CN100473691C - Biaxially oriented film - Google Patents
Biaxially oriented film Download PDFInfo
- Publication number
- CN100473691C CN100473691C CNB2005800037132A CN200580003713A CN100473691C CN 100473691 C CN100473691 C CN 100473691C CN B2005800037132 A CNB2005800037132 A CN B2005800037132A CN 200580003713 A CN200580003713 A CN 200580003713A CN 100473691 C CN100473691 C CN 100473691C
- Authority
- CN
- China
- Prior art keywords
- film
- biaxially oriented
- layer
- weight
- polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000098 polyolefin Polymers 0.000 claims abstract description 97
- 229920000728 polyester Polymers 0.000 claims abstract description 65
- 125000003118 aryl group Chemical group 0.000 claims abstract description 58
- 239000003990 capacitor Substances 0.000 claims abstract description 46
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims description 345
- 229920005992 thermoplastic resin Polymers 0.000 claims description 84
- 239000011342 resin composition Substances 0.000 claims description 79
- -1 polyethylene terephthalate Polymers 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000002356 single layer Substances 0.000 claims description 21
- 239000005001 laminate film Substances 0.000 claims description 20
- 230000015556 catabolic process Effects 0.000 claims description 17
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 229920006127 amorphous resin Polymers 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 33
- 239000010408 film Substances 0.000 description 564
- 239000002245 particle Substances 0.000 description 80
- 238000000034 method Methods 0.000 description 55
- 230000000052 comparative effect Effects 0.000 description 49
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 39
- 229920005989 resin Polymers 0.000 description 34
- 239000011347 resin Substances 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000000576 coating method Methods 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 230000003746 surface roughness Effects 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229920006267 polyester film Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000009998 heat setting Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- 239000004593 Epoxy Substances 0.000 description 1
- 229920003115 HPC-SL Polymers 0.000 description 1
- 101000619488 Homo sapiens Protein LTO1 homolog Proteins 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FQORROGUIFBEFC-UHFFFAOYSA-N OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O Chemical compound OC(=O)C1=CC([Na])=CC(C(O)=O)=C1S(O)(=O)=O FQORROGUIFBEFC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 102100022152 Protein LTO1 homolog Human genes 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001620 poly(3-methyl styrene) Polymers 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
An object of the present invention is to provide a thin biaxially oriented film excellent in dimensional stability against humidity change, as well as a magnetic recording medium and a film capacitor using the same. The present invention provides a single layered or laminated biaxially oriented film comprising an aromatic polyester (a) and a polyolefin (b) having a melting point of from 230 to 280 DEG C, wherein the ratio of the polyolefin (b) is from 2 to 60 % by weight based on the entire weight of the film, and the film thickness is from 1 to 10 m.
Description
Technical Field
The present invention relates to a thin biaxially oriented film having excellent dimensional stability against humidity change. More specifically, the present invention relates to a thin biaxially oriented film having excellent withstand voltage characteristics. Further, the present invention relates to a biaxially oriented film suitable for use as a base film for magnetic recording media and thin film capacitors.
Background
Polyester films have excellent thermal and mechanical properties, and therefore are used in various applications such as magnetic recording media, capacitors, flexible substrates, optical members, food packaging, and decoration.
In magnetic recording media, particularly magnetic recording media for storing data, the requirements for the properties of the base film have become more stringent as the capacity and density of the magnetic tape have become higher. Magnetic recording media for storing data using a linear track system, such as QIC, DLT, and super DLT and LTO with high capacity, have a very narrow track pitch in order to achieve high capacity of data. Therefore, when a dimensional change occurs in the width direction of the tape, a track skew is caused, and there is a problem that an error occurs. These dimensional changes include dimensional changes due to changes in temperature and humidity, and dimensional changes due to shrinkage in the width direction over time that occurs when the device is repeatedly operated under high tension in a high-temperature and high-humidity state. When the dimensional change is large, a track skew is caused, and an error in electromagnetic switching occurs. For convenience of explanation, the direction of travel in the continuous production of a film is sometimes referred to as the film-forming direction, continuous film-forming direction, longitudinal direction, or MD direction, and the in-plane direction of the film orthogonal to the film-forming direction is sometimes referred to as the transverse direction or width direction.
In order to solve such dimensional changes, Japanese unexamined patent publication Hei 5-212787 discloses a biaxially oriented polyethylene-2, 6-naphthalate film having a Young's modulus in the machine direction (EM), a Young's modulus in the transverse direction (ET), and a ratio of the Young's moduli (ET/EM) defined within a specific range, and having a shrinkage ratio in the machine direction and a temperature expansion ratio in the machine direction defined thereinThe ratio (α t), and the coefficient of humidity expansion (α h) in the longitudinal direction. Further, International publication No. 99/29488 pamphlet discloses a biaxially oriented polyester film in which the coefficient of thermal expansion in the transverse direction α t (× 10)-6/° c), coefficient of lateral humidity expansion α h (× 10)-6/% RH) and the transverse shrinkage P (ppm/g) with respect to a longitudinal load under the load are specified to be within specific ranges. Further, international publication No. 00/76749 pamphlet discloses a biaxially oriented polyester film, in which dimensional change in the width direction and thermal expansion coefficient α t (× 10) in the transverse direction when it is left standing with a load applied in the longitudinal direction are set-6/° c), coefficient of lateral humidity expansion α h (× 10)-6/% RH) and the transverse shrinkage P (ppm/g) with respect to a longitudinal load under the load are specified to be within specific ranges.
However, the methods proposed in these publications are achieved by setting the stretching conditions and the subsequent heat-setting treatment conditions in specific ranges, and for example, the longitudinal young's modulus of the base film can be improved by increasing the shrinkage in the width direction with time when a load is applied in the longitudinal direction, but on the other hand, from the viewpoint of polymer properties and film formability, the upper limit of the transverse young's modulus is smaller as the longitudinal young's modulus is increased, and as a result, dimensional change due to temperature and humidity change becomes large, and the like, which cannot be fundamentally solved.
Further, the capacitor is manufactured by the following method: a thermoplastic resin film such as polyethylene terephthalate or polypropylene and a metal film such as aluminum foil are laminated and wound or laminated. In recent years, with the demand for miniaturization of electric or electronic circuits, thin film capacitors have been also miniaturized and mounted, and further heat resistance is required in addition to electric characteristics. In addition, in automotive applications, the range of use is expanded not only in the cabin but also in the engine room, and there is a demand for a film capacitor suitable for dimensional stability under higher temperature and high humidity in addition to electrical characteristics.
Therefore, for the purpose of solving the heat resistance of films for capacitors, Japanese patent laid-open No. 2000-173855 discloses a method of using a polyethylene-2, 6-naphthalate film, and proposes a method of controlling the crystalline state, the limiting viscosity, and the like for the purpose of improving the electrical characteristics thereof. However, this method has a limit to further improvement in electrical characteristics because it is a polar polymer.
On the other hand, as a thermoplastic resin having excellent electrical characteristics, a syndiotactic polystyrene-based polymer is known. However, syndiotactic polystyrene-based polymers are difficult to form into films as compared with polyester resins, and the resulting films are also prone to cracking, so that improvement in workability in the production of capacitors is required.
International publication No. 97/32223 pamphlet proposes a film comprising syndiotactic polystyrene and polyethylene 2, 6-naphthalate. However, these films are optical materials for controlling optical characteristics such as reflectance and transmittance, and are substantially uniaxially oriented films.
In addition, Japanese patent application laid-open No. H08-176329 and the like propose a void-containing polyester film in which a polyester resin is blended with syndiotactic polystyrene as a void-developing agent, and disclose that the susceptibility to deformation of syndiotactic polystyrene at a stretching temperature affects the development of voids. However, since voids have a large influence on various properties as the thickness of the film becomes thinner, various properties required for those applications, for example, mechanical properties such as young's modulus and withstand voltage properties, may be lowered in applications requiring a thin film thickness.
In addition, as a film in which syndiotactic polystyrene and polyester are laminated, a laminated film in which the ratio of syndiotactic polystyrene layer is 70% or more is described in Japanese unexamined patent publication No. 8-48008.
Further, Japanese patent application laid-open No. 2000-326467 proposes a multilayer laminated film in which a layer containing polyethylene 2, 6-naphthalate and a layer containing syndiotactic polystyrene are alternately laminated in 11 or more layers. However, these films are intended to selectively reflect light of a specific wavelength by light interference due to a refractive index difference between layers.
Disclosure of Invention
The purpose of the present invention is to provide a thin biaxially oriented film having excellent dimensional stability against humidity changes.
Another object of the present invention is to provide a thin biaxially oriented film having excellent withstand voltage characteristics.
Another object of the present invention is to provide a biaxially oriented film suitable for use as a base film for a magnetic recording medium or a thin film capacitor.
