretched 5.0 times in the longitudinal direction of the film. Further, for the purpose of improving the stretchability of the film, heat was applied from both sides of the film stretching portion with a radiation heater, so that the film was not broken in the longitudinal stretching and the film forming property was excellent. After longitudinal stretching, the film was passed through a 30 ° C. cooling roll and cooled to room temperature.
- a radiation heater was installed on both sides before the entrance of the tenter type stretching machine, the distance between the radiation heater and the film was 6 mm, and the output of the radiation heater was 7 kW.
- the end portion was held with a clip and stretched 12 times in the width direction at 160 ° C. Furthermore, heat treatment was performed at 160 ° C., and relaxation was performed by 10% in the width direction.
- the cooling chamber is divided into three chambers, the cooling chamber temperature of cooling chamber 1 is 1.1 seconds or more at 120 ° C., the cooling chamber temperature of cooling chamber 2 is 1.1 seconds or more at 90 ° C., and the cooling chamber temperature of cooling chamber 3 is It was kept at 60 ° C. for 1.1 seconds or longer.
- one side of the film was subjected to corona discharge treatment at a treatment strength of 25 W ⁇ min / m 2 , and the film ears held by the clips were cut and removed.
- the surface treated surface is referred to as A surface
- the untreated surface is referred to as B surface.
- the film from which the end portion was removed was wound up with a winder to obtain an intermediate film roll having a thickness of 2.5 ⁇ m.
- this intermediate film roll was slit at a speed of 400 m / min, an oscillation speed of 125 mm / min, an oscillation width of 80 mm, an unwinding tension of 6.0 kg / m, and a winding tension of 6.5 kg / m as the winding conditions.
- the slit was made with a tension taper of 65%, a surface pressure of 45 kg / m, a width of 620 mm, and a length of 75,000 m. Table 1 shows the physical properties of the obtained film.
- Example 2 After the longitudinal stretching cooling, an intermediate film roll was obtained in the same manner as in Example 1 except that the distance between the radiation heater and the film before the entrance of the tenter type stretching machine was 8 mm and the output of the radiation heater was 9 kW.
- this intermediate film roll was slit in the same manner as in Example 1 except that the winding conditions were a winding tension of 3.0 kg / m and a tension taper of 75%, and a polypropylene film roll having a thickness of 2.5 ⁇ m was formed. Obtained. Table 1 shows the physical properties of the obtained film.
- Example 3 After the longitudinal stretching cooling, a polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the output of the radiation heater before entering the tenter type stretching machine was 10 kW. Table 1 shows the physical properties of the obtained film.
- Example 4 After the longitudinal stretching cooling, a polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the output of the radiation heater before the entrance of the tenter type stretching machine was 6 kW. Table 1 shows the physical properties of the obtained film.
- Example 5 After the longitudinal stretching cooling, a polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the distance between the radiation heater before the entrance of the tenter type stretching machine and the film was 10 mm. Table 1 shows the physical properties of the obtained film.
- Example 6 After the longitudinal stretching cooling, a polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the distance between the radiation heater and the film before the entrance of the tenter type stretching machine was 5 mm. Table 1 shows the physical properties of the obtained film.
- Example 7 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was 7.5 kg / m. Table 1 shows the physical properties of the obtained film.
- Example 8 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was 2.0 kg / m. Table 1 shows the physical properties of the obtained film.
- Example 9 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was 8.0 kg / m. Table 1 shows the physical properties of the obtained film.
- Example 10 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was 1.0 kg / m. Table 1 shows the physical properties of the obtained film.
- Example 11 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the tension taper of the slitter was changed to 60%. Table 1 shows the physical properties of the obtained film.
- Example 12 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the holding time of the cooling chambers 1, 2 and 3 was 0.6 seconds. Table 1 shows the physical properties of the obtained film.
- Example 13 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was 7.5 kg / m and the tension taper was 55%. Table 2 shows the physical properties of the obtained film.
- Example 14 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the temperature of the cooling drum was 110 ° C. Table 2 shows the physical properties of the obtained film.
- Example 2 After the longitudinal stretching cooling, a polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the distance between the radiation heater before the entrance of the tenter stretching machine and the film was 4 mm. Table 2 shows the physical properties of the obtained film.
- Example 3 After the longitudinal stretching cooling, a polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the output of the radiation heater before the entrance of the tenter type stretching machine was 11 kW. Table 2 shows the physical properties of the obtained film.
- Example 4 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was changed to 0.8 kg / m. Table 2 shows the physical properties of the obtained film.
