WO2012144015A1 - コンデンサ用二軸延伸ポリプロピレンフィルム、金属化フィルムおよびフィルムコンデンサ - Google Patents
コンデンサ用二軸延伸ポリプロピレンフィルム、金属化フィルムおよびフィルムコンデンサ Download PDFInfo
- Publication number
- WO2012144015A1 WO2012144015A1 PCT/JP2011/059592 JP2011059592W WO2012144015A1 WO 2012144015 A1 WO2012144015 A1 WO 2012144015A1 JP 2011059592 W JP2011059592 W JP 2011059592W WO 2012144015 A1 WO2012144015 A1 WO 2012144015A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- biaxially stretched
- polypropylene film
- stretched polypropylene
- capacitor
- Prior art date
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 206
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 204
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 203
- 239000003990 capacitor Substances 0.000 title claims abstract description 110
- 239000010408 film Substances 0.000 title claims description 342
- 239000011104 metalized film Substances 0.000 title claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 13
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 description 69
- 238000005266 casting Methods 0.000 description 38
- 238000005259 measurement Methods 0.000 description 27
- 230000015556 catabolic process Effects 0.000 description 22
- 239000013078 crystal Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000007740 vapor deposition Methods 0.000 description 20
- 230000005855 radiation Effects 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 238000004804 winding Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 239000000155 melt Substances 0.000 description 10
- 230000003746 surface roughness Effects 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000003851 corona treatment Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 239000003484 crystal nucleating agent Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 208000028659 discharge Diseases 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 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
- 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
- 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
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 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
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- MBSRTKPGZKQXQR-UHFFFAOYSA-N 2-n,6-n-dicyclohexylnaphthalene-2,6-dicarboxamide Chemical compound C=1C=C2C=C(C(=O)NC3CCCCC3)C=CC2=CC=1C(=O)NC1CCCCC1 MBSRTKPGZKQXQR-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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 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
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 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
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0072—Roughness, e.g. anti-slip
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y99/00—Subject matter not provided for in other groups of this subclass
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
- Y10S977/948—Energy storage/generating using nanostructure, e.g. fuel cell, battery
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to a biaxially oriented polypropylene film suitable for packaging, industrial use, and the like. More specifically, the present invention relates to a biaxially oriented polypropylene for a capacitor excellent in high voltage resistance and suitable element workability as a dielectric for a capacitor. Related to film.
- Biaxially stretched polypropylene films are excellent in transparency, mechanical properties, electrical properties, etc., and are therefore used in various applications such as packaging, tapes, cable wrapping and electrical applications including capacitors.
- capacitors are particularly preferably used for high voltage capacitors because of their excellent withstand voltage characteristics and low loss characteristics, not limited to DC applications and AC applications.
- Such a biaxially stretched polypropylene film needs to be appropriately roughened from the viewpoint of voltage endurance and device processability, and this is particularly effective in improving the slipping property and oil impregnation property of the film or in the deposition capacitor. It is particularly important for imparting sex. In particular, in an oil-impregnated type capacitor, if the impregnation property is poor, performance such as pressure resistance and safety is remarkably impaired. Therefore, proper surface roughening is important.
- the term “security” refers to a metal-deposited capacitor that uses a metal-deposited film formed on the dielectric film as an electrode. In the event of abnormal discharge, the deposited metal scatters due to discharge energy, thereby recovering insulation and preventing short circuits. Thus, the function of the capacitor is maintained or prevented from being destroyed, and it is an extremely useful function from the viewpoint of safety.
- Such roughening methods include mechanical methods such as embossing and sandblasting, chemical methods such as chemical etching with solvents, methods of stretching sheets mixed with different types of polymers such as polyethylene, and generating ⁇ crystals.
- a method of stretching a sheet (see, for example, Patent Documents 1 and 2) has been proposed.
- the mechanical method and the chemical method have a low roughness density, and the method of stretching the sheet on which the ⁇ crystal is formed tends to generate coarse protrusions, which is not necessarily sufficient in terms of the roughness density, the coarse protrusions, and the number of protrusions.
- the film roughened by these methods may be insufficiently impregnated with oil between the film layers at the time of capacitor formation, and partly unimpregnated portions are likely to be formed, and the capacitor life may be reduced.
- the biaxially oriented polypropylene film produced by any of the methods has a problem in terms of reliability due to insufficient safety under a severe condition where the potential gradient is 200 V / ⁇ m or more as the use condition of the capacitor.
- the potential gradient is obtained by dividing the voltage applied to the dielectric film by the film thickness, and is the applied voltage per unit film thickness.
- Patent Document 4 For the roughness density and the uniformity of the protrusions, a high melt tension polypropylene film (see, for example, Patent Document 4) or a laminate of such a high melt tension polypropylene film and a normal polypropylene film (see, for example, Patent Document 3).
- Patent Document 5 discloses a biaxially stretched polypropylene film having a controlled surface roughness and a method for producing the same, but it is insufficient and difficult to sufficiently control the roughness of both surfaces of the film. It is.
- An object of the present invention is to provide a biaxially stretched polypropylene film for a capacitor that solves the above-described problems and exhibits excellent voltage resistance and reliability, particularly in applications for capacitors for AC voltage, and ensures stable device processability.
- the present invention for solving the above problems has the following features.
- SRzA 10-point average roughness of surface A (nm)
- SRzB 10-point average roughness of B surface (nm)
- PBmin Minimum protrusion height on the B surface (nm)
- PBmax Maximum protrusion height on the B surface (nm)
- PB450-750 Number of protrusions present on the B surface with a height of 450 nm or more and less than 750 nm per 0.1 mm 2 (pieces / 0.1 mm 2 )
- PB Total number of protrusions on the B surface per 0.1 mm 2 (pieces / 0.1 mm 2 )
- PB ′ 250 (pieces / 0.1 mm 2 )
- PB ′ Sum of count values (slices / 0.1 mm 2 ) at a slice value larger than the slice value at which the count value on the B surface measured by the non-contact three-dimensional fine shape measuring instrument is maximum
- PAmin A surface minimum protrusion height (nm)
- PAmax Maximum protrusion height on the A surface (nm)
- PA-PB ⁇ 200 (pieces / 0.1mm 2 )
- PA Total number of protrusions on the A surface per 0.1 mm 2 (pieces / 0.1 mm 2 ) (5) The biaxially stretched polypropylene film for capacitors according to any one of (1) to (4), wherein all of the following formulas are satisfied.
- a film that can be suitably used for an impregnation type capacitor for AC applications by having excellent surface characteristics on the front and back surfaces, and in particular, withstand voltage and safety, and suitable for device processing.
- An excellent biaxially oriented polypropylene film for a capacitor can be provided.
- each index of the present invention described below is defined as representing the minimum film thickness, the gap between film layers, and the ease of sliding, which are closely related to the voltage resistance of the polypropylene film and the workability of the capacitor element. It represents a surface form that cannot be expressed by a three-dimensional or three-dimensional centerline surface roughness and is difficult to realize.
- the present invention differs from the conventional roughness in that the number density of protrusions having a certain range of heights is defined to provide suitable device processability, safety, high withstand voltage, and particularly high withstand voltage for AC applications. A film having a voltage can be obtained.
- the biaxially stretched polypropylene film for a capacitor according to the present invention has protrusions on both sides, a thickness t1 ( ⁇ m) of 4 to 20 ⁇ m, and the film surface on the side having a small SRz value is the A surface, and the other surface is the B surface.
- the feature is that all of the following expressions are satisfied.
- the film thickness t1 by the micrometer method is preferably 4 to 20 ⁇ m from
- the film thickness t1 by the micrometer method is more preferably 5 to 15 ⁇ m, and particularly preferably 6 to 12.0 ⁇ m.
- the film thickness t1 is less than 4 ⁇ m, the mechanical strength and the dielectric breakdown strength may be inferior.
- the film thickness t1 exceeds 20 ⁇ m, it becomes difficult to form a film having a uniform thickness, and when used as a dielectric for a capacitor, the capacity per volume becomes small.
- the 10-point average roughness SRzB of the B surface is preferably 800 nm or more and 1,300 nm or less.
- SRzB is less than 800 nm, the film cannot be wound well due to poor air escape, etc., and the roll shape may be disturbed, and the slit process and capacitor element formation may not be performed successfully.
- SRzB is more preferably 900 nm or more and 1,200 nm or less, and further preferably 950 nm or more and 1,150 nm or less.
- the 10-point average roughness SRzA of the A surface is preferably 400 nm or more and 900 nm or less, more preferably 500 nm or more and 800 nm or less, and further preferably 550 nm or more and 750 nm or less.