The present inventors have assiduously studied to solve the above problems and, as a result, have found that a single-layer or laminated biaxially oriented film using an aromatic polyester and a polyolefin having a melting point of 230-280 ℃ in a specific ratio can reduce the dimensional change against humidity change while maintaining mechanical properties even when the film is thin, and have completed the present invention.
That is, the present invention is a biaxially oriented film which is a single-layer or laminated biaxially oriented film comprising an aromatic polyester (a) and a polyolefin (b) having a melting point of 230-280 ℃,
the polyolefin (b) is contained in an amount of 2 to 60 wt% based on the total weight of the film, and the film has a thickness of 1 to 10 μm.
The present invention also includes a magnetic recording medium and a thin film capacitor using the biaxially oriented film.
The biaxially oriented film of the present invention has a small thickness, but the dimensional change against humidity change is within a predetermined range. Therefore, the biaxially oriented film of the present invention can be suitably used as a base film for a magnetic recording medium.
The magnetic recording medium of the present invention is particularly suitable as a magnetic recording medium for storing data because it is less likely to cause track deviation and is excellent in terms of high density and high capacity.
Further, the biaxially oriented film of the present invention has a dimensional change against a change in humidity within a predetermined range and has excellent withstand voltage characteristics. Therefore, the biaxially oriented film of the present invention can be suitably used as a base film for a film capacitor.
The film capacitor of the present invention is suitable as a film capacitor for electric and electronic devices and automobile parts, which is thin, has excellent withstand voltage characteristics, and is required to be small and heat resistant.
Detailed Description
(biaxially oriented film)
The biaxially oriented film of the present invention is a single layer film or a laminated film, and specifically, the following configuration is illustrated. The biaxially oriented film of the present invention comprises an aromatic polyester (a) and a polyolefin (b) having a melting point of 230-280 ℃, and the proportion of the polyolefin (b) is required to be in the range of 2 to 60% by weight based on the total weight of the film. When the content of the polyolefin (b) is less than the lower limit, the improvement of the dimensional stability against humidity change is insufficient. In addition, when the content of the polyolefin (b) exceeds the upper limit, the obtained biaxially oriented film is a film lacking in mechanical properties. The proportion of the polyolefin (b) is preferably 3 to 55% by weight, more preferably 3 to 50% by weight, still more preferably 5 to 50% by weight, and particularly preferably 5 to 30% by weight. When the content of the polyolefin (b) is less than the lower limit, the improvement of the dimensional stability against humidity change may be insufficient and the withstand voltage characteristics may not be sufficiently improved. When the proportion of the polyolefin (b) exceeds 50% by weight, it may be difficult to stretch-form the film.
The thickness of the biaxially oriented film of the present invention is required to be in the range of 1 to 10 μm, preferably 2 to 10 μm, more preferably 2 to 7 μm, and particularly preferably 3 to 7 μm. When its thickness exceeds the upper limit, the film thickness is too thick, and in the case of use for a magnetic recording medium, for example, the tape length contained in the cartridge becomes short, and a sufficient magnetic recording capacity cannot be obtained. In addition, in the case of using the capacitor, miniaturization of the capacitor becomes difficult. On the other hand, when the amount is less than the lower limit, the film tends to be broken more often during film formation due to the small thickness of the film, and the winding property of the film tends to be poor.
(aromatic polyester (a))
The aromatic polyester (a) in the present invention is a polymer obtained by polycondensation of a diol and an aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, and 4, 4' -biphenyldicarboxylic acid, and examples of the diol include ethylene glycol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, and 1, 6-hexanediol. Among these polymers, polyethylene terephthalate and polyethylene 2, 6-naphthalate are preferable, and polyethylene 2, 6-naphthalate is particularly preferable from the viewpoint of mechanical properties and heat resistance.
The polyester resin in the present invention may be a single polyester resin or 1 selected from a copolymer with another polyester and a mixture of 2 or more polyesters, but from the viewpoint of mechanical properties and heat resistance, a single polyester resin is preferred. The other components in the copolymer or the blend are preferably 10 mol% or less, more preferably 5 mol% or less, based on the number of moles of the repeating structural unit. The copolymerization component includes a diol component such as diethylene glycol, neopentyl glycol or polyalkylene glycol, and a dicarboxylic acid component such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid or 5-sodiosulfoisophthalic acid.
The intrinsic viscosity of the polyester resin in the present invention is preferably 0.40 or more, more preferably 0.40 to 0.80 in o-chlorophenol at 35 ℃. When the intrinsic viscosity is less than 0.4, the film is often cut in many cases, and the strength of the molded product is insufficient. On the other hand, when the intrinsic viscosity exceeds 0.8, the yield at the time of polymerization is lowered.
The melting point of the polyester resin in the present invention is preferably 200-300 ℃, more preferably 240-300 ℃, and particularly preferably 260-290 ℃. When the melting point is less than the lower limit, the heat resistance of the polyester film tends to be insufficient. When the melting point exceeds the upper limit, it may be difficult to mix the polyolefin (b) with the polymer.
The polyester resin of the present invention preferably has a dielectric constant of 2.7 to 3.4 under the conditions of 23 ℃ and 1 MHz. This dielectric constant is a characteristic inherent to the polyester resin.
(polyolefin (b))
The polyolefin (hereinafter sometimes referred to as polyolefin (b)) in the present invention is a polyolefin having a melting point of 230-280 ℃. Examples of the polyolefin include poly-3-methylbutene-1, poly-4-methylpentene-1, polyvinylt-butane, 1, 4-trans-poly-2, 3-dimethylbutadiene, polyvinylcyclohexane, polystyrene, polymethylstyrene, polydimethylstyrene, and polybutylstyrene. Among these polyolefins, a styrene-based polymer having a syndiotactic structure (hereinafter, sometimes referred to as syndiotactic styrene-based polymer) is preferable in terms of heat resistance and mechanical properties.
The syndiotactic styrene polymer in the present invention is polystyrene having a syndiotactic structure in a stereochemical structure, which is prepared by a nuclear magnetic resonance method (13C-NMR method), the diad (2 constituent units) is 75% or more, preferably 85% or more, and the pentad (5 constituent units) is 30% or more, preferably 50% or more.
The syndiotactic styrenic polymer includes polystyrene, poly (methylstyrene) as a poly (alkylstyrene), poly (ethylstyrene), poly (propylstyrene), poly (butylstyrene) and poly (phenylstyrene), and among these, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene) and poly (p-t-butylstyrene) are preferably exemplified. The syndiotactic styrene polymer in the present invention may be a single syndiotactic styrene polymer or 2 or more syndiotactic styrene polymers may be used in combination.
The syndiotactic styrenic polymer in the present invention preferably has a weight average molecular weight of 10,000 or more, more preferably 50,000 or more. When the weight average molecular weight is less than the lower limit, the heat resistance and mechanical properties are insufficient. On the other hand, the upper limit of the weight average molecular weight is preferably 500,000 or less. When the amount exceeds the upper limit, the film-forming property tends to be poor.
The melting point of the polyolefin in the present invention is preferably 240-275 ℃. When the melting point is less than the lower limit, mixing with the aromatic polyester (a) is difficult, and the heat resistance of the obtained biaxially oriented film may be insufficient. In addition, the melting point exceeds the upper limit of the case and aromatic polyester mixed difficult.
The polyolefin of the present invention preferably has a dielectric constant of less than 3.0, more preferably in the range of 2.2 to 2.9 under the conditions of 23 ℃ and 1 MHz. When the dielectric constant exceeds the upper limit, the voltage resistance of the biaxially oriented film may not be sufficiently improved. When the dielectric constant is less than the lower limit, the polyolefin tends to be poor in processability.
The polyolefin of the present invention preferably has a dielectric loss of less than 0.001. Here, the dielectric loss is represented by the dielectric tangent (tan. delta.) at 23 ℃ under 1 MHz. When the dielectric loss is 0.001 or more, the insulation property is lowered, and the withstand voltage characteristics of the obtained biaxially oriented film are not sufficiently improved in some cases.
(Single layer film)
The biaxially oriented film of the present invention is preferably a single layer film. The single-layer film is preferably formed from a thermoplastic resin composition (c) which is a mixture of an aromatic polyester (a) and a polyolefin (b). In the single-layer film, the proportions of the aromatic polyester (a) and the polyolefin (b) are 40 to 98% by weight and 2 to 60% by weight, based on the weight of the film-forming thermoplastic resin composition (c). The content of the aromatic polyester (a) is preferably 45 to 97% by weight, more preferably 50 to 97% by weight, still more preferably 50 to 95% by weight, and particularly preferably 70 to 95% by weight. When the content of the aromatic polyester is less than the lower limit, the obtained biaxially oriented film is a film having poor mechanical properties. When the amount is less than 50% by weight, the stretching film formation may not be sufficiently improved. On the other hand, when the content of the aromatic polyester exceeds the upper limit, the improvement of the dimensional stability against humidity change may be insufficient, and the withstand voltage characteristics may be insufficient.