- Example 5 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the winding tension of the slitter was 9.0 kg / m. Table 2 shows the physical properties of the obtained film.
- Example 6 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the slitter tension taper was 50%. Table 2 shows the physical properties of the obtained film.
- Example 7 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the slitter tension taper was 95%. Table 2 shows the physical properties of the obtained film.
- Example 8 A polypropylene film roll having a thickness of 2.5 ⁇ m was obtained in the same manner as in Example 1 except that the holding time of the cooling chambers 1, 2 and 3 was changed to 0.2 seconds. Table 2 shows the physical properties of the obtained film.
- the polypropylene film roll of the present invention can prevent troubles such as winding misalignment and vertical wrinkles of the film roll in the vapor deposition process, meandering during wrinkling, and wrinkles in the capacitor application, particularly when producing a vapor deposition capacitor. Furthermore, it is possible to provide a polypropylene film roll for a capacitor excellent in processability in each capacitor production.
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Abstract
Description
ポリプロピレンフィルムをコアに巻いてなるフィルムロールであり、ロール最表層の平均硬度が84.0~94.0°、かつロール最表層の幅方向の硬度バラツキが±2.0°以内であるポリプロピレンフィルムロール、である。
1.00<H(L/5)/H(0)≦1.02 式(1)
1.00<H(2L/5)/H(L/5)≦1.02 式(2)
1.00<H(3L/5)/H(2L/5)≦1.02 式(3)
1.00<H(4L/5)/H(3L/5)≦1.02 式(4)
かつロール最表層からL/5、2L/5、3L/5、4L/5地点における幅方向の硬度バラツキが±2.0°以内であることが好ましい。
1.00<H(L/5)/H(0)≦1.02
1.00<H(2L/5)/H(L/5)≦1.02
1.00<H(3L/5)/H(2L/5)≦1.02
1.00<H(4L/5)/H(3L/5)≦1.02
より好ましくは下記式を満たす場合である。
1.00<H(L/5)/H(0)≦1.01
1.00<H(2L/5)/H(L/5)≦1.01
1.00<H(3L/5)/H(2L/5)≦1.01
1.00<H(4L/5)/H(3L/5)≦1.01
上記式でH(L/5)/H(0)、H(2L/5)/H(L/5)、H(3L/5)/H(2L/5)、H(4L/5)/H(3L/5)が上記好ましい範囲である場合、外層硬度が内層硬度よりも高くならないため、内層フィルムが潰されて変形することはなく、内部でシワが入ることがない。また、内層は外層から巻き締まりの圧力が大きくならず、内層フィルムが潰されて変形することもない。一方、内層硬度が高くならず、内層でシワやタルミが生じにくく加工性に優れる。上記の範囲内とするためには、上述したポリプロピレン樹脂を使用して、後述する通り、フィルム製膜時のスリット工程を特定の条件とすることで達成できる。
ポリプロピレン樹脂試料0.5gを135℃のキシレン100mLに溶解して放冷後、20℃の恒温水槽で1時間再結晶させた後にろ過液に溶解しているポリプロピレン系成分を液体クロマトグラフ法にて定量する(Xg)。試料0.5gの精量値(X0g)を用いて下記式から算出した。
ポリプロピレン樹脂、またはポリプロピレンフィルムを試料として溶媒に溶解し、13C-NMRを用いて、以下の条件にてメソペンタッド分率(mmmm)を求めた(参考文献:新版 高分子分析ハンドブック 社団法人日本分析化学会・高分子分析研究懇談会 編 1995年 P609~611)。
装置:Bruker社製 DRX-500
測定核:13C核(共鳴周波数:125.8MHz)
測定濃度:10wt%
溶媒:ベンゼン/重オルトジクロロベンゼン=質量比1:3混合溶液
測定温度:130℃
スピン回転数:12Hz
NMR試料管:5mm管
パルス幅:45°(4.5μs)
パルス繰り返し時間:10秒
データポイント:64K
換算回数:10,000回
測定モード:complete decoupling
B.解析条件