- SRzA and SRzB are preferably in a preferable range, it is possible to obtain a film having improved workability and improved workability in the slit process and the capacitor element process.
- a preferable range of the ratio of SRzA and SRzB is 0.1 or more and 0.8 or less, and more preferably 0.3 or more and 0.7 or less.
- the above value is less than 0.1, the difference in height between the protrusions on both sides is too large, and the pressure resistance tends to deteriorate due to the influence of the protrusion difference.
- it exceeds 0.8 the protrusion disparity tends to be small, and the security is likely to be lowered.
- the film of the present invention has protrusions on both sides, but when the minimum protrusion height of the B surface is PBmin, a preferable value is PBmin ⁇ 100 nm, and more preferably PBmin ⁇ 200 nm. .
- PBmin is less than 100 nm, the film cannot be wound well due to poor air escape, and in the vapor deposition process, the slit process and the capacitor element winding process, there is a tendency that the film is easily damaged and becomes a defect.
- the minimum protrusion height PAmin on the A surface is also preferably 100 nm or more, and more preferably PAmin ⁇ 150 nm.
- the maximum protrusion height on the B surface is PBmax
- a preferable value is PBmax ⁇ 1,500 nm, and more preferably 1,100 nm to 1,500 nm.
- PBmax exceeds 1,500 nm, the dielectric breakdown characteristics are liable to be reduced due to coarse protrusions, the minimum film thickness is reduced, and the voltage resistance is liable to be lowered.
- the maximum protrusion height PAmax on the A surface is preferably 1,000 nm or less, and more preferably 600 nm or more and 950 nm or less.
- PB450-750 / PB is preferably 0.4 or more and 0.7 or less, more preferably 0.5 or more and 0.7 or less. If the above-mentioned range is not satisfied with respect to the protrusion on the B surface, the film cannot be wound due to poor air escape, and in the vapor deposition process, the slit process and the capacitor element winding process, it is easily damaged and becomes a defect. Tend.
- the interlayer gap is narrow and local interlayer adhesion occurs, and the withstand voltage property is likely to be lowered due to electric field concentration.
- the uniformity between the film interlayer gaps is inferior and uniform impregnation cannot be performed, so that local corona discharge occurs and the voltage resistance tends to decrease.
- PB ′ is preferably 250 / 0.1 mm 2 or more, more preferably 300 / 0.1 mm 2 or more.
- the total number (per 0.1 mm 2 ) of protrusions existing on the A surface is PA, and the value of
- the biaxially stretched polypropylene film for capacitors of the present invention has SRaA of 20 nm or more and 40 nm or less, and SRaB of 30 nm or more when the centerline average roughness of the A surface is SRaA and the centerline average roughness of the B surface is SRaB. It is preferable that it is 50 nm or less.
- SRaA is larger than 40 nm and SRaB is larger than 50 nm, when the films are laminated, air easily enters between the layers, leading to deterioration of the capacitor element.
- SRaA is less than 20 nm and SRaB is less than 30 nm, the slipperiness of the film will be poor and the handling properties will be poor.
- the capacitor element is impregnated with insulating oil, the insulating oil will penetrate evenly between the film layers. However, the capacity change tends to increase during continuous use.
- SRaA is more preferably 25 nm to 35 nm
- SRaB is more preferably 35 nm to 45 nm.
- the biaxially oriented polypropylene film for capacitors of the present invention preferably has the above-mentioned centerline average roughness (SRa) and 10-point average roughness (SRz) within a certain range. That is, on at least one surface, the SRz / SRa value (SRzA / SRaA or SRzB / SRaB) is preferably in the range of 20 to 35, more preferably in the range of 22 to 33, and particularly preferably 25. It is in the range of ⁇ 30. It is more preferable that the above range satisfies both the A side and the B side.
- SRa centerline average roughness
- SRz 10-point average roughness
- the film satisfies the above-mentioned regulations regarding roughness and protrusions, it becomes a film having a characteristic surface with excellent surface uniformity and excellent balance of roughness density. And when such a biaxially stretched polypropylene film for a capacitor is used as a capacitor, even if dielectric breakdown occurs, an appropriate gap (clearance) is maintained between the film layers. It has the outstanding function of maintaining (demonstrating the said safety
- the biaxially oriented polypropylene film for capacitors of the present invention preferably contains 0.05 to 10% by mass of branched polypropylene.
- the branched polypropylene (H) mentioned here is a polypropylene having 5 or less internal 3-substituted olefins per 10,000 carbon atoms. The presence of this internal trisubstituted olefin can be confirmed by the proton ratio in the 1 H NMR spectrum.
- the size of the spherulite generated in the cooling process of the melt-extruded resin sheet can be easily controlled to be small, and the generation of insulation defects generated in the stretching process can be reduced.
- a polypropylene film having excellent voltage resistance can be obtained.
- the branched polypropylene has the function of an ⁇ crystal nucleating agent, and can form a rough surface by crystal transformation as long as the addition amount is within a certain range.
- a biaxially oriented polypropylene film having a typical surface roughness can be provided.
- the content of branched polypropylene is more preferably 0.05 to 7% by mass, still more preferably 0.05 to 3% by mass.
- the content of the branched polypropylene is in the above range, a film excellent in element workability and capacitor characteristics can be obtained with improved winding properties and voltage resistance.
- a typical method is to obtain the desired protrusions and surface roughness by using crystal transformation from the viewpoint that electrical characteristics such as dielectric breakdown voltage are not deteriorated without adding electrical impurities. Can be adopted.
- the surface formation method by crystal transformation is, for example, a surface using two crystal systems possessed by polypropylene as described in M. Fujiyama, Journal of Applied Polymer Science 36, P.985-1948 (1988).
- ⁇ crystal monoclinic crystal system, crystal density 0.936 g / cm 2
- ⁇ crystal hexagonal system, crystal density 0.922 g / cm 2
- It is formed in an unstretched sheet, and irregularities are formed on the film surface by transforming thermally unstable ⁇ crystals into ⁇ crystals in the stretching step.
- the shape may exhibit a crater shape formed in an elliptical shape or an arc shape by the projection group.
- the surface shape obtained by the crystal transformation may be formed by the existence of many crater shapes, and may have a crater shape by connecting individual protrusions in an elliptical shape or an arc shape.
- the unevenness is not formed and it is relatively flat.
- the crater-shaped protrusions described above change corresponding to the ratio of the vertical and horizontal stretching ratios when biaxially stretching, and the aspect ratio is 1, that is, substantially circular when isotropic stretching, and flattened as the aspect ratio increases.
- the shape usually obtained by the sequential biaxial stretching method has a major axis in the transverse direction of the film (the width direction of the film roll).
- a plurality of craters having different shapes may be overlapped, and the arc may be arcuate or semi-arc shaped without being circularly closed.
- a method of increasing the nucleation ability by adding a material having a nucleating agent effect can be adopted.
- the number of nuclei is increased so that a large number of small fine protrusions are present, the number of relatively flat portions (portions where no protrusions are present) is reduced, and a surface form in which protrusions are uniformly formed as a whole can be obtained. . Since such a surface has projections densely formed, it is easy to satisfy the above-described surface shape defined by the present invention.
- Examples of the raw material having a nucleating agent effect include the above-described branched polypropylene. Since the above crater shape can be controlled by controlling the amount of branched polypropylene added and the film forming conditions, the characteristic surface shape of the present invention can be generated as a result.
- the biaxially stretched polypropylene film for capacitors of the present invention is preferably composed of a mixture of the aforementioned branched polypropylene and linear polypropylene.
- the melt crystallization temperature of ordinary polypropylene is about 110 ° C., but can be increased to 115 ° C. or higher. That is, in the process of self-healing of the capacitor, the high crystallization temperature makes it easy to recover the safety, and the breakdown voltage is improved without breaking.
- the vapor deposition metal around the discharge part is scattered by the discharge energy generated when the dielectric film causes dielectric breakdown for some reason, and the film itself partially melts due to partial high temperature at that time.
- High crystallization temperature makes it easy to recrystallize immediately and to recover the insulating property.
- the ambient temperature of the capacitor becomes high, it is difficult to recrystallize normally and it is difficult to recover the insulation.
- melt crystallization temperature as described above, it is easy to recrystallize at high temperatures during dielectric breakdown. Thus, security can be improved.
- by controlling the surface roughness for example, by roughening the surface and securing a gap between the film layers, the recovery of the insulating property is further improved, and the withstand voltage is further improved.
- the branched polypropylene is not particularly limited, but from the viewpoint of film forming property, the melt flow index (MFR) is preferably in the range of 1 to 20 g / 10 minutes, and preferably 1 to 10 g / 10 minutes. Those within the range are more preferred.