The content of the polyolefin (b) in the thermoplastic resin composition (c) is preferably 3 to 55% by weight, more preferably 3 to 50% by weight, still more preferably 5 to 50% by weight, and particularly preferably 5 to 30% by weight. When the content of the polyolefin (b) is less than the lower limit, the improvement of the dimensional stability against humidity change may be insufficient, and the withstand voltage characteristics may be insufficient. On the other hand, when the content of the polyolefin (b) exceeds the upper limit, the obtained biaxially oriented film becomes a film lacking in mechanical properties. When the amount exceeds 50% by weight, it may be difficult to stretch the film.
(laminated film)
(biaxially oriented film (X))
The biaxially oriented film of the present invention is preferably a laminated film. The biaxially oriented film is preferably a biaxially oriented film (X) comprising a film layer a formed of a thermoplastic resin composition (c') which is a mixture of an aromatic polyester (a) and a polyolefin (B), and a film layer B comprising the aromatic polyester (a) laminated on at least one surface thereof. In the film layer a, the ratio of the aromatic polyester (a) to the polyolefin (b) is preferably in the following range based on the weight of the thermoplastic resin composition (c') forming the film layer a. That is, in the thermoplastic resin composition (c'), the aromatic polyester (a) is in the range of 5 to 95% by weight, preferably 7 to 93% by weight, more preferably 10 to 90% by weight, particularly preferably 50 to 90% by weight, and the polyolefin (b) is in the range of 5 to 95% by weight, preferably 7 to 93% by weight, more preferably 10 to 90% by weight, particularly preferably 10 to 50% by weight. In the thermoplastic resin composition (c'), when the content of the aromatic polyester (a) exceeds the upper limit or the content of the polyolefin (b) is less than the lower limit, the intended effect of improving the dimensional stability against humidity change is lacking. On the other hand, when the content of the aromatic polyester (a) is less than the lower limit or the content of the polyolefin (b) exceeds the upper limit, the obtained biaxially oriented film becomes a film lacking in mechanical properties. When the content of the aromatic polyester (a) exceeds 50% by weight, particularly excellent film-forming properties can be obtained, and the adhesiveness to the film layer B becomes high.
The thickness of the film layer a is preferably 5 to 95%, more preferably 7 to 93%, and particularly preferably 10 to 90% of the thickness of the laminated film. When the thickness of the film layer a is less than the lower limit, the effect of improving the dimensional stability against humidity change is poor, and on the other hand, when the thickness of the film layer a exceeds the upper limit, the obtained biaxially oriented film becomes a film lacking in mechanical properties.
The film layer B may be a film layer substantially containing the aromatic polyester (a), and may contain other thermoplastic resins, for example, polyolefin (B), within a range not impairing the object of the present invention. The content of the aromatic polyester (a) in the film layer B is preferably 90% by weight or more, and more preferably 95% by weight or more, based on the weight of the film layer B.
The amount of the polyolefin (b) in the biaxially oriented film (X) is in the range of 2 to 60% by weight, preferably 3 to 55% by weight, more preferably 3 to 50% by weight, further preferably 5 to 50% by weight, and particularly preferably 5 to 30% by weight, based on the weight of the laminated film. When the amount of the polyolefin (b) is less than the lower limit, the effect of improving the dimensional stability against humidity change tends to be insufficient, and the withstand voltage characteristics may be insufficient. On the other hand, when the amount of the polyolefin (b) exceeds the upper limit, the obtained biaxially oriented film tends to be a film lacking in mechanical properties. When the amount exceeds 50% by weight, it may be difficult to stretch the film.
The biaxially oriented film (X) may have a preferred layer structure, for example: i) a 2-layer structure in which a film layer B is laminated on one surface of a film layer A; ii) a 3-layer structure in which a film layer B is laminated on both surfaces of a film layer A; iii) a multilayer structure in which at least 4 film layers A and B are stacked in terms of the total number of layers. in the case of the 3-layer structure of ii), the curl resistance is further improved. In the case of the multilayer structure of iii), even if a film layer containing a different resin is laminated, the film can be formed without deterioration of the process due to peeling between layers or the like. in the case of the multilayer structure of iii), the number of all layers is preferably 8 or more, more preferably 16 or more, and particularly preferably 32 or more, and the upper limit is not particularly limited, but from the viewpoint of preventing the process from being complicated, the number of layers is about 500, and preferably 250. Here, the film layers a and B are preferably alternately laminated, and a film layer containing another resin may be laminated as long as the object of the present invention is not impaired. iii) the thickness of each layer of the film layer A is preferably in the range of 0.02 to 1.5 μm, more preferably 0.04 to 1.0. mu.m, and the thickness of each layer of the film layer B is preferably in the range of 0.02 to 1.5. mu.m, more preferably 0.04 to 1.0. mu.m. When the thickness of each of the film layer a or the film layer B is less than the lower limit, extremely many layers need to be stacked, and the process is troublesome and complicated. On the other hand, when the thickness of each of the film layers a or B exceeds the upper limit, delamination may occur between the layers. The thickness of the film can be measured by cutting the laminated film in the thickness direction with a microtome or the like to prepare an ultrathin sheet, and observing the ultrathin sheet with a transmission electron microscope.
(biaxially oriented film (Y))
In another preferred embodiment of the laminated film, the biaxially oriented film (Y) is preferably composed of a film layer B containing an aromatic polyester (a) and a film layer C containing a polyolefin (B) laminated on at least one side thereof.
In the biaxially oriented film (Y), the film layer B contains the aromatic polyester (a), and other resins may be mixed or copolymerized within a range not impairing the object of the present invention. The content of the aromatic polyester (a) in the film layer B is preferably 90% by weight or more, and more preferably 95% by weight or more, based on the weight of the film layer B.
In the biaxially oriented film (Y), the film layer C contains the polyolefin (b), and other resins may be mixed or copolymerized within a range not impairing the object of the present invention. The content of the polyolefin (b) in the film layer C is preferably 90% by weight or more, and more preferably 95% by weight or more, based on the weight of the film layer C.
The amount of the polyolefin (b) in the biaxially oriented film (Y) is in the range of 2 to 60% by weight, preferably 3 to 55% by weight, more preferably 3 to 50% by weight, further preferably 5 to 50% by weight, and particularly preferably 5 to 30% by weight, based on the weight of the laminated film. When the amount of the polyolefin (b) is less than the lower limit, the effect of improving the dimensional stability against humidity change tends to be insufficient, and the withstand voltage characteristics may be insufficient. On the other hand, when the amount of the polyolefin (b) exceeds the upper limit, the obtained biaxially oriented film tends to be a film lacking in mechanical properties. When the amount exceeds 50% by weight, it may be difficult to stretch the film.
The biaxially oriented film (Y) may have a preferred layer structure, for example: i) a 2-layer structure in which a film layer B is laminated on one surface of a film layer C; ii) a 3-layer structure in which the film layer B is laminated on both surfaces of the film layer C; iii) a multilayer structure in which at least 4 film layers C and B are stacked in terms of the total number of layers. in the case of the 3-layer structure of ii), the curl resistance is further improved. In the case of the multilayer structure of iii), even if a film layer containing a different resin is laminated, the film can be formed without deterioration of the process due to peeling between layers or the like. in the case of the multilayer structure of iii), the number of all layers is preferably 8 or more, more preferably 16 or more, and particularly preferably 32 or more, and the upper limit is not particularly limited, but from the viewpoint of preventing the process from being complicated, the number of layers is about 500, and preferably 250. Here, the film layers B and C are preferably alternately laminated, and a film layer containing another resin may be laminated as long as the object of the present invention is not impaired. iii) the thickness of each layer of the film layer B is preferably in the range of 0.02 to 1.5 μm, more preferably 0.04 to 1.0. mu.m, and the thickness of each layer of the film layer C is preferably in the range of 0.02 to 1.5. mu.m, more preferably 0.04 to 1.0. mu.m. When the thickness of each layer of the film layer B or the film layer C is less than the lower limit, extremely many layers need to be stacked, and the process is easy to be complicated. On the other hand, when the thickness of each of the film layers B or C exceeds the upper limit, delamination may occur between the layers. The thickness of the film can be measured by cutting the laminated film in the thickness direction with a microtome or the like to prepare an ultrathin sheet, and observing the ultrathin sheet with a transmission electron microscope.