LB(ラインブロードニングファクター)を1.0としてフーリエ変換を行い、mmmmピークを21.86ppmとした。WINFITソフト(Bruker社製)を用いて、ピーク分割を行う。その際に、高磁場側のピークから以下のようにピーク分割を行い、さらに付属ソフトの自動フィッティングを行った。ピーク分割の最適化を行った上で、mmmmのピーク分率の合計を求めた。なお、上記測定を5回行い、その平均値を本試料のメソペンタッド分率(mmmm)とした。
(a)mrrm
(b)(c)rrrm(2つのピークとして分割)
(d)rrrr
(e)mrmr
(f)mrmm+rmrr
(g)mmrr
(h)rmmr
(i)mmmr
(j)mmmm 。
JIS K 7210(1995)の条件M(230℃、2.16kg)に準拠して測定した。メルトフローレートの単位はg/10分である。
JIS K 7210(1999)に示されるMFR測定用の装置に準じて測定した。株式会社東洋精機社製メルトテンションテスターを用いて、樹脂試料を230℃に加熱し、溶融ポリマーを押出速度15mm/分で吐出しストランドとした。このストランドを6.5m/分の速度で引き取る際の張力を測定し、溶融張力を求めた。溶融張力の単位はcNである。
JIS C 2330(2001)の7.4.1.1に準じ、マイクロメーター法厚みを測定した。
ポリプロピレンフィルムの長手方向もしくは幅方向について、測定方向200mm、測定方向と直角の方向10mmとなるように試料を5本切り出し、両端から50mmの位置に印を付けて試長(l0:100mm)とした。次に、荷重3gを付けて80℃に保温されたオーブン内に吊し、15分加熱後に取り出して、室温で冷却後、両印間の寸法(l1)を測定して下記式にて求め、長手方向、幅方向ともにそれぞれ5本の平均値を本発明の二軸配向ポリプロピレンフィルムの熱収縮率とした。
ホルムアルデヒドとエチレングリコールモノエチルエーテルとの混合液によるJIS K 6768(1999)に規定された測定方法に基づいて測定した。
JIS B 0601(1982)により、株式会社小坂研究所社製非接触三次元微細形状測定器(ET-30HK)、および三次元粗さ分析装置(MODEL SPA-11)を用いて測定した。測定は任意の10箇所において測定を行い、その平均値として算術平均粗さSRa、最大谷深さSRv、最大山高さSRpを求めた。1回の測定の詳細条件については下記の通りとした。
測定面処理:測定面にアルミニウムを真空蒸着し、非接触法とした。
幅方向送り速度:0.1mm/秒
測定範囲(幅方向×長さ方向):1.0mm×0.249mm
高さ方向寸法の基準面:LOWER(下側)
幅方向サンプリング間隔:2μm
長さ方向サンプリング間隔:10μm
長さ方向サンプリング本数:25本
カットオフ:0.25mm/秒
幅方向拡大倍率:200倍
長さ方向拡大倍率:20,000倍
うねり、粗さカット:なし。
JIS K 6301の規定による高分子計器株式会社製ゴム硬度計ASKER“TypeC”を用いてポリプロピレンフィルムロールの表面(最表層)を幅方向にロール両端10mmを除いて均等に7点測定し、その平均値を求めた。ロールの内層についてはロール最表層からコアまでの直径方向の距離Lとしたとき、所定の位置までロールを切開し、ロール表面と同じ方法で測定値を求めた。なお、硬度計の抑え圧を一定にするため、硬度計と合わせた重量が3.5kgになるように、荷重を硬度計に取り付けた。また、硬度計のロールと接触する加圧面は、加圧面の辺の長い方をロールの幅方向に平行となるよう測定した。硬度バラツキとは、該平均硬度と各測定点の最も離れた硬度との差(該平均硬度-各測定点の硬度のうち該平均硬度から最も離れた硬度)とする。
(株)東洋精機製デジベック平滑度試験機を用いて、25℃、65%RHにて測定した。まず、一方の面と反対面を重ね合わせたフィルム(5cm×5cm、そのうち下側の1枚に直径10mmφの孔をあけ)を試料台にセットする。このとき孔の中心部が試料台の中心にくるようにする。この状態で0.2kg/cm2の荷重を加えて、真空到達度を383mmHgに設定する。383mmHgに到達後、自動的に真空ポンプが停止し、その後、フィルム間を空気が通過して系内に流入するため、真空度が低下する。このとき、382mmHgから381mmHgに変化する所要時間を測定し、5回測定した平均値を空気漏れ指数とした。
フィルムロールの外周長さを寸法精度10μmの巻き尺を用いて測定し、外周よりロール直径を求める。外周は、どちらかのロール端部より5mm内側の点より、50mm毎に全幅にわたり測定し、その平均値を用いる。空気含有率は下記の式で示される値である。
α :空気含有率(%)
t1:重量法フィルム厚み(μm)
LR:ロール長さ(m)
d1:ロール直径(mm)
d2:コア直径(mm)。
後述する各実施例および比較例で得られたフィルムに、抵抗加熱型金属蒸着装置を用い、真空室の圧力を10-4Torr以下として、ポリプロピレンフィルムの片面に、表面抵抗が2Ω/□となるようにアルミニウムを真空蒸着して巻き取った。その際、長手方向に走るマージン部を有するストライプ状(蒸着部の幅8.0mm、マージン部の幅1.0mmの繰り返し)に蒸着した。
100% 優
90%以上100%未満 良
70%以上90%未満 可
70%未満 不良
(13)蒸着コンデンサ特性の評価
後述する各実施例および比較例で得られたフィルムに、株式会社ULVAC社製真空蒸着機でアルミニウムを膜抵抗が9Ω/□で長手方向に垂直な方向にマージン部を設けた所謂T型マージンパターンを有する蒸着パターンを施し、幅60mmの蒸着リールを得た。
<耐電圧性>
優:300V/μm以上
良:250V/μm以上、300V/μm未満
可:200V/μm以上、250V/μm未満
不良:200V/μm未満。