- the melt tension is preferably in the range of 1 to 30 cN, more preferably in the range of 2 to 20 cN.
- the ratio (SRz / SRa) between the 10-point average roughness SRz and the centerline average surface roughness SRa increases, and it becomes easy to form coarse protrusions. The higher the melt tension, the higher the uniformity of the projections, and the ratio (SRz / SRa) tends to be smaller.
- the melt tension is less than 1 cN, the uniformity of the protrusion is inferior, while when it is 30 cN or more, the preferable protrusion height cannot be maintained.
- a method of blending an oligomer or polymer having a branched structure, a method of introducing a long chain branched structure into a polypropylene molecule as described in JP-A-62-1121704, or A method as described in Japanese Patent No. 2869606 is preferably used.
- Specific examples include “Profax PF-814” manufactured by Basell, and “Daploy HMS-PP” manufactured by Borealis.
- the resin obtained by the electron beam cross-linking method has few gel components in the resin. Preferably used.
- melt crystallization temperature of PP is usually around 110 ° C., but rises to a range of 115 to 130 ° C. That is.
- the melting peak observed when measuring with 2nd-Run can have a shoulder peak temperature of 148 to 157 ° C. in addition to the first melting peak temperature of 160 to 172 ° C. It is possible to obtain a film having a dense surface shape with few coarse protrusions. In addition, with such a content, excellent surface uniformity with excellent protrusion uniformity and few coarse protrusions, and excellent workability and high resistance even under a wide range of atmospheric temperatures exceeding -40 ° C to 80 ° C. A biaxially stretched polypropylene film for a capacitor that exhibits voltage characteristics can be produced.
- the polymer is usually used for a packaging material or a capacitor, and preferably has a cold xylene-soluble part (hereinafter CXS) of 4% by mass or less.
- CXS cold xylene-soluble part
- the cold xylene soluble part (CXS) is a polypropylene component which is dissolved in xylene after being completely dissolved in xylene and then precipitated at room temperature.
- Reasons such as low stereoregularity and low molecular weight This is considered to correspond to a component that is difficult to crystallize. If many such components are contained in the resin, problems such as inferior thermal dimensional stability of the film or reduction in dielectric breakdown voltage at high temperatures may occur.
- CXS is preferably 4% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.
- the linear polypropylene to be used preferably satisfies the above range, but it is also preferable that the entire film containing the polymer as a constituent component satisfies the above range.
- the mesopentad fraction of the linear polypropylene is preferably 0.95 or more, more preferably 0.97 or more.
- the mesopentad fraction is an index indicating the stereoregularity of the crystal phase of polypropylene measured by a nuclear magnetic resonance method (NMR method). The higher the numerical value, the higher the crystallinity, the higher the melting point, and the higher the temperature. This is preferable because the dielectric breakdown voltage is increased.
- Such linear polypropylene is more preferably one having a melt flow index (MFR) of 1 to 10 g / 10 minutes, particularly preferably 2 to 7 g / 10 minutes, and further preferably 2 to 5 g / 10 minutes.
- MFR melt flow index
- the range is preferable from the viewpoint of film forming property.
- Such linear polypropylene is mainly composed of a propylene homopolymer, but may contain other unsaturated hydrocarbon copolymerization components or the like as long as the object of the present invention is not impaired.
- No polymer may be blended.
- the copolymerization amount or blend amount is preferably less than 1 mol% in copolymerization amount and less than 10
- the linear polypropylene has various additives such as a crystal nucleating agent, an antioxidant, a heat stabilizer, a slip agent, an antistatic agent, an antiblocking agent, and a filler as long as the object of the present invention is not impaired. , A viscosity modifier, a coloring inhibitor, and the like can also be contained.
- the selection of the type and content of the antioxidant may be preferable for 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.
- BHT 2,6-di-t-butyl-p-cresol
- 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
- Irganox registered trademark 1330: molecular weight 775.2 manufactured by Ciba Geigy
- tetrakis [methylene-3 (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] methane
- Irganox 1010 manufactured by Ciba Geigy, Inc., molecular weight 1,177.7
- Irganox 1010 manufactured by Ciba Geigy, Inc., molecular weight 1,177.7
- the total content of these antioxidants is preferably in the range of 0.03 to 1% by mass relative to the total amount of polypropylene. If the amount of the antioxidant is too small, the long-term heat resistance may be poor. If the amount of the antioxidant is too large, the capacitor element may be adversely affected by blocking at a high temperature due to bleeding out of these antioxidants.
- a more preferable content is 0.1 to 0.9% by mass, particularly preferably 0.2 to 0.8% by mass.
- a crystal nucleating agent can be added as long as it does not contradict the purpose of the present invention.
- branched polypropylene already has an ⁇ -crystal or ⁇ -crystal nucleating agent effect itself, but another ⁇ -crystal nucleating agent (dibenzylidene sorbitols, sodium benzoate, etc.), It is also preferable to add ⁇ crystal nucleating agents (amide compounds such as potassium 1,2-hydroxystearate, magnesium benzoate, N, N′-dicyclohexyl-2,6-naphthalene dicarboxamide, quinacridone compounds, etc.) and the like. .
- the amount is preferably less than 0.1% by mass, more preferably not substantially added.
- the glossiness of the film surface of the present invention is preferably in the range of 90 to 130%, more preferably 100 to 120%. That is, lowering the glossiness means increasing the light scattering density on the film surface, that is, increasing the unevenness of the film surface, and means increasing the number of protrusions per unit area.
- the glossiness is reduced to less than 90%, the liquid (oil) impregnation property is improved, but the air quantity between the protrusions increases due to the increase in the number of protrusions due to the formation of dense protrusions, and the film layers are slippery. There is a tendency that the element winding property is deteriorated and it is difficult to wind the film into a roll.
- glossiness exceeds 130%, it is difficult to form a flat capacitor element that is difficult to slip between the film layers, and there is a problem that the safety is deteriorated because sufficient clearance between the film layers cannot be maintained. May occur. If glossiness is the said range, element winding property, pressure
- the ash content of the biaxially stretched polypropylene film for capacitors of the present invention is preferably 50 ppm or less (mass basis, the same shall apply hereinafter), more preferably 30 ppm or less, and particularly preferably 20 ppm or less.
- the ash content exceeds 50 ppm, the dielectric breakdown resistance of the film is lowered, and the dielectric breakdown strength may be lowered when a capacitor is used.
- the biaxially stretched polypropylene film for capacitors of the present invention is preferably used as a dielectric film for capacitors, but is not limited to a specific type of capacitor.
- the electrode configuration may be either a foil-wound capacitor or a metal-deposited film capacitor, and is preferably used for a dry-type capacitor that does not use insulating oil at all from an oil-immersion type capacitor impregnated with insulating oil. This is particularly useful in an oil immersion type capacitor impregnated with insulating oil.
- a winding type or a lamination type may be used. Among the above, it is particularly preferably used as a wound capacitor of a metal vapor deposition film because of the characteristics of the film of the present invention.
- polypropylene film has a low surface energy, and it is difficult to stably deposit metal. Therefore, it is preferable to perform surface treatment in advance in order to improve the metal adhesion.
- Specific examples of the surface treatment include corona discharge treatment, plasma treatment, glow treatment, and flame treatment.
- the surface wetting tension of polypropylene film is about 30 mN / m, but by these surface treatments, the wetting tension is set to 37 to 50 mN / m, preferably about 39 to 48 mN / m. And a film with good security.
- the biaxially stretched polypropylene film for capacitors of the present invention can be obtained by biaxially stretching using a raw material that can give the above-described properties.
- the biaxial stretching method can be obtained by any of the inflation simultaneous biaxial stretching method, the stenter simultaneous biaxial stretching method, and the stenter sequential biaxial stretching method.
- high melt tension polypropylene resin (branched polypropylene) is blended with linear polypropylene, melt extruded, passed through a filtration filter, extruded from a slit die at a temperature of 220-280 ° C, and solidified on a cooling drum An unstretched sheet is obtained.
- it is preferable to appropriately generate ⁇ crystals and it is important to appropriately control the temperature of the cooling drum.
- the process may be appropriately determined 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 temperature of the cooling drum to be selected is preferably 60 to 120 ° C., more preferably 65 to 100 ° C., particularly preferably, although there is some degree of freedom because other factors influence as described above. Is in the range of 65-85 ° C. If the casting drum temperature is too high, the crystallization of the film may proceed excessively, making stretching in subsequent steps difficult, and voids may be formed in the film, resulting in reduced dielectric breakdown resistance.
- any method of an electrostatic application method, an adhesion method using the surface tension of water, an air knife method, a press roll method, an underwater casting method, etc. may be used.