The biaxially oriented film in the present invention includes the above-mentioned single layer film and laminated film as specific examples, and the biaxially oriented film (X) and biaxially oriented film (Y) as specific examples of the laminated film, and a layer structure suitable for further required characteristics can be used according to the application. Among these layer structures, a monolayer film or a biaxially oriented film (X) is preferable from the viewpoint of layer peeling. In particular, in the case of a single-layer film, the blend exhibits excellent dimensional stability against humidity change due to the polyolefin (b) and excellent mechanical properties and film-forming properties due to the aromatic polyester (a). In the case of the single-layer film of the present invention, even if the amount of the polyolefin (b) blended is small, the single-layer film can have the same withstand voltage characteristics as the polyolefin (b). In addition, in the biaxially oriented film (X), in the case of 2-layer structure, by further laminating the film layer B, the excellent mechanical properties and film-forming properties due to the aromatic polyester (a) are easily exhibited. In addition, from the viewpoint of curl resistance, a 3-layer structure of the biaxially oriented film (X) is preferable.
(dispersed state of film layer comprising thermoplastic resin composition)
The film layer comprising the thermoplastic resin composition (c) or the thermoplastic resin composition (c') of the present invention is formed using a mixture of the aromatic polyester (a) and the polyolefin (b), and the polyolefin (b) is preferably dispersed in island form. The island-like dispersed shape may be any of a spherical shape, an elliptical shape, and a rod shape. In the present invention, a rod-like dispersion shape elongated in the MD direction is observed in many cases, and the average length in the MD direction is more preferably 20 μm or less. The average length is determined by measuring the length in the MD direction of 100 dispersed phases containing olefin (b) in a film thickness cross section parallel to the MD direction observed at 200 times using an optical microscope (oppthot-2 manufactured by Nikon corporation).
The average length in the MD direction is more preferably 15 μm or less, and particularly preferably 10 μm or less. When the average length exceeds the upper limit, the film may be easily broken in a stretching process. Further, as the film thickness becomes thinner, the influence of the size of the dispersed phase becomes remarkable, and the film is likely to be broken in the stretching step.
Examples of the method of setting the average length in the MD to 20 μm or less include a physical method using a kneading method and a chemical method using a compatibilizing agent. From the viewpoint of being processable with an existing apparatus, it is more preferable that the thermoplastic resin composition (c) or the thermoplastic resin composition (c') further contains a compatibilizing agent.
The compatibilizing agent herein includes, in addition to the definition of the usual compatibilizing agent, an agent having a function of reducing the size of the dispersed phase containing the polyolefin (b). The compatibilizing agent having such a function is not particularly limited, and examples thereof include a thermoplastic amorphous resin (d) having an intermediate solubility parameter (hereinafter, may be abbreviated as an SP value) between the aromatic polyester (a) and the polyolefin (b). The SP values of the aromatic polyester (a) and the polyolefin (b) are determined depending on the kind of the resin used and the copolymerization components. For example, among the aromatic polyesters (a), the SP value of polyethylene terephthalate calculated by the Fedor method (hereinafter, abbreviated as the Fedor method) is 23.6 (MJ/m)3)0.5The polyethylene-2, 6-naphthalate was 24.8 (MJ/m)3)0.5(Fedor method), and among the polyolefins (b), polystyrene was 20.7 (MJ/m)3)0.5(Fedor method).
Examples of the thermoplastic amorphous resin (d) include acrylic copolymerized polyolefin and vinyl oxazoline copolymerized polyolefin resin, and among these copolymers, styrene is more preferable as a monomer constituting the olefin component. In addition, among the copolymers, as monomers constituting the acrylic component, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are exemplified. The thermoplastic amorphous resin (d) may further contain an epoxy group to improve the compatibilizing effect.
The thermoplastic amorphous resin (d) is preferably contained in an amount of 0.1 to 10% by weight based on the weight of the thermoplastic resin composition (c) or the thermoplastic resin composition (c'). The content of the thermoplastic amorphous resin (d) is more preferably 0.2 to 5% by weight, particularly preferably 0.3 to 3% by weight. When the content is less than the lower limit, the effect as a compatibilizing agent is not exhibited, and therefore the average length of the polyolefin (b) is not in a desired range, and the film-forming property may be poor. On the other hand, when the content exceeds the upper limit, gelation may occur due to a crosslinking reaction.
The film layer comprising the thermoplastic resin composition (c) or the thermoplastic resin composition (c') of the present invention preferably has no voids. Here, the void refers to a void generated at the interface between the aromatic polyester (a) forming the matrix phase and the polyolefin (b) forming the island phase. The voids can be determined by 200-fold observation using an optical microscope (OPTPHOT-2 manufactured by Nikon Co., Ltd.) in the same manner as the method of determining the average length of the polyolefin (b). The term "having no voids" means that: in the observation by the optical microscope, the number of dispersed phases having voids around the dispersed phase is 10 or less, and more preferably 5 or less, among 100 dispersed phases containing the polyolefin (b).
When voids are present, the film may be easily broken in the film stretching step. Further, as the film thickness becomes thinner, the portion of the void becomes defective, and the mechanical properties and the withstand voltage properties may be lowered.
In order to have no voids, it is preferable to select the polyolefin (b) having a Tg lower than the glass transition point (Tg) of the aromatic polyester (a), and the stretching temperature of the film is equal to or higher than the Tg of the aromatic polyester (a). Among polyolefins, resins having a compatibility parameter close to that of aromatic polyesters are preferably used. Further, by containing a compatibilizing agent, voids can also be eliminated.
(inert particle)
The biaxially oriented film of the present invention may contain inert particles, for example, inorganic particles containing an element of group IIA, group IIB, group IVA or group IVB of the periodic table (for example, kaolin, alumina, titanium oxide, calcium carbonate, silica, etc.), fine particles comprising a highly heat-resistant polymer such as a crosslinked silicone resin, crosslinked polystyrene, crosslinked acrylic resin particles, etc., and the like.
When the inert particles are contained, the average particle diameter of the inert particles is preferably 0.001 to 5 μm, and the inert particles are preferably contained in a range of 0.01 to 10 wt% based on the total weight of the film.
In the case of use in a magnetic recording medium, preferable average particle diameter and content of the inert particles are exemplified below with respect to a single layer film or a laminated film.
That is, in the case where the monolayer film is used for the magnetic recording medium, the average particle diameter of the inert particles is preferably 0.01 to 1.0. mu.m, more preferably 0.03 to 0.8. mu.m, and particularly preferably 0.05 to 0.6. mu.m. The content of the inert particles is preferably 0.01 to 1.0% by weight, more preferably 0.03 to 0.8% by weight, particularly preferably 0.05 to 0.5% by weight, based on the weight of the thermoplastic resin composition (c). The inert particles contained in the film may be a single component or a multicomponent system, but from the viewpoint of having both the electromagnetic conversion property of the tape and the winding property of the film, it is preferable to contain 2-component or more than 2-component inert particles. The surface roughness (WRa) of the film surface can be adjusted by appropriately selecting the average particle diameter and the addition amount of the inert particles from the above ranges.
When the biaxially oriented film (X) or the biaxially oriented film (Y) is used as a laminated film for a magnetic recording medium, the average particle diameter of the inert particles is preferably 0.01 to 0.8. mu.m, more preferably 0.02 to 0.6. mu.m, and particularly preferably 0.03 to 0.4. mu.m. The content of the inert particles is not more than 0.5% by weight, preferably 0.4% by weight, and more preferably 0.3% by weight based on the weight of the film layer forming the surface on the flat surface side even when the inert particles are contained or contained. On the other hand, the surface on the rough surface side preferably contains 0.01 to 1.0 wt%, more preferably 0.03 to 0.8 wt%, and particularly preferably 0.05 to 0.6 wt% of inert particles with respect to the weight of the film layer forming the surface. In the case of a laminated structure of 4 or more layers, the film layer having the same composition as the film layer forming the rough surface side surface may contain the same inert particles as the rough surface side surface layer. The inert particles contained in the film may be a single component or a multicomponent system, but particularly in the polymer on the nonmagnetic layer side, it is preferable to contain 2 or more components of multicomponent inert particles from the viewpoint of having both the electromagnetic conversion property of the tape and the winding property of the film. The surface roughness (WRa) of the film surface can be adjusted by appropriately selecting the average particle diameter and the addition amount of the inert particles from the above ranges. In addition, in the case of a single-layer film, the roughness of one surface and the roughness of the other surface cannot be easily changed, but in the case of a laminated film, the roughness of one surface and the roughness of the other surface can be easily changed, and there is an advantage that both the electromagnetic conversion characteristic and the film running property are easily obtained.
(additives)
The biaxially oriented film of the present invention may contain a small amount of an ultraviolet absorber, an antioxidant, an antistatic agent, a light stabilizer, and a heat stabilizer, if necessary.
The biaxially oriented film of the present invention may contain a phosphorus compound. The phosphorus compound is not particularly limited in its kind if it functions as a heat stabilizer, and examples thereof include phosphoric acid esters such as phosphoric acid, methyl phosphate and ethyl phosphate, phosphorous acid and phosphorous acid esters, and among the phosphorus compounds, triethyl phosphonoacetate is particularly preferable.