ポリプロピレン樹脂(プライムポリマー社製、融点:166℃、MFR:2.5g/10分、mmmm:0.991)100質量%を単軸の溶融押出機に供給し、250℃で溶融押出を行い、25μmカットの焼結フィルターで異物除去を行った。Tダイから吐出された溶融シートを95℃に表面温度を制御した冷却ドラム上に密着させ、冷却ドラムに1.5秒間接させることで未延伸シートを得た。溶融シートを冷却ドラム上に密着させるためにエアーナイフを用いた。ついで、130℃に加熱したセラミックロールを用いて予熱を行いフィルムの長手方向に5.0倍延伸を行った。また、フィルムの延伸性を向上させる目的でフィルム延伸部の両側からラジエーションヒーターにより熱量を与えることで、縦延伸においてフィルム破れの発生はなく製膜性に優れていた。縦延伸後に30℃の冷却ロールに通して室温まで冷却した。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターとフィルムの距離を8mm、ラジエーションヒーターの出力は9kWとした以外は実施例1と同様にして中間フィルムロールを得た。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターの出力を10kWとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターの出力を6kWとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターとフィルムの距離を10mmとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターとフィルムの距離を5mmとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
スリッターの巻取張力を7.5kg/mとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
スリッターの巻取張力を2.0kg/mとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
スリッターの巻取張力を8.0kg/mとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
スリッターの巻取張力を1.0kg/mとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
スリッターの張力テーパを60%とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
冷却室1、2、3の保持時間を0.6秒とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表1に示す。
スリッターの巻取張力を7.5kg/m、張力テーパを55%とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
冷却ドラムの温度を110℃とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターを設置しなかった以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターとフィルムの距離を4mmとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
縦延伸冷却後、テンター式延伸機入り口前のラジエーションヒーターの出力を11kWとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
スリッターの巻取張力を0.8kg/mとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
スリッターの巻取張力を9.0kg/mとした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
スリッターの張力テーパを50%とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
スリッターの張力テーパを95%とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
冷却室1、2、3の保持時間を0.2秒とした以外は実施例1と同様に作製し、厚み2.5μmのポリプロピレンフィルムロールを得た。得られたフィルムの物性を表2に示す。
Claims (12)
- ポリプロピレンフィルムをコアに巻いてなるフィルムロールであり、ロール最表層の平均硬度が84.0~94.0°、かつロール最表層の幅方向の硬度バラツキが±2.0°以内であるポリプロピレンフィルムロール。
- ポリプロピレンフィルムの少なくとも片面の最大山高さSRpが0.4~2.0μmである請求項1に記載のポリプロピレンフィルムロール。
- ロール最表層からコアまで直径方向の距離をLとしたとき、ロール最表層から0、L/5、2L/5、3L/5、4L/5の距離におけるロール幅方向平均硬度をそれぞれH(0)、H(L/5)、H(2L/5)、H(3L/5)、H(4L/5)としたとき、式(1)~(4)を満たし、
1.00<H(L/5)/H(0)≦1.02 式(1)
1.00<H(2L/5)/H(L/5)≦1.02 式(2)
1.00<H(3L/5)/H(2L/5)≦1.02 式(3)
1.00<H(4L/5)/H(3L/5)≦1.02 式(4)
かつロール最表層からL/5、2L/5、3L/5、4L/5地点における幅方向の硬度バラツキが±2.0°以内である請求項1または2に記載のポリプロピレンフィルムロール。 - ロール最表層からコアまで直径方向の距離Lが20~300mmである請求項1~3のいずれかに記載のポリプロピレンフィルムロール。
- ポリプロピレンフィルムの80℃熱収縮率が、長手方向について0.4~2.0%、幅方向について-0.5~0.5%である請求項1~4のいずれかに記載のポリプロピレンフィルムロール。
- 一方の面と反対面を重ね合わせたときの空気漏れ指数が100~1,500秒である請求項1~5のいずれかに記載のポリプロピレンフィルムロール。