- the air knife method is preferable because it is good and the surface roughness can be controlled.
- this unstretched film is biaxially stretched to be biaxially oriented.
- the unstretched film is preheated by passing it through a plurality of rolls maintained at 120 to 150 ° C. However, preheating is performed so that a temperature difference is applied to the roll so that heat is applied to the B side.
- the roll that contacts the A side is 120 to 140 ° C.
- the roll that contacts the B side is 130 to 150 ° C.
- the film is passed between rolls provided with a difference in peripheral speed, stretched at a temperature of 130 to 150 ° C. 2 to 6 times in the longitudinal direction, and cooled to room temperature.
- the preheating roll temperature and the contact time of the film sheet need to be in an appropriate relationship, and even if only the temperature is appropriate, the contact time of the preheating roll is too short or too long. Is unlikely to occur. On the other hand, even if the roll contact time is appropriate, if the preheating temperature is inappropriate, the difference between the front and back is not likely to occur.
- the preheating process time is A-side preheating
- 20 to 40% is B-side preheating
- the B-side surface temperature during preheating is higher than that of A-side.
- a high-output radiation heater for example, heater output 10.5 kW
- the controllability of the heat history is further enhanced, which is preferable.
- the appropriate time distribution is that the time when the film sheet is in contact with the preheating roll is 4 seconds on the A side and 3 seconds on the B side ( The remaining 4 seconds are not in contact with the roll).
- the preferred film surface temperature is 110 ° C. on the A side and 125 ° C. on the B side.
- the desired difference between the front and back is obtained by the film temperature history of the front and back sides. It is also preferable to use a radiation heater that instantaneously raises the film temperature immediately before stretching on the B-side when stretching in the longitudinal direction.
- a corona discharge treatment is performed in air, nitrogen, carbon dioxide, or a mixed gas thereof to obtain a film.
- the discharge treatment is performed with an output of about 10 to 20 kW.
- a metallized film by providing a metal film on at least one side of the above-described biaxially stretched polypropylene film for capacitors.
- the method of providing the metal film is not particularly limited.
- a method of providing a metal film such as an aluminum vapor deposited film that is used to form an internal electrode of the film capacitor by depositing aluminum on at least one surface of the polypropylene film is preferably used.
- other metal components such as nickel, copper, gold, silver, chromium, and zinc can be deposited simultaneously or sequentially with aluminum.
- a protective layer can be provided on the deposited film with oil or the like.
- the thickness of the metal film is preferably in the range of 20 to 100 nm from the viewpoint of the electric characteristics and self-heeling property of the film capacitor.
- the surface electric resistance value of the metal film is preferably in the range of 1 to 20 ⁇ / ⁇ . Since the metal type has a specific resistance value, and the resistance value is inversely proportional to the film thickness, the surface electrical resistance value can be controlled by the metal type and film thickness to be used.
- the metallized film obtained after forming the metal film can be subjected to an aging treatment at a specific temperature or a heat treatment. Further, for insulation or other purposes, at least one surface of the metallized film can be coated with polyphenylene oxide or the like.
- the metallized film thus obtained can be laminated or wound to form a film capacitor.
- An example of a preferred method for producing a wound film capacitor is as follows.
- the vapor deposition is performed in a stripe shape having a margin portion running in the longitudinal direction of one surface, and the margin portion in the longitudinal direction is positioned at the center of the rear surface side vapor deposition portion on the other surface. Vapor deposition in stripes.
- a tape-like take-up reel having a margin on one side (for example, a margin on the right side of the front surface and a margin on the left side of the back surface) is prepared on both sides of the front and back margins with a blade. Two each of the obtained reel and undeposited laminated film are overlapped and wound so that the metallized film protrudes from the laminated film in the width direction, and a wound body is obtained.
- the core material is removed from the wound body and pressed, and the metallicon is sprayed on both end faces to form external electrodes, and a lead wire is welded to the metallicon to obtain a wound capacitor element.
- Film capacitors are used for various purposes such as for vehicles, household appliances (TVs, refrigerators, etc.), general noise prevention, automobiles (hybrid cars, power windows, wipers, etc.) and power supplies.
- the modified film can be suitably used for any of them.
- sample preparation> A sample of 5 mg is enclosed in an aluminum pan for measurement. In addition, when metal vapor deposition etc. are given to the film, it removes suitably.
- A. Measurement conditions Apparatus: Bruker, DRX-500 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. NMR sample tube: 5 mm tube Pulse width: 45 ° (4.5 ⁇ s) Pulse repetition time: 10 seconds 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).
- peak splitting is performed as follows from the peak on the high magnetic field side, soft automatic fitting is performed, peak splitting is optimized, and mmmm and ss (mmmm spinning sideband peak) The sum of the peak fractions is defined as the mesopentad fraction (mmmm).
- the measurement is performed 5 times and the average value is obtained.
- Measurement conditions Apparatus: ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL Measurement nucleus: 1 H nucleus (resonance frequency: 500 MHz) Measurement concentration: 2 wt% Solvent: Heavy orthodichlorobenzene Measurement temperature: 120 ° C Pulse width: 45 ° Pulse repetition time: 7 seconds Conversion count: 512 times Measurement mode: non decoupling B.
- CXS Cold xylene soluble part
- CXS (mass%) (X / X0) ⁇ 100 (8) Centerline average roughness (SRaA, SRaB), Ten-point average roughness (SRzA, SRzB) Measured according to JIS B-0601 (1982) using a “non-contact three-dimensional fine shape measuring instrument (ET-30HK)” and “three-dimensional roughness analyzer (MODEL SPA-11)” manufactured by Kosaka Laboratory Ltd. . The measurement is repeated 10 times in the longitudinal direction, and the average value is obtained as center line average roughness (SRa), ten-point average roughness (SRz), protrusion height, number of protrusions, and further the ratio (SRz / SRa) is determined. It was. Detailed conditions for one measurement and data processing were as follows.
- the minimum protrusion height is a slice width lower limit value of the slice value (Z) from which the count value is first output. That is, if the slice value (Z) from which the count value is first output is a column of 200 nm, the minimum protrusion height Pmin is 200 nm.
- the maximum protrusion height is a slice value that is one greater than the slice value (Z) from which the count value was last output. That is, if the slice value (Z) from which the count value was last output is a column of 1000 nm, the maximum protrusion height Pmax is 1050 nm.
- the total number of protrusions indicates the sum of all the values obtained by converting the number of protrusions detected at the sampling interval in the width direction and the length direction shown in the measurement condition item to the number per 0.1 mm 2 .
- the total of the number of detected protrusions corresponding to a height of 450 nm or more and less than 750 nm is shown. Specifically, it is the sum of the count values in the columns corresponding to slice values (Z) of 450, 500, 550, 600, 650, and 700 nm.
- PB ' -Sum of count values at slice values larger than the slice value at which the count value on surface B is maximum
- the maximum slice value is confirmed as the count value on the B-side of the histogram, and the sum of the count values of slice values larger than that slice (slices greater than the maximum slice value by 50 nm or more) is shown.
- the sum of the slice values is 450, 500, 550, 600, 650, 700, and 750. 800 nm.
- 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 the 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 ⁇ Measurement method Sample holder for measurement Is used. The sample holder is a detachable metal plate with a circular hole in the center. The sample holder is sandwiched between the sample holders, and the film is stretched to the four sides of the sample holder. It was measured.
- Table 1 shows examples of measurement results obtained by the above method. When the data is shown in Table 1, each parameter of the present invention is read as follows.
- raw sheet slit yield the ratio of the number of rejected parts to the total number of production was expressed as a percentage and used as an index of workability (hereinafter referred to as raw sheet slit yield). Called rate). The higher the raw fabric slit yield, the better. 95% or more was judged as “A”, “ ⁇ 95%” as “B”, and less than 90% as “C”. “B” or higher is a practical level.
- the corona treatment applied to the polypropylene film was vapor-deposited in a stripe shape having a margin portion running in the longitudinal direction (repetition of a vapor deposition portion width of 39.0 mm and a margin portion width of 1.0 mm).
- a blade was put in the center of each vapor deposition part and the center of each margin part and slitted, and a take-up reel was formed into a tape having a width of 20 mm and a margin of 0.5 mm on the left or right.
- Two reels each having a left margin and a right margin, were overlapped and wound so that the vapor deposition portion protruded 0.5 mm from the margin portion in the width direction, and wound with a capacitance of about 10 ⁇ F.
- the core material was removed from the wound body and pressed, and metallicon was sprayed on both end surfaces to form external electrodes, and lead wires were welded to the metallicon to obtain a wound capacitor element.