The phosphorus compound is preferably contained in an amount of 20 to 300ppm, more preferably 30 to 250ppm, and particularly preferably 50 to 200ppm, in terms of the molar concentration of the phosphorus element in the phosphorus compound relative to the total dicarboxylic acid components of the polyester. When the content of the phosphorus compound is less than the lower limit, the transesterification catalyst is not completely deactivated, and sometimes the thermal stability is poor and the mechanical properties are lowered. On the other hand, when the content of the phosphorus compound exceeds the upper limit, the thermal stability is poor and the mechanical properties are sometimes degraded.
(coefficient of humidity expansion in width direction)
In the biaxially oriented film of the present invention, the moisture expansion coefficient α h in the width direction of the film is preferably 0.1 × 10-6～13×10-6/% RH. Further preferably,. alpha.h is 0.5X 10-6～11×10-6/% RH, particularly preferably 0.5X 10-6～10×10-6/% RH.
When α h is less than the lower limit, the polyolefin (b) is excessively present, and the film formability is sometimes lowered and the mechanical properties are sometimes lowered. On the other hand, if the upper limit is exceeded, the film is stretched by the change in humidity, and when used in a magnetic recording medium, track deviation or the like may occur, and when used in a thin film capacitor, the capacitor characteristics may be insufficient in applications required in high humidity environments such as an engine room of an automobile. Such α h is obtained by: the Young's modulus in the measurement direction is increased by stretching and is achieved by blending with polyolefin. When the film is not stretched in the width direction, the Young's modulus in the width direction is low, and therefore, even when polyolefin is blended, the coefficient of humidity expansion in the above range cannot be obtained.
(coefficient of thermal expansion in the width direction)
In the biaxially oriented film of the present invention, the temperature expansion coefficient α t in the width direction of the film is preferably-10X 10-6～+15×10-6Range/° c. Preferred alphat is-8X 10-6～+10×10-6Per DEG C, particularly preferably-5X 10-6～+5×10-6Range/° c. When α t is less than the lower limit, shrinkage occurs, and when α t exceeds the upper limit, the film stretches due to changes in humidity, and when the film is used for a magnetic recording medium, track deviation or the like may occur, and when α t exceeds the upper limit, the film may have insufficient capacitor characteristics when used for a capacitor, and in applications required in high-temperature environments such as an engine room of an automobile. Such α t is obtained by: the Young's modulus in the measurement direction is improved by stretching, and the amount of polyolefin present is not more than the above upper limit. In the widthWhen the film is not stretched in the transverse direction, the Young's modulus in the transverse direction is low, and therefore, even when a polyolefin is blended, the temperature expansion coefficient in the above range cannot be obtained.
(Young's modulus)
In the biaxially oriented film of the present invention, it is preferable that the young's modulus in both the film formation direction (MD direction) and the width direction (hereinafter, may be referred to as transverse direction or TD direction) of the film is 5GPa or more. When the young's modulus of either one is less than the lower limit, even if the dimensional change due to the change in humidity is small, the magnetic recording medium may not be able to withstand the load applied thereto or deformation due to the change in temperature and humidity. Further, the sum of the Young's modulus in the film forming direction and the Young's modulus in the width direction is preferably at most 22 GPa. When the sum of the young's modulus in the film forming direction and the young's modulus in the width direction exceeds the upper limit, the stretching ratio becomes excessively high in film formation, and film breakage occurs frequently, and the product yield tends to be significantly low. The upper limit of the sum of the Young's modulus in the film formation direction and the Young's modulus in the width direction is preferably 20GPa or less, and more preferably 18GPa or less.
In the case of providing a magnetic tape as a linear track system, it is preferable that the young's modulus in the film forming direction is larger than the young's modulus in the width direction from the viewpoint of reducing the elongation in the film forming direction. The young's modulus in the film-forming direction is preferably larger than the young's modulus in the width direction, the young's modulus in the film-forming direction is 6GPa or more, preferably 7GPa or more, particularly preferably 8GPa or more, and the young's modulus in the width direction is 5GPa or more, further preferably 6GPa or more, particularly preferably 7GPa or more. In addition, from the viewpoint of minimizing the elongation in the width direction, the young's modulus in the width direction is preferably larger than the young's modulus in the film formation direction. The young's modulus in the width direction is preferably larger than the young's modulus in the film formation direction, the young's modulus in the width direction is 7GPa or more, preferably 8GPa or more, and particularly preferably 9GPa or more, and the young's modulus in the film formation direction is 5GPa or more, more preferably 6GPa or more, and particularly preferably 7GPa or more. From the viewpoint of reducing the elongation in both the film-forming direction and the width direction, the difference between the young's modulus in the film-forming direction and the young's modulus in the width direction is 2GPa or less, particularly preferably 1GPa or less, the young's modulus in the film-forming direction is 6GPa or more, preferably 7GPa or more, particularly preferably 8GPa or more, and the young's modulus in the width direction is 6GPa or more, more preferably 7GPa or more, particularly preferably 8GPa or more.
(dielectric breakdown voltage)
The biaxially oriented film of the present invention preferably has a dielectric breakdown voltage of more than 400V/. mu.m. The dielectric breakdown voltage is more preferably 410V/μm or more, still more preferably 460V/μm or more, and particularly preferably 470V/μm or more. When the dielectric breakdown voltage is not more than the lower limit, the electrical characteristics when used in a capacitor may be insufficient. Here, the dielectric breakdown voltage is a value measured by a flat electrode method according to JIS C2151 using a device ITS-6003, manufactured by Tokyo Seiki Seikagaku corporation, at a DC current of 160V/s.
(Heat resistance temperature)
The heat resistant temperature of the biaxially oriented film of the present invention is preferably 110 ℃ or higher. The heat-resistant temperature is more preferably 115 ℃ or higher, and particularly preferably 120 ℃ or higher. When the heat-resistant temperature is less than the lower limit, the heat resistance may be insufficient when used in a capacitor. Here, the heatproof temperature is a temperature defined as a temperature that can withstand 20000 hours, in which an Arrhenius (Arrhenius) graph is plotted as a relationship between a time and a temperature of a half-life period of an insulation breakdown voltage in accordance with a temperature index of IEC 60216.
(coating layer)
The biaxially oriented film of the present invention may have a coating layer (hereinafter, sometimes referred to as a coating layer) on at least one surface of the outermost layer. The coating layer is obtained by coating a coating agent containing a binder resin and a solvent on a biaxially oriented film. As the binder resin, various resins of thermoplastic resins or thermosetting resins can be used, and examples thereof include polyesters, polyimides, polyamides, polyesteramides, polyolefins, polyvinyl chlorides, poly (meth) acrylates, polyurethanes, polystyrenes, copolymers thereof, and mixtures thereof. Among these binder resins, a polyester copolymer is particularly preferred. Examples of the solvent include organic solvents such as toluene, ethyl acetate, and methyl ethyl ketone, and mixtures thereof, and water may be used.
The coating layer in the present invention may further contain a crosslinking agent, a surfactant and inert particles as components for forming a coating film. The surfactant is, for example, a polyalkylene oxide.
The coating film layer in the present invention may further contain, in addition to the above components, other resins such as melamine resin, soft polymer, filler, heat stabilizer, weather stabilizer, aging inhibitor, marking agent (ラベリング), antistatic agent, slip agent, anti-blocking agent, anti-halation agent, dye, pigment, natural oil, synthetic oil, wax, emulsifier, curing agent, flame retardant, and the like, and the compounding ratio thereof is appropriately selected within a range not impairing the object of the present invention.
In the present invention, the method of laminating the coating film layer on the biaxially oriented film may be any of the following methods: a method of coating and drying a coating agent on at least one side of a biaxially stretched film; a method of applying a coating agent to a stretchable film, drying and stretching the film, and if necessary, performing a heat treatment. Here, the stretchable film is an unstretched film, a uniaxially stretched film or a biaxially stretched film, and among these films, a longitudinally stretched film which is uniaxially stretched in the direction of film extrusion (longitudinal direction) is particularly preferable.
When the coating agent is applied to the film, the coating agent is preferably applied in a clean atmosphere, that is, in a film formation step, and the adhesion of the coating film to the film is improved. In the case where a film subjected to heat fixation after biaxial stretching, which is a normal coating process, is applied in a process separated from the film production process, dust, dirt, and the like are easily entrained.
As a method for applying the coating agent to the film, any known coating method can be used, and for example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, a dipping method, and a curtain coating method can be used alone or in combination.
(surface layer)
The biaxially oriented film of the present invention may be a laminate in which another layer is further laminated on at least one surface for the purpose of imparting another function.
For example, in the case of use in a magnetic recording medium, a polyester film layer substantially free of inert particles may be laminated on the surface of the biaxially oriented film of the present invention on the magnetic layer side in order to make the magnetic layer side a more flat surface. In order to make the traveling surface (non-magnetic layer) side more excellent in traveling property, a polyester film layer containing a large amount of relatively large inert particles may be laminated on the non-magnetic layer side surface of the biaxially oriented film of the present invention. Such a laminated film is preferable as a magnetic recording medium in that both electromagnetic conversion characteristics and ease of film winding are obtained.