- 空気含有率が0.1~8.0%である請求項1~6のいずれかに記載のポリプロピレンフィルムロール。
- ポリプロピレンフィルムの少なくとも一方の表面の表面粗さ(中心面平均粗さ)SRaが0.01~0.05μmである請求項1~7のいずれかに記載のポリプロピレンフィルムロール。
- マイクロメーター法によるフィルム厚みが、0.5~7.0μmである請求項1~8のいずれかに記載のポリプロピレンフィルムロール。
- フィルム長さが20,000m以上である請求項1~9のいずれかに記載のポリプロピレンフィルムロール。
- フィルム幅が500mm以上1,050mm以下である請求項1~10のいずれかに記載のポリプロピレンフィルムロール。
- コンデンサ用である請求項1~11のいずれかに記載のポリプロピレンフィルムロール。
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JP2020076088A (ja) * | 2018-11-09 | 2020-05-21 | 東レ株式会社 | フィルムロール |
JP2020132877A (ja) * | 2019-02-18 | 2020-08-31 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
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JP6988243B2 (ja) * | 2016-08-10 | 2022-01-05 | 東レ株式会社 | ポリプロピレンフィルムロール |
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- 2017-08-07 CN CN201780049793.8A patent/CN109563286B/zh active Active
- 2017-08-07 EP EP17841407.4A patent/EP3502172B1/en active Active
- 2017-08-07 WO PCT/JP2017/028571 patent/WO2018034182A1/ja active Application Filing
- 2017-08-07 JP JP2017546260A patent/JP6477909B2/ja active Active
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TWI795590B (zh) * | 2018-09-11 | 2023-03-11 | 日商三菱化學股份有限公司 | 聚乙烯醇系薄膜輥及其製法 |
WO2020054509A1 (ja) * | 2018-09-11 | 2020-03-19 | 三菱ケミカル株式会社 | ポリビニルアルコール系フィルムロールおよびその製法 |
CN112533848A (zh) * | 2018-09-11 | 2021-03-19 | 三菱化学株式会社 | 聚乙烯醇系薄膜卷及其制造方法 |
JPWO2020054509A1 (ja) * | 2018-09-11 | 2021-08-30 | 三菱ケミカル株式会社 | ポリビニルアルコール系フィルムロールおよびその製法 |
JP7334622B2 (ja) | 2018-09-11 | 2023-08-29 | 三菱ケミカル株式会社 | ポリビニルアルコール系フィルムロールおよびその製法 |
JP2020076088A (ja) * | 2018-11-09 | 2020-05-21 | 東レ株式会社 | フィルムロール |
JP7287240B2 (ja) | 2018-11-09 | 2023-06-06 | 東レ株式会社 | フィルムロール |
JP2020132877A (ja) * | 2019-02-18 | 2020-08-31 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
JP7375599B2 (ja) | 2019-02-18 | 2023-11-08 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム、金属膜積層フィルムおよびフィルムコンデンサ |
WO2020246322A1 (ja) * | 2019-06-05 | 2020-12-10 | 王子ホールディングス株式会社 | ポリプロピレンフィルムロール及び金属化ポリプロピレンフィルムロール |
KR20220018550A (ko) | 2019-06-05 | 2022-02-15 | 오지 홀딩스 가부시키가이샤 | 폴리프로필렌 필름 롤 및 금속화 폴리프로필렌 필름 롤 |
WO2022210693A1 (ja) * | 2021-03-31 | 2022-10-06 | 東レ株式会社 | ポリプロピレンフィルム |
WO2022210688A1 (ja) * | 2021-03-31 | 2022-10-06 | 東レ株式会社 | ポリプロピレンフィルム |
Also Published As
Publication number | Publication date |
---|---|
CN109563286B (zh) | 2021-07-30 |
EP3502172B1 (en) | 2021-06-09 |
KR102386611B1 (ko) | 2022-04-13 |
EP3502172A4 (en) | 2020-05-13 |
EP3502172A1 (en) | 2019-06-26 |
CN109563286A (zh) | 2019-04-02 |
KR20190042498A (ko) | 2019-04-24 |
JPWO2018034182A1 (ja) | 2018-11-22 |
JP6477909B2 (ja) | 2019-03-06 |
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