- striped deposition having a margin portion running in the longitudinal direction of one surface (deposition of a deposition portion width of 39.0 mm and a margin portion width of 1.0 mm).
- the other surface is subjected to striped vapor deposition (repeating the vapor deposition portion width of 39.0 mm and the margin portion width of 1.0 mm) so that the margin in the longitudinal direction is located at the center of the rear surface side vapor deposition portion. It was.
- each margin part is slit with a blade, and both sides have a 0.5 mm margin on one side (for example, if there is a 0.5 mm margin on the right side of the front surface, a 0.5 mm margin on the left side of the back surface).
- a take-up reel was formed into a tape having a total width of 20 mm. Two pieces of each of the obtained reel and undeposited laminated film were overlapped and wound so that the metallized film protruded from the laminated film in the width direction, and a wound body having a capacitance of about 10 ⁇ F was obtained. The core material was removed from the wound body and pressed, and metallicon was sprayed on both end surfaces to form external electrodes, and lead wires were welded to the metallicon to obtain a wound capacitor element.
- KAW-4NHB made by Minato Seisakusho was used for the element winding described above. At that time, from the beginning of winding to the end of winding was visually observed, those with wrinkles and misalignment were rejected, and the ratio of the number of rejected to the total number of production was expressed as a percentage as an index of workability (Hereinafter referred to as element winding yield). The higher the element winding yield, the better. 95% or more was evaluated as good “A”, less than 95% as 80% or more as “B”, and less than 80% as defective “C”. “B” or higher is a practical level.
- a film obtained in each of the examples and comparative examples described later is a margin part that runs in the longitudinal direction with an aluminum and zinc alloy metal with a film resistance of 8 ⁇ / sq using a vacuum vapor deposition machine made by ULVAC. Vapor deposition was performed in a stripe shape having a width of 48.0 mm for the vapor deposition portion and 2.0 mm for the width of the margin portion, thereby obtaining a vapor deposition reel having a width of 50 mm.
- the capacitor element was wound up with an element winding machine (KAW-4NHB) manufactured by Minato Manufacturing Co., Ltd., metallized, and then heat-treated at a temperature of 105 ° C. for 10 hours in a vacuum. A capacitor element was finished by mounting. The capacitance of the capacitor element at this time was 5 ⁇ F.
- KAW-4NHB element winding machine manufactured by Minato Manufacturing Co., Ltd.
- A can be used without problems, but B can be used depending on conditions. C and D cause practical problems.
- Example 1 Polypropylene resin with a polypropylene mesopentad fraction of 0.985 and a melt mass flow rate (MFR) of 2.6 g / 10 min is mixed with 0.5 mass of branched polypropylene resin (high melt tension polypropylene Profax PF-814).
- MFR melt mass flow rate
- % was fed to an extruder having a temperature of 260 ° C., melt-extruded into a sheet form from a T-type slit die at a resin temperature of 255 ° C., and the molten sheet was cooled and solidified on a cooling casting drum maintained at 70 ° C. At this time, the holding time for the film temperature to be 110 to 135 ° C. was 3.2 seconds.
- the A side (casting drum side) of the sheet is preheated at 130 ° C.
- the B side (non-casting drum side) is preheated at 140 ° C., and then kept at a temperature of 148 ° C. between rolls provided with a peripheral speed difference.
- the film was stretched 4.6 times in the longitudinal direction.
- the drawing portion was stretched by using a radiation heater output of 10.5 kW to supplement the amount of heat.
- the film was guided to a tenter, stretched 10 times in the width direction at a temperature of 165 ° C., then heat-treated at 155 ° C. while giving a relaxation of 6% in the width direction, and then cooled to a film thickness of 7.0 ⁇ m.
- An axially stretched polypropylene film was obtained. Further, a corona discharge treatment was performed on the one surface of the film in the air at a treatment strength of 20 W ⁇ min / m 2 . The corona discharge treatment is preferably performed on the film surface having a smaller SRz value.
- the properties of the biaxially stretched polypropylene film thus obtained are as shown in Tables 2 to 4.
- Tables 2 to 4 also show the breakdown voltage and device processability of the obtained film. Both withstand voltage and device processability were excellent.
- Example 2 Except that the casting drum temperature was 80 ° C., a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 3 Except that the casting drum temperature was 65 ° C., film formation was carried out in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 4 The film was formed in the same manner as in Example 1 except that the A-plane stretching preheating temperature was 135 ° C., the B-plane stretching preheating temperature was 135 ° C., and the temperature during 4.6-fold stretching in the longitudinal direction was 140 ° C. A stretched polypropylene film was obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 5 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 6.5 ⁇ m. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 6 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 6.5 ⁇ m and the casting drum temperature was 80 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 7 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 6.5 ⁇ m and the casting drum temperature was 65 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 8 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 6.0 ⁇ m and the casting drum temperature was 75 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 9 The thickness of the biaxially oriented polypropylene film is 6.0 ⁇ m, the casting drum temperature is 75 ° C., and the corona discharge treatment is performed in the atmosphere with a treatment strength of 20 W ⁇ min / m 2 on both the A and B sides of the biaxially oriented polypropylene film.
- a biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 10 The film was formed in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 4.0 ⁇ m, the casting drum temperature was 85 ° C., and the temperature at which it was guided to the tenter and stretched 10 times in the width direction was 160 ° C. A biaxially stretched polypropylene film was obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 11 The film was formed in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 4.0 ⁇ m, the casting drum temperature was 90 ° C., and the temperature at which it was guided to the tenter and stretched 10 times in the width direction was 160 ° C. A biaxially stretched polypropylene film was obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 12 The film was formed in the same manner as in Example 1 except that the thickness of the biaxially stretched polypropylene film was 4.0 ⁇ m, the casting drum temperature was 80 ° C., and the temperature at which it was guided to the tenter and stretched 10 times in the width direction was 160 ° C. A biaxially stretched polypropylene film was obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 13 The thickness of the biaxially stretched polypropylene film is 12.0 ⁇ m, the casting drum temperature is 70 ° C., the temperature to be stretched 4.6 times in the longitudinal direction is 140 ° C., the radiation heater output is 13.5 kW, the tenter is led to the width direction A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the 10-fold stretching temperature was 170 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 14 The thickness of the biaxially stretched polypropylene film is 12.0 ⁇ m, the casting drum temperature is 75 ° C., the temperature at which the film is stretched 4.6 times in the longitudinal direction is 140 ° C., the radiation heater output is 13.5 kW, the tenter is led in the width direction.
- a biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the 10-fold stretching temperature was 170 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 15 The thickness of the biaxially stretched polypropylene film is 12.0 ⁇ m, the casting drum temperature is 75 ° C., the temperature at which it is stretched 4.6 times in the longitudinal direction is 140 ° C., the radiation heater output is 5.0 kW, the tenter is led in the width direction
- a biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the 10-fold stretching temperature was 170 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 16 The thickness of the biaxially oriented polypropylene film is 12.0 ⁇ m, the casting drum temperature is 80 ° C., the temperature for stretching 4.6 times in the longitudinal direction is 140 ° C., and the temperature for guiding the tenter to 10 times in the width direction is 170 ° C. Except that, a film was formed in the same manner as in Example 1 to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 17 The thickness of the biaxially stretched polypropylene film is 15.0 ⁇ m, the casting drum temperature is 70 ° C., the temperature to be stretched 4.6 times in the longitudinal direction is 140 ° C., the radiation heater output is 13.5 kW, the tenter is led in the width direction A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the 10-fold stretching temperature was 170 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 18 The thickness of the biaxially stretched polypropylene film is 15.0 ⁇ m, the casting drum temperature is 75 ° C., the temperature to be stretched 4.6 times in the longitudinal direction is 140 ° C., the radiation heater output is 13.5 kW, the tenter is led in the width direction A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the 10-fold stretching temperature was 170 ° C. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 19 Example 1 except that the thickness of the biaxially stretched polypropylene film is 8.0 ⁇ m, the casting drum temperature is 70 ° C., the temperature at which the film is stretched 4.6 times in the longitudinal direction is 140 ° C., and the radiation heater output is 13.5 kW. Film formation was performed in the same manner as above to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 20 Example 1 except that the thickness of the biaxially stretched polypropylene film is 8.0 ⁇ m, the casting drum temperature is 75 ° C., the temperature at which the film is stretched 4.6 times in the longitudinal direction is 140 ° C., and the radiation heater output is 13.5 kW. Film formation was performed in the same manner as above to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 21 Example 1 except that the thickness of the biaxially stretched polypropylene film is 8.0 ⁇ m, the casting drum temperature is 65 ° C., the temperature at which the film is stretched 4.6 times in the longitudinal direction is 140 ° C., and the radiation heater output is 13.5 kW. Film formation was performed in the same manner as above to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 22 In Example 1, a film was formed in the same manner except that the casting drum temperature was 65 ° C. and the radiation heater output was 13.5 kW to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 1 (Comparative Example 1) In Example 1, a film was formed in the same manner except that the branched polypropylene resin was not added to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 2 (Comparative Example 2) In Example 1, a film was formed in the same manner except that the casting drum temperature was 85 ° C. to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 3 (Comparative Example 3) In Example 1, a film was formed in the same manner except that the casting drum temperature was 55 ° C. to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 4 (Comparative Example 4) In Example 1, a film was formed in the same manner except that the radiation heater output was 3.5 kW, and a biaxially stretched polypropylene film was obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 5 (Comparative Example 5)
- the casting drum temperature was set to 80 ° C.