In the case of using the biaxially oriented film for a thin film capacitor, for example, a layer D of a compound containing an oxygen atom may be further provided on at least one surface of the biaxially oriented film for the purpose of further improving the self-repairability (セルフヒ - リング properties). The ratio of oxygen atoms to carbon atoms on the surface, as measured by X-ray photoelectron spectroscopy, is preferably 10% or more, and more preferably 15% or more. When the (oxygen atom/carbon atom) ratio is less than the lower limit, the self-repairability at the time of voltage loading may sometimes become poor. Examples of the compound containing an oxygen atom include cellulose and SiO2. In the case of cellulose, the binder component of the coating layer contains cellulose in an amount of 5 to 50 wt%, and the cellulose can be laminated by a coating method. In the presence of SiO2In the case of (2), any method of vacuum evaporation, ion plating, or sputtering may be used for lamination.
The thickness of the layer D containing the compound containing an oxygen atom is preferably 30% or less of the total thickness of the film. When the thickness is larger than 30%, electrical characteristics such as capacitance, temperature of dielectric tangent, frequency characteristics, and the like may be poor. The lower limit of the thickness is not particularly limited, but when it is thinner than 0.005 μm, the effect of improving the self-repairability may be hardly obtained.
(surface roughness WRa)
The biaxially oriented film of the present invention preferably has a surface roughness WRa (center plane average roughness) suitable for the use according to the use.
For example, in the case of use in a magnetic recording medium, the surface roughness WRa (center plane average roughness) of one surface of the biaxially oriented film is preferably 1 to 10nm, more preferably 2 to 10nm, and particularly preferably 2 to 8 nm. When the surface roughness WRa is more than 10nm, the surface of the magnetic layer becomes rough, and satisfactory electromagnetic conversion characteristics tend to be difficult to obtain. On the other hand, when the surface roughness WRa is less than 1nm, the surface is too flat, and therefore, the slip on the transfer roll (パスロ - ル) or the calender is deteriorated, wrinkles are generated, and the magnetic layer may not be smoothly applied, and the calendering may not be smoothly performed.
The surface roughness WRa of the other surface may be the same as WRa or larger than WRa, and is preferably 5 to 20nm, more preferably 6 to 15nm, and particularly preferably 8 to 12 nm. When the surface roughness WRa of the other surface is greater than the upper limit, the irregularities on the surface on the traveling surface side are transferred to the surface on the magnetic layer side, and the surface on the magnetic layer side becomes rough, so that satisfactory electromagnetic conversion characteristics may not be obtained. On the other hand, when the surface roughness WRa is less than the lower limit, the surface becomes too flat, the slip on the transfer roll or the calender is deteriorated, wrinkles are generated, and the magnetic layer may not be smoothly applied. In the case of a biaxially stretched laminate film, it is preferable that 2 surfaces have different surface morphologies from the viewpoint of easier adjustment of electromagnetic conversion characteristics and running properties.
These surface roughness WRa can be adjusted by including inert particles in the film or by surface treatment for forming fine irregularities, for example, coating treatment with a coating agent.
In addition, in the case of using the biaxially oriented film for a film capacitor, the surface roughness WRa (center plane average roughness) of the biaxially oriented film is preferably 1 to 150nm, more preferably 10 to 120nm, and particularly preferably 30 to 100 nm. When the surface roughness WRa is larger than the upper limit, the film protrusion becomes too large when processed into a capacitor, and the dielectric characteristics may be unstable due to the action of air interposed between the films, and the dielectric breakdown voltage may be easily lowered due to the action of the protrusion. On the other hand, if the surface roughness WRa is less than the lower limit, the film may be too flat, which may cause problems such as workability in the metal deposition step and the film winding step, deformation in the capacitor heat treatment step and the pressing step, and adhesion between films.
(method for producing film)
The biaxially oriented film of the present invention is preferably produced by the following method.
The biaxially oriented film of the present invention is produced by using a known film-forming method such as a tenter method or an inflation method after extruding the above-mentioned aromatic polyester (a) and polyolefin (b) as raw materials in a molten state into a sheet shape in the case of a single layer film, and includes, for example: a method in which a predetermined amount of an aromatic polyester (a) and a predetermined amount of a polyolefin (b) are mixed, dried, and then supplied to an extruder heated to 300 ℃ to be molded into a sheet from a T die.
Preferably, the film is produced by extruding the aromatic polyester at a temperature of from the melting point (Tm:. degree. C.) to (Tm + 70). degree.C.), rapidly cooling and solidifying the extruded film to give an unstretched film, stretching the unstretched film in a uniaxial direction (longitudinal or transverse direction) to a predetermined magnification at a temperature of from (Tg-10) to (Tg + 70). degree.C., then stretching the unstretched film in a direction perpendicular to the stretching direction (in the case where the first step is the longitudinal direction, the second step is the transverse direction) to a predetermined magnification at a temperature of from Tg to (Tg + 70). degree.C., and further carrying out a heat treatment. In this case, the stretching ratio, stretching temperature, heat treatment conditions, and the like are selected and determined according to the properties of the film. The area stretch ratio is preferably 6 to 35 times, and in the case of a capacitor, it is preferably 6 to 25 times, and more preferably 7 to 16 times. In the case of the magnetic recording medium, the amount is preferably 15 to 35 times, and more preferably 20 to 30 times. The thermal fixing temperature can be determined from the range of 190-250 ℃ and the treatment time can be determined from the range of 1-60 seconds. Particularly, when heat resistance is required, it is preferable to perform thermal fixation in the range of 210 ℃ and 240 ℃ in order to improve dimensional stability under high temperature conditions. By performing such heat-fixing treatment, the heat shrinkage ratio of the obtained biaxially oriented film at 200 ℃ can be made to be-3.5 to 3.5%, more preferably-3 to 3%, and particularly preferably 0 to 3%. When the heat shrinkage ratio is within these ranges, the film is less likely to wrinkle when processed into a capacitor. In order to suppress the heat shrinkage, annealing treatment may be further performed in an off-line step by heat treatment at 150-220 ℃ for 1-60 seconds and then slow cooling at 50-80 ℃.
In addition to the sequential biaxial stretching method described above, a biaxial stretching method may be used simultaneously. In the sequential biaxial stretching method, the number of times of stretching in the longitudinal direction and the transverse direction is not limited to1, and the longitudinal-transverse stretching can be performed by several times of stretching treatment, and the number of times is not limited. For example, in the case of magnetic recording medium applications, when it is desired to further improve the mechanical properties, the biaxially oriented film before the heat-fixing treatment is heat-treated at a temperature of (Tg +20) to (Tg +70) DEG C, stretched in the longitudinal or transverse direction at a temperature 10 to 40 ℃ higher than the heat-treatment temperature, and then further stretched in the transverse or longitudinal direction at a temperature 20 to 50 ℃ higher than the stretching temperature, preferably, the total stretch ratio in the longitudinal direction is 3.0 to 7.0 times, and the total stretch ratio in the transverse direction is 3.0 to 6.0 times.
In the case of producing a 2-layer or 3-layer laminated film, a coextrusion method is exemplified. Preferably, the raw materials constituting each layer are laminated in a die by coextrusion in a molten state and then extruded into a sheet, or 2 or more kinds of molten polyesters are extruded from a die and then laminated, rapidly cooled and solidified to form a laminated unstretched film, and then biaxially stretched and heat-treated by the same method and conditions as in the case of the single-layer film to form a laminated biaxially oriented film.
In the case of producing a laminate film having 4 or more layers, for example, it can be produced by a simultaneous multilayer extrusion method using a feed block as proposed in paragraph 0028 of Japanese patent laid-open No. 2000-326467. That is, the aromatic polyester (a) constituting the film layer B, the thermoplastic resin composition (C') constituting the film layer a, or the polyolefin (B) constituting the film layer C are dried, then supplied to an extruder heated to about 300 ℃, and, for example, the respective melts are alternately laminated using a feed block, developed and extruded in a die to form a laminated unstretched film, and then biaxially stretched and heat-treated by the same method and conditions as in the case of the single-layer film to form a laminated biaxially oriented film.
When a coating layer is provided, a desired coating liquid is preferably applied to one surface or both surfaces of the unstretched film or the uniaxially stretched film.
(magnetic recording Medium)
According to the present invention, there is provided a magnetic recording medium having the above biaxially oriented film of the present invention as a base film and having a magnetic layer on one surface thereof.
The magnetic recording medium is not particularly limited as long as the biaxially oriented film of the present invention is used as a base film, and examples thereof include a linear track type magnetic tape for storing data such as QIC, DLT, and high capacity type S-DLT and LTO. Further, since the dimensional change of the base film due to the temperature and humidity change is extremely small, even if the track pitch is narrowed to secure a high capacity of the magnetic tape, the magnetic recording medium is suitable for a high density and high capacity, in which the track deviation is hardly caused.