- the A surface stretching preheating temperature was set to 125 ° C.
- the B surface stretching preheating temperature was set to 135 ° C.
- the temperature at 4.6 times stretching in the longitudinal direction was set to 140 ° C.
- a film was formed in the same manner except that the heater output was 3.5 kW to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 6 (Comparative Example 6) In Example 1, a film was formed in the same manner except that the temperature at 4.6 times stretching in the longitudinal direction was set to 152 ° C., and a biaxially stretched polypropylene film was obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 7 a biaxially stretched polypropylene film was prepared in the same manner except that the branched polypropylene resin was not added, the A-plane stretching preheating temperature was 140 ° C., and the B-plane stretching preheating temperature was 130 ° C. Obtained. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 8 A biaxially stretched polypropylene film having a thickness of 6.0 ⁇ m in Example 8 was formed in the same manner except that the casting drum temperature was 85 ° C., to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 9 A biaxially stretched polypropylene film having a thickness of 6.0 ⁇ m in Example 8 was formed in the same manner except that the casting drum temperature was 55 ° C., to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 10 A biaxially stretched polypropylene film having a thickness of 4.0 ⁇ m in Example 10 was formed in the same manner except that the casting drum temperature was 95 ° C., to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 11 The biaxially stretched polypropylene film of Example 10 having a thickness of 4.0 ⁇ m was formed in the same manner except that the casting drum temperature was 75 ° C., to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 12 In Example 1, the thickness of the biaxially stretched polypropylene film was 3.0 ⁇ m, the casting drum temperature was 90 ° C., the radiation heater output was 3.5 kW, and the temperature for stretching 10 times in the width direction was 160 ° C. Film formation was performed to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 13 In Example 1, the thickness of the biaxially stretched polypropylene film was 3.0 ⁇ m, the casting drum temperature was 95 ° C., the radiation heater output was 3.5 kW, and the temperature for stretching 10 times in the width direction was 160 ° C. Film formation was performed to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 14 In Example 1, the thickness of the biaxially stretched polypropylene film was 3.0 ⁇ m, the casting drum temperature was 90 ° C., the radiation heater output was 10.5 kW, and the temperature for stretching 10 times in the width direction was 160 ° C. Film formation was performed to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 15 A biaxially stretched polypropylene film was obtained in the same manner as in Example 10 except that the biaxially stretched polypropylene film having a thickness of 4.0 ⁇ m was formed except that the casting drum temperature was 90 ° C. and the radiation heater output was 3.5 kW. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 16 A biaxially stretched polypropylene film was obtained in the same manner as in Example 8 except that the thickness of the 6.0 ⁇ m biaxially stretched polypropylene film was changed to 3.5 kW. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 17 The biaxially stretched polypropylene film having the thickness of 12.0 ⁇ m in Example 13 was formed in the same manner except that the casting drum temperature was set to 60 ° C. to obtain a biaxially stretched polypropylene film. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
- Example 18 A biaxially stretched polypropylene film was obtained in the same manner as in Example 14 except that the biaxially stretched polypropylene film having a thickness of 12.0 ⁇ m was changed to a radiation heater output of 5.0 kW. Properties of the obtained biaxially stretched polypropylene film are shown in Tables 2 to 4.
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Abstract
Description
0.1≦SRzA/SRzB≦0.8
PBmin≧100(nm)
PBmax≦1,500(nm)
0.4≦PB450-750/PB≦0.7
但し、
SRzA:A面の10点平均粗さ(nm)
SRzB:B面の10点平均粗さ(nm)
PBmin:B面の最小突起高さ(nm)
PBmax:B面の最大突起高さ(nm)
PB450-750:B面に存在する高さ450nm以上750nm未満の突起の0.1mm2あたりの個数(個/0.1mm2)
PB:B面に存在する突起の0.1mm2あたりの総個数(個/0.1mm2)
(2)下記式を満足している、(1)に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
PB’≧250(個/0.1mm2)
但し、
PB’: 非接触三次元微細形状測定器で測定したB面でのカウント値が最大となるスライス値よりも大きいスライス値でのカウント値の総和(個/0.1mm2)
(3)下記式を全て満足している、上記(1)または(2)に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
PAmin≧100(nm)
PAmax≦1,000(nm)
但し、
PAmin:A面の最小突起高さ(nm)
PAmax:A面の最大突起高さ(nm)
(4)PAとPBとが下記式を満足している、上記(1)~(3)のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
PA:A面に存在する突起の0.1mm2あたりの総個数(個/0.1mm2)
(5)下記式を全て満足している、上記(1)~(4)のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
30≦SRaB≦50(nm)
但し、
SRaA:A面の中心線平均粗さ(nm)
SRaB:B面の中心線平均粗さ(nm)
(6)A面の中心線平均粗さをSRaA(nm)、B面の中心線平均粗さをSRaB(nm)としたとき、SRzA/SRaAまたはSRzB/SRaBの少なくとも一方の値が20以上35以下である、上記(1)~(5)のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
0.1≦SRzA/SRzB≦0.8
PBmin≧100(nm)
PBmax≦1,500(nm)
0.4≦PB450-750/PB≦0.7
但し、
SRzA:A面の10点平均粗さ(nm)
SRzB:B面の10点平均粗さ(nm)
PBmin:B面の最小突起高さ(nm)
PBmax:B面の最大突起高さ(nm)
PB450-750:B面に存在する高さ450nm以上750nm未満の突起の0.1mm2あたりの個数(個/0.1mm2)
PB:B面に存在する突起の0.1mm2あたりの総個数(個/0.1mm2)
本発明のコンデンサ用二軸延伸ポリプロピレンフィルムにおいて、コンデンサ素子サイズと製膜安定性の点から、マイクロメータ法によるフィルム厚みt1が4~20μmであることが好ましい。マイクロメータ法によるフィルム厚みt1は、より好ましくは5~15μmであり、特に好ましくは6~12.0μmである。フィルムの厚みt1が4μmを下回ると、機械的強度や絶縁破壊強度に劣る場合がある。また、フィルムの厚みt1が20μmを超えると、均一な厚みのフィルムを製膜することが困難になり、またコンデンサ用の誘電体として用いた場合、体積当たりの容量が小さくなる。なお、本発明においてはA面に金属膜を設けることが好ましい。
JIS C-2330(2001)の7.4.1.1によりマイクロメータ法厚みを測定した。
JIS K-7105(1981)に準じ、スガ試験機株式会社製 デジタル変角光沢計UGV-5Dを用いて入射角60°受光角60°の条件で測定した5点のデータの平均値を光沢度とする。
JIS-K7210(1999)に準じて、測定温度230℃、荷重21.18Nで測定した。