(film capacitor)
According to the present invention, there is provided a film capacitor comprising the above biaxially oriented film of the present invention as a base film and having a metal layer on at least one side thereof. The material of the metal layer is not particularly limited, and examples thereof include aluminum, zinc, nickel, chromium, tin, copper, and alloys thereof. In addition, in the case of providing the layer D containing a compound containing an oxygen atom for the purpose of improving self-repairability, the structure of the thin film capacitor is exemplified by base film/layer D/metal layer, layer D/base film/metal layer.
The film capacitor is not particularly limited as long as the biaxially oriented film of the present invention is used as a base film, and is used in electric and electronic applications requiring downsizing, in a cab for automobile applications, in an engine room requiring heat resistance and moisture resistance, and the like. Further, since the dimensional change of the base film due to the temperature/humidity change is extremely small and the heat resistance and the withstand voltage characteristic expressed by the breakdown voltage are excellent, the thin film capacitor can be further miniaturized and can be suitably used under high temperature and high humidity.
Examples
The present invention is described below based on examples. The characteristic values and evaluation methods were measured and evaluated by the following methods. In the examples, parts and% refer to parts by weight and% by weight, respectively.
(1) Melting point and glass transition point
10mg of the aromatic polyester (a) or the polyolefin (b) was sealed in an aluminum dish for measurement, and measured at a temperature rise rate of 20 ℃/min from 25 ℃ to 300 ℃ using a differential calorimeter DSC2920 manufactured by TAinstinstruments, to obtain the melting point (melting point of the aromatic polyester (a: Tma, melting point of the polyolefin (b: Tmb)) and the glass transition point (glass transition point of the aromatic polyester (a: Tga, glass transition point of the polyolefin (b: Tgb)) of each of them.
(2) Average particle size of inert particles
The measurement was carried out by using a CP-50 centrifugal particle Size Analyzer (centrifugal particle Size Analyzer) manufactured by Shimadzu corporation. From the cumulative curve of the particle diameters of the respective particles and the amounts thereof present, which was calculated based on the obtained centrifugal sedimentation curve, the particle diameter corresponding to 50 mass% (masspropecent) was read, and the value was defined as the above-mentioned average particle diameter.
(3) Coefficient of humidity expansion (α h)
A film sample was cut into a length of 15mm and a width of 5mm with the width direction set as the measurement direction, placed in a vacuum processing TMA3000, and the length of the sample at that time was measured while keeping the humidity of 30% RH and the humidity of 70% RH constant in a nitrogen atmosphere at 30 ℃ to calculate the humidity expansion coefficient by the following formula (1). The measurement direction is the longitudinal direction of the sample, and 10 samples were measured, and the average value thereof was defined as α h.
αh＝(L70-L30)/(L30×ΔH)。···(1)
Wherein L is30: sample length at 30% RH (mm)
L70: sample length at 70% RH (mm)
ΔH：40(＝70-30)％RH。
(4) Coefficient of thermal expansion (α t)
The film sample was cut into a length of 15mm and a width of 5mm with the width direction set as the measurement direction, placed in a vacuum processing TMA3000, pretreated under a nitrogen atmosphere (0% RH) at 60 ℃ for 30 minutes, and then cooled to room temperature. Thereafter, the temperature was raised from 25 ℃ to 70 ℃ at 2 ℃/min, the length of the sample at each temperature was measured, and the temperature expansion coefficient (. alpha.t) was calculated from the following formula (2). The measurement direction is the longitudinal direction of the sample, and the average value is used after 10 measurements.
αt＝{(L60-L40)/(L40×ΔT)}+0.5×10-6··(2)
Wherein L is40: sample length at 40 ℃ (mm)
L60: sample length at 60 ℃ (mm)
ΔT：20(＝60-40)℃
0.5×10-6: temperature coefficient of expansion of quartz glass.
(5) Young's modulus
The film was cut into a specimen having a width of 10mm and a length of 15cm at a chuck interval of 100mm, and was subjected to stretching at a stretching speed of 10mm/min and a recording paper speed of 500mm/min by an inward-type universal tensile testing apparatus, and the Young's modulus was calculated from a tangent line to the rising portion of the obtained load-elongation curve.
The measurement direction is the longitudinal direction of the sample, and the Young's modulus is measured 10 times and the average value is used.
(6) Surface roughness (WRa)
A measurement magnification was 25 times and a measurement area was 246.6. mu. m.times.187.5. mu.m (0.0462 mm) using a non-contact three-dimensional roughness meter (NT-2000) manufactured by WYKO2) Under the conditions (2), the center plane roughness was obtained by the following equation (3) using surface analysis software incorporated in the roughness meter (WRa). Further, the measurement was repeated 10 times, and the average value thereof was used.
Wherein,
here, Zjk is the height on the 3-dimensional roughness chart at the j-th and k-th positions in each direction when the measurement direction (246.6 μ M) and the direction (187.5 μ M) perpendicular thereto are divided into M and N, respectively.
(7) Thickness of each layer
The laminated film was cut into a triangular shape, fixed in an embedding カプセル, and then embedded with an epoxy resin. The film was cut with a microtome (ULTRACUT-S) in a direction parallel to the casting direction and the thickness direction to form a 50 nm-thick film section. Then, the film was photographed at a magnification of 1 to 10 ten thousand times under observation at an accelerating voltage of 1000kV using a transmission electron microscope, and the thickness of each layer was measured from the photograph.
(8) Dispersibility and voids of the olefin (b)
The film sample was observed with an optical microscope (OPTPHOT-2 manufactured by Nikon corporation) at 200X thickness in a cross section parallel to the MD direction, and the lengths in the MD direction of 100 dispersed phases containing the olefin (b) were measured to determine the average length.
Further, the number of dispersed phases in which voids occurred among 100 dispersed phases containing olefin (b) was determined by observing voids around the dispersed phase containing olefin (b) at that time, and was determined by the following criteria.
O: the number of dispersed phases having voids is 10 or less.
X: more than 10 dispersed phases with voids.
(9) Heat resistance
An arrhenius curve is drawn by using the temperature index of the film sample according to IEC60216, and the relationship between the time and the temperature of the half-life of the dielectric breakdown voltage is calculated, and the temperature which can endure 20000 hours is obtained.
(10) Dielectric constant
The dielectric constant at 23 ℃ and 1MHz was measured according to JIS C2151 using a thermoplastic resin.
(11) Dielectric loss
The dielectric loss at 23 ℃ and 1MHz was measured according to JIS C2151 using a thermoplastic resin.
(12) Breakdown voltage of insulation
Using the film sample, the dielectric breakdown voltage was measured by a flat electrode method described in JIS C2151 using ITS-6003, manufactured by Tokyo Seiki Seiko K.K., using a direct current of 160V/s.
(13) Film curling property
The film samples were sampled to have a length of 30mm × 200mm and a length of 200mm × 30mm, and were visually evaluated by the following criteria while being placed on a flat plate.
O: the curl was hardly visible.
Δ: curl was slightly visible.
X: curling up significantly.
(14) Resistance to peeling
On one surface of the sample film, 6 lines were drawn at 2mm intervals in the longitudinal and transverse directions by a cutter knife to prepare 25 checkerboards. Then, a 24mm wide tape (product name: ゼロテ - プ (registered trademark) manufactured by ニチパン) was stuck to both surfaces of the sample film, and the tape on the checkered side was rapidly peeled at a peeling angle of 180 degrees, and then the peeled surface was observed to evaluate on the following criteria.
O: the area was not peeled off, and the interlayer adhesion was good.
And (delta): the peeled area was less than 20%, and the interlayer adhesion was poor.
X: the peeled area was 20% or more, and the adhesion between layers was extremely poor.
(15) Film forming property
The film formation was observed and classified according to the following criteria.
O: the conditions for forming the film are limited to a narrow range, but an ultra-long roll can be used.
X: the continuous film forming property is poor, and film formation can be performed only for a very short time.
(16) Track skew
After recording at 10 ℃ and 10% RH using a LTO1 driver manufactured by ヒユ - レツトパツカ - ド, the recording was reproduced at 30 ℃ and 80% RH, and the track skew width of the magnetic tape with respect to the magnetic head due to the temperature and humidity change was measured.
The smaller the absolute values of these offset magnitudes, the better the representation.
(17) Moisture resistance of capacitor
4192A LF IMPEDANCENALYZER manufactured by ヒユ - レツトパツカ - ド was used, and the capacitor was aged for 500 hours with a voltage of 100V (DC) applied thereto at 60 ℃ and 95% RH, and the rate of change in electrostatic capacitance of the capacitor was measured and evaluated by the following criteria. Here, the electrostatic capacitance change rate is represented by Δ C/C (%), where C is the electrostatic capacitance before aging, and Δ C is the absolute value of the value obtained by subtracting the electrostatic capacitance before aging from the electrostatic capacitance after aging.