セイコー社製RDC220示差走査熱量計を用いて、下記以下の条件で測定を行った。
検体5mgを測定用のアルミパンに封入する。尚、フィルムに金属蒸着等が施されている場合は適宜除去する。
以下の(a)→(b)→(c)のステップでフィルムを溶融・再結晶・再溶融させる。樹脂の融点は2nd Runで観測される融解ピークの内で最も高い融解ピーク温度を融点とした。3点の測定値の平均値を求めた。
(b)Tmc 280℃で5分保持後に20℃/分で 30℃まで冷却
(c)2nd Run 30℃→280℃(昇温速度20℃/分)
(5)メソペンタッド分率(mmmm)
試料を溶媒に溶解し、13C NMRを用いて、以下の条件にてメソペンタッド分率(mmmm)を求める(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℃
NMR試料管:5mm管
パルス幅:45°(4.5μs)
パルス繰り返し時間:10秒
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、更にソフトの自動フィッテイングを行い、ピーク分割の最適化を行った上で、mmmmとss(mmmmのスピニングサイドバンドピーク)のピーク分率の合計をメソペンタッド分率(mmmm)とする。
(a)mrrm
(b)(c)rrrm(2つのピークとして分割)
(d)rrrr
(e)mrmm+rmrr
(f)mmrr
(g)mmmr
(h)ss(mmmmのスピニングサイドバンドピーク)
(i)mmmm
(j)rmmr
(6)内部3置換オレフィン個数
試料を溶媒に溶解し、1H NMRを用いて、以下の条件にて内部3置換オレフィンの個数を求める。
装置:日本電子製ECX400P型核磁気共鳴装置
測定核:1H核(共鳴周波数:500MHz)
測定濃度:2wt%
溶媒:重オルトジクロロベンゼン
測定温度:120℃
パルス幅:45°
パルス繰り返し時間:7秒
換算回数:512回
測定モード:non decoupling
B.解析条件
オルトジクロロベンゼンの化学シフト7.10ppmを基準とし、5.0~5.2ppm領域のシグナルを内部3置換オレフィンのプロトンと帰属、0.5~2.0ppmのブロードなシグナルとの積分比から内部3置換オレフィンのプロトン比を求める。
ポリプロピレンフィルム試料0.5gを沸騰キシレン100mlに溶解して放冷後、20℃の恒温水槽で1時間再結晶化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(X(g))。試料0.5gの精量値(X0(g))を用いて以下の式で求める。
(8)中心線平均粗さ(SRaA、SRaB)、十点平均粗さ(SRzA、SRzB)
JIS B-0601(1982)により、株式会社小坂研究所製「非接触三次元微細形状測定器(ET-30HK)」及び「三次元粗さ分析装置(MODEL SPA-11)」を用いて測定した。測定は長手方向に10回繰り返し、その平均値として中心線平均粗さ(SRa)、十点平均粗さ(SRz)、突起高さ、突起個数を求め、更にその比(SRz/SRa)を求めた。1回の測定の詳細条件とデータ処理については下記の通りとした。
上記測定器により検出された検出値は、50nm間隔のヒストグラムとして出力される。たとえば検出値として200nm以上250nm未満の突起が存在した場合には、スライス値(Z)として200nmと表記された欄にカウントされる。ここで、最小突起高さは、最初にカウント値が出力されたスライス値(Z)のスライス幅下限値である。すなわち、最初にカウント値が出力されたスライス値(Z)が200nmの欄であれば、最小突起高さPminは200nmとなる。同様に、最大突起高さは、最後にカウント値が出力されたスライス値(Z)の一つ大きいスライス値である。すなわち、最後にカウント値が出力されたスライス値(Z)が1000nmの欄であれば、最大突起高さPmaxは1050nmとなる。
・総突起個数(PA、PB)(単位:個/0.1mm2)
総突起個数は測定条件の項目に示す幅方向、長さ方向サンプリング間隔で検出された突起個数を0.1mm2あたりの個数に換算した値を全て合計したものを示す。
上記ヒストグラムのB面側の値について、高さ450nm以上750nm未満に該当する突起検出個数を全て総和したものを示す。具体的には、スライス値(Z)が450,500,550,600,650,700nmに対応する欄のカウント値の合計である。
上記ヒストグラムのB面側のカウント値として最大となるスライス値を確認し、そのスライスよりも大きいスライス値(最大となるスライス値よりも50nm以上大きいスライス)でのカウント値を総和したものを示す。具体的には、突起個数が最大となるスライス値が400nm、最後にカウントされたスライス値が800nmの時、総和の対象となるのはスライス値450,500,550,600,650,700,750,800nmである。
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
・測定方法
測定には専用のサンプルホルダーを使用する。サンプルホルダーは中心に円形の穴が空いた脱着可能な2枚の金属板であり、その間にサンプルを挟んでサンプルホルダーの四方までフィルムを張って装着することで固定し、中央円形部のフィルムを測定した。
上記方法によって得られた測定結果の例を表1に示す。データが表1の場合、本発明の各パラメータは次の通り読み取る。
SRzA 678nm(小数点以下四捨五入)
SRaB 48.9nm(小数点第2位を四捨五入)
SRzB 1,225nm(小数点以下四捨五入)
PAmin 150nm
PAmax 750nm
PA 264個/0.1mm2(小数点以下四捨五入)
PBmin 300nm
PBmax 1,250nm
PB450-750 453個/0.1mm2(小数点以下四捨五入)
PB 749個/0.1mm2(小数点以下四捨五入)
PB’ 467個/0.1mm2(小数点以下四捨五入)
|PA-PB| 485個/0.1mm2
(9)フィルム原反特性(絶縁破壊電圧、原反スリット収率)
絶縁破壊電圧は、JIS C2330(2001)7.4.11.2 B法(平板電極法)に準じて、平均値を求め、測定したサンプルのフィルム厚み(μm)で除し、V/μmで表記した。
金属化フィルムを長さ方向に10mm幅方向に全幅(50mm)の長方形にカットして試料とし、4端子法により、幅方向30mm間の金属膜の抵抗を測定し、得られた測定値に測定幅(10mm)を乗じて電極間距離(30mm)を除して、10mm×10mm当たりの膜抵抗を算出した。
後述する各実施例および比較例で得られたポリプロピレンフィルムのコロナ処理面に、ULVAC製真空蒸着機でアルミニウムを膜抵抗が8Ω/sqとなるようにアルミニウムを真空蒸着した。
後述する各実施例および比較例で得られたフィルムに、ULVAC製真空蒸着機でアルミニウムと亜鉛のアロイ金属を膜抵抗が8Ω/sqで、長手方向に走るマージン部を有するストライプ状に蒸着し(蒸着部の幅48.0mm、マージン部の幅2.0mmの繰り返し)、幅50mmの蒸着リールを得た。
950+50×53/180=965V
算出電圧をフィルム厚みで割り返して耐電圧評価とした。
ポリプロピレンのメソペンタッド分率が0.985で、メルトマスフローレイト(MFR)が2.6g/10分であるポリプロピレン樹脂に、分岐鎖状ポリプロピレン樹脂(高溶融張力ポリプロピレンProfax PF-814)を0.5質量%ブレンドし、温度260℃の押出機に供給し、樹脂温度255℃でT型スリットダイよりシート状に溶融押出し、該溶融シートを70℃に保持された冷却キャスティングドラム上で冷却固化した。このとき、フィルム温度が110~135℃となる保持時間は3.2秒であった。
キャスティングドラム温度を80℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
キャスティングドラム温度を65℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
A面延伸予熱温度を135℃、B面延伸予熱温度を135℃とし、長手方向に4.6倍延伸時の温度を140℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを6.5μmとした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを6.5μmとし、キャスティングドラム温度を80℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを6.5μmとし、キャスティングドラム温度を65℃とした以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを6.0μmとし、キャスティングドラム温度を75℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを6.0μmとし、キャスティングドラム温度を75℃、二軸延伸ポリプロピレンフィルムのA面とB面の両面に20W・min/m2の処理強度で大気中でコロナ放電処理を行った以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを4.0μmとし、キャスティングドラム温度が85℃、テンターに導いて幅方向に10倍延伸する温度が160℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを4.0μmとし、キャスティングドラム温度が90℃、テンターに導いて幅方向に10倍延伸する温度が160℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを4.0μmとし、キャスティングドラム温度が80℃、テンターに導いて幅方向に10倍延伸する温度が160℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを12.0μmとし、キャスティングドラム温度が70℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kW、テンターに導いて幅方向に10倍延伸する温度が170℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを12.0μmとし、キャスティングドラム温度を75℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kW、テンターに導いて幅方向に10倍延伸する温度が170℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを12.0μmとし、キャスティングドラム温度が75℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が5.0kW、テンターに導いて幅方向に10倍延伸する温度が170℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを12.0μmとし、キャスティングドラム温度が80℃、長手方向に4.6倍に延伸する温度が140℃、テンターに導いて幅方向に10倍延伸する温度が170℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを15.0μmとし、キャスティングドラム温度を70℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kW、テンターに導いて幅方向に10倍延伸する温度が170℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを15.0μmとし、キャスティングドラム温度が75℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kW、テンターに導いて幅方向に10倍延伸する温度が170℃であること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを8.0μmとし、キャスティングドラム温度が70℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kWであること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを8.0μmとし、キャスティングドラム温度が75℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kWであること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
二軸延伸ポリプロピレンフィルムの厚みを8.0μmとし、キャスティングドラム温度が65℃、長手方向に4.6倍に延伸する温度が140℃、ラジエーションヒーター出力が13.5kWであること以外は実施例1と同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、キャスティングドラム温度を65℃とし、ラジエーションヒーター出力を13.5kWとした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、分岐鎖状ポリプロピレン樹脂を添加しないこと以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、キャスティングドラム温度を85℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、キャスティングドラム温度を55℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、ラジエーションヒーター出力を3.5kWとした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、キャスティングドラム温度を80℃とし、A面延伸予熱温度を125℃とし、B面延伸予熱温度を135℃とし、長手方向に4.6倍延伸時の温度を140℃とし、ラジエーションヒーター出力を3.5kWとした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、長手方向に4.6倍延伸時の温度を152℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、分岐鎖状ポリプロピレン樹脂を添加せず、A面延伸予熱温度を140℃とし、B面延伸予熱温度を130℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例8における厚み6.0μmの二軸延伸ポリプロピレンフィルムについて、キャスティングドラム温度を85℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例8における厚み6.0μmの二軸延伸ポリプロピレンフィルムについて、キャスティングドラム温度を55℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例10における厚み4.0μmの二軸延伸ポリプロピレンフィルムについて、キャスティングドラム温度を95℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例10の厚み4.0μmの二軸延伸ポリプロピレンフィルムにおいて、キャスティングドラム温度を75℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、二軸延伸ポリプロピレンフィルムの厚みを3.0μmとし、キャスティングドラム温度を90℃、ラジエーションヒーター出力を3.5kW、幅方向に10倍延伸する温度が160℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、二軸延伸ポリプロピレンフィルムの厚みを3.0μmとし、キャスティングドラム温度を95℃、ラジエーションヒーター出力を3.5kW、幅方向に10倍延伸する温度が160℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例1において、二軸延伸ポリプロピレンフィルムの厚みを3.0μmとし、キャスティングドラム温度を90℃、ラジエーションヒーター出力を10.5kW、幅方向に10倍延伸する温度が160℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例10における厚み4.0μm二軸延伸ポリプロピレンフィルムについて、キャスティングドラム温度を90℃、ラジエーションヒーター出力を3.5kWとした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例8における厚み6.0μm二軸延伸ポリプロピレンフィルムについて、ラジエーションヒーター出力を3.5kWとした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例13における厚み12.0μm二軸延伸ポリプロピレンフィルムについて、キャスティングドラム温度を60℃とした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
実施例14における厚み12.0μm二軸延伸ポリプロピレンフィルムについて、ラジエーションヒーター出力を5.0kWとした以外は同様に製膜を行い、二軸延伸ポリプロピレンフィルムを得た。得られた二軸延伸ポリプロピレンフィルムの特性を表2~4に示す。
Claims (10)
- 両面に突起を有するコンデンサ用二軸延伸ポリプロピレンフィルムであって、厚みt1(μm)が4~20μmであり、SRzが小さい側のフィルム表面をA面、他方の面をB面としたとき、下記式を全て満足しているコンデンサ用二軸延伸ポリプロピレンフィルム。
800≦SRzB≦1,300(nm)
0.1≦SRzA/SRzB≦0.8
PBmin≧100(nm)
PBmax≦1,500(nm)
0.4≦PB450-750/PB≦0.7
但し、
SRzA:A面の10点平均粗さ(nm)
SRzB:B面の10点平均粗さ(nm)
PBmin:B面の最小突起高さ(nm)
PBmax:B面の最大突起高さ(nm)
PB450-750:B面に存在する高さ450nm以上750nm未満の突起の0.1mm2あたりの個数(個/0.1mm2)
PB:B面に存在する突起の0.1mm2あたりの総個数(個/0.1mm2) - 下記式を満足している、請求項1に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
PB’≧250(個/0.1mm2)
但し、
PB’: B面において非接触三次元微細形状測定器を用いて高さ0nmから測定した50nm刻みの測定高さ(スライス値)のうち、カウントされる値が最大となるスライス値よりも大きいスライス値でカウントされる突起個数の総和(個/0.1mm2) - 下記式を全て満足している、請求項1または2に記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
400≦SRzA≦900(nm)
PAmin≧100(nm)
PAmax≦1,000(nm)
但し、
PAmin:A面の最小突起高さ(nm)
PAmax:A面の最大突起高さ(nm) - PAとPBとが下記式を満足している、請求項1~3のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
|PA-PB|≧200
但し、
PA:A面に存在する突起の0.1mm2あたりの総個数(個/0.1mm2) - 下記式を全て満足している、請求項1~4のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
20≦SRaA≦40(nm)
30≦SRaB≦50(nm)
但し、
SRaA:A面の中心線平均粗さ(nm)
SRaB:B面の中心線平均粗さ(nm) - A面の中心線平均粗さをSRaA(nm)、B面の中心線平均粗さをSRaB(nm)としたとき、SRzA/SRaAまたはSRzB/SRaBの少なくとも一方の値が20以上35以下である、請求項1~5のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
- 分岐鎖状ポリプロピレンを0.05~10.0質量%含有する、請求項1~6のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルム。
- 請求項1~7のいずれかに記載のコンデンサ用二軸延伸ポリプロピレンフィルムの少なくとも片面に金属膜が設けられてなる金属化フィルム。
- 金属膜の表面電気抵抗が1~20Ω/□の範囲内にある、請求項8に記載の金属化フィルム。
- 請求項8または9に記載の金属化フィルムを用いてなるフィルムコンデンサ。
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CN201180070198.5A CN103503094B (zh) | 2011-04-19 | 2011-04-19 | 电容器用双轴拉伸聚丙烯膜、金属化膜和膜电容器 |
US14/112,591 US9991052B2 (en) | 2011-04-19 | 2011-04-19 | Biaxially stretched polypropylene film for capacitor, metallized film, and film capacitor |
PCT/JP2011/059592 WO2012144015A1 (ja) | 2011-04-19 | 2011-04-19 | コンデンサ用二軸延伸ポリプロピレンフィルム、金属化フィルムおよびフィルムコンデンサ |
ES11863937.6T ES2573799T3 (es) | 2011-04-19 | 2011-04-19 | Película de polipropileno estirada biaxialmente para condensador, película metalizada y condensador de película |
EP11863937.6A EP2701165B1 (en) | 2011-04-19 | 2011-04-19 | Biaxially stretched polypropylene film for capacitor, metallized film, and film capacitor |
KR1020137029295A KR101728585B1 (ko) | 2011-04-19 | 2011-04-19 | 콘덴서용 2축 연신 폴리프로필렌 필름, 금속화 필름 및 필름 콘덴서 |
BR112013026977A BR112013026977A2 (pt) | 2011-04-19 | 2011-04-19 | película de polipropileno biaxialmente estirada para capacitor, película metalizada, e capacitor de película |
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PCT/JP2011/059592 WO2012144015A1 (ja) | 2011-04-19 | 2011-04-19 | コンデンサ用二軸延伸ポリプロピレンフィルム、金属化フィルムおよびフィルムコンデンサ |
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US (1) | US9991052B2 (ja) |
EP (1) | EP2701165B1 (ja) |
KR (1) | KR101728585B1 (ja) |
CN (1) | CN103503094B (ja) |
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US20170240733A1 (en) * | 2014-09-11 | 2017-08-24 | Borealis Ag | Polypropylene compositions for capacitor film |
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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KR20160071239A (ko) | 2014-12-11 | 2016-06-21 | 도레이첨단소재 주식회사 | 박막 콘덴서용 이축 연신 폴리에스테르 필름 |
KR101638573B1 (ko) | 2014-12-26 | 2016-07-20 | 도레이첨단소재 주식회사 | 전기절연 특성과 표면 특성이 향상된 박막 콘덴서용 이축 연신 폴리에스테르 필름 |
WO2017022706A1 (ja) * | 2015-08-03 | 2017-02-09 | 東レ株式会社 | オレフィン系積層フィルムおよびフィルムコンデンサ |
WO2018142922A1 (ja) * | 2017-02-03 | 2018-08-09 | 株式会社村田製作所 | フィルムコンデンサ、フィルムコンデンサの製造方法、誘電体樹脂フィルム、及び、誘電体樹脂フィルムの製造方法 |
US20230265270A1 (en) | 2020-05-27 | 2023-08-24 | Borealis Ag | Bopp film for use in capacitor |
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BR112013026977A2 (pt) | 2017-01-10 |
EP2701165A4 (en) | 2015-01-28 |
US9991052B2 (en) | 2018-06-05 |
EP2701165A1 (en) | 2014-02-26 |
CN103503094A (zh) | 2014-01-08 |
US20140268493A1 (en) | 2014-09-18 |
KR20140027222A (ko) | 2014-03-06 |
KR101728585B1 (ko) | 2017-04-19 |
CN103503094B (zh) | 2016-05-25 |
ES2573799T3 (es) | 2016-06-10 |
EP2701165B1 (en) | 2016-04-06 |
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