O: the ratio of Δ C/C (%) is 5 or less.
X: Δ C/C (%) exceeding 5.
< comparative example >
After the transesterification of dimethyl naphthalene-2, 6-dicarboxylate and ethylene glycol in the presence of manganese acetate by conventional methods, triethyl phosphonoacetate was added. Next, antimony trioxide was added thereto and polycondensation was carried out by a conventional method to obtain a polyethylene-2, 6-naphthalate resin (intrinsic viscosity (o-chlorophenol, 35 ℃ C.) 0.62, hereinafter abbreviated as PEN). The results of measuring the concentrations of the respective elements in the resin by the atomic absorption method were: mn is 50ppm, Sb is 300ppm, and P is 50 ppm. Further, in PEN, 0.02% by weight of silicone particles having an average particle diameter of 0.5 μm and 0.3% by weight of silica particles having an average particle diameter of 0.1 μm were previously added in the polymerization stage based on the weight of the resin composition.
The obtained PEN was dried at 180 ℃ for 6 hours, supplied to an extruder heated to 300 ℃ and extruded using a T-die to be rapidly cooled and solidified on a casting drum having a surface smoothness of 0.3S and a surface temperature of 60 ℃ to obtain an unstretched film. The unstretched film was preheated at 75 ℃ and heated from above 14mm between low-speed and high-speed rolls with an infrared heater having a surface temperature of 830 ℃ to be stretched 5.1 times in the film-forming direction of the film, quenched, then fed to a tenter, and stretched 4.8 times in the transverse direction at 125 ℃. Further, after heat-fixing at 240 ℃ for 10 seconds, a 1.0% relaxation treatment was carried out at 120 ℃ in the transverse direction to obtain a biaxially oriented film having a thickness of 4.5. mu.m. The Young's modulus of the resulting film was 8GPa in the machine direction and 6.5GPa in the transverse direction.
On the other hand, the following compositions were charged into a ball mill, kneaded and dispersed for 16 hours, and then 5 parts by weight of an isocyanate compound (デスモジユ - ル L, バイエル Co.) was added thereto, and the mixture was subjected to high-speed shearing dispersion for 1 hour to obtain a magnetic paint.
The magnetic paint comprises the following components:
acicular Fe particles 100 parts by weight
Vinyl chloride-vinyl acetate copolymer 15 parts by weight
(エスレツク 7A manufactured by Water-binding chemistry)
Thermoplastic polyurethane resin 5 parts by weight
Chromium oxide 5 parts by weight
5 parts by weight of carbon black
Lecithin 2 parts by weight
Fatty acid ester 1 part by weight
50 parts by weight of toluene
50 parts by weight of methyl ethyl ketone
50 parts by weight of cyclohexanone
The magnetic coating material was applied to one side of the PEN film to a coating thickness of 0.5. mu.m, followed by orientation treatment in a DC magnetic field of 2,500 Gauss, drying by heating at 100 ℃ and then multi-roll calendering (line pressure 2000N/cm, temperature 80 ℃) to perform winding. The wound roll was placed in an oven at 55 ℃ for 3 days.
Further, the other surface of the PEN film was coated with a back coating paint having the following composition to a thickness of 1 μm, dried, and cut to 12.65mm (1/2 inches), thereby obtaining a magnetic tape.
Composition of the back coating:
carbon black 100 parts by weight
60 parts by weight of thermoplastic polyurethane resin
18 parts by weight of an isocyanate Compound
(コロネ - ト L manufactured by Japan ポリウレタン Industrial Co., Ltd.)
0.5 part by weight of silicone oil
Methyl ethyl ketone 250 parts by weight
50 parts by weight of toluene
The properties of the obtained biaxially oriented films and magnetic tapes are shown in tables 1 and 5.
< example 1>
The PEN of comparative example 1 was changed to a thermoplastic resin composition (c1) prepared by uniformly blending 90 wt% PEN and 10 wt% syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.), and the stretching ratio was changed to obtain a biaxially oriented film having a Young's modulus of 8GPa in the machine direction, 6.5GPa in the transverse direction, and a thickness of 4.5 μm. In addition, 0.02 wt% of silicone particles having an average particle size of 0.5 μm and 0.3 wt% of silica particles having an average particle size of 0.1 μm were previously added to the thermoplastic resin composition (c1) in the polymerization stage of PEN, based on the weight of the thermoplastic resin composition (c 1).
The same operation as in comparative example 1 was repeated with respect to the obtained biaxially oriented film to prepare a magnetic tape.
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< example 2>
The same operation as in example 1 was repeated except that a thermoplastic resin composition (c2) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 10% by weight to 30% by weight was used instead of the thermoplastic resin composition (c1) and the draw ratio was changed.
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< example 3>
The same operation as in example 1 was repeated except that a thermoplastic resin composition (c3) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 10% by weight to 50% by weight was used instead of the thermoplastic resin composition (c1) and the draw ratio was changed.
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< example 4>
The same operation as in example 2 was repeated except that the stretching ratio was changed to obtain a biaxially oriented film having a Young's modulus of 8GPa in the machine direction, 8GPa in the transverse direction, and a thickness of 4.5. mu.m.
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< example 5>
The same operation as in example 2 was repeated except that the stretching ratio was changed to obtain a biaxially oriented film having a Young's modulus of 5.5GPa in the machine direction, a Young's modulus of 12GPa in the transverse direction, and a thickness of 4.5. mu.m.
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< example 6>
The same operation as in example 1 was repeated except that a thermoplastic resin composition (c4) was used in place of the thermoplastic resin composition (c1), and the PEN content was changed from 90% by weight to 89% by weight, and 1% by weight of epoxy group-containing acrylic copolymerized polystyrene (アルフオン UG-4070, manufactured by east asia synthetic company, SP value 21.5(Fedor method)) was added as a compatibilizing agent. Further, the SP value of PEN was 24.8(Fedor method), and the SP value of syndiotactic polystyrene was 20.7(Fedor method).
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< example 7>
The same operation as in example 2 was repeated except that a thermoplastic resin composition (c5) was used in place of the thermoplastic resin composition (c2), and 1 wt% of oxazoline group-containing polystyrene (エポクロス RPS-1005, SP value 22.2(Fedor method), manufactured by japan catalyst co., ltd.) was added to the thermoplastic resin composition (c5) in which the PEN content was changed from 70 wt% to 69 wt%. Further, the SP value of PEN was 24.8(Fedor method), and the SP value of syndiotactic polystyrene was 20.7(Fedor method).
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
< comparative example 2>
The same operation as in example 1 was repeated except that a thermoplastic resin composition (c6) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 10% by weight to 70% by weight was used instead of the thermoplastic resin composition (c1) and the draw ratio was changed.
Table 1 shows the properties of the obtained biaxially oriented film and magnetic tape.
TABLE 1
| Unit of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 | |
| Film thickness | μm | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 |
| Proportion of polyolefin | Wt％ | 10 | 30 | 50 | 30 | 30 | 10 | 30 | 0 | 70 |
| Compatibilizing agents | Wt％ | 1 | 1 | |||||||
| Young's modulus in the film formation direction | GPaGPa | 8.06.5 | 8.06.5 | 8.06.5 | 8.08.0 | 5.512 | 8.06.5 | 8.06.5 | 8.06.5 | 8.06.5 |
| Coefficient of thermal expansion | ppm/℃ | 7 | 7 | 8 | -2 | -8 | 7 | 7 | 7 | 8 |
| Coefficient of humidity expansion | ppm/％RH | 11 | 9 | 6 | 6 | 4 | 11 | 9 | 12 | 4 |
| Track skew | ppm | 862 | 705 | 548 | 367 | 100 | 870 | 705 | 940 | 391 |
| Film forming property | ◎ | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | × |
< example 8>
After the transesterification of dimethyl naphthalene-2, 6-dicarboxylate and ethylene glycol in the presence of manganese acetate by conventional methods, triethyl phosphonoacetate was added. Subsequently, antimony trioxide was added and polycondensation was carried out by a conventional method to obtain polyethylene 2, 6-naphthalate resin (PEN). The results of measuring the concentrations of the respective elements in the resin by the atomic absorption method were: mn is 50ppm, Sb is 300ppm, and P is 50 ppm.
A thermoplastic resin composition (c7) prepared by uniformly blending 90% by weight of the obtained PEN (intrinsic viscosity: 0.62) and 10% by weight of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was dried at 180 ℃ for 6 hours, then supplied to an extruder heated to 300 ℃ and molded into a sheet shape from a die at 290 ℃. The sheet was cooled and solidified on a cooling drum having a surface temperature of 60 ℃ to obtain an unstretched film, which was introduced into a roll stack heated to 140 ℃ and stretched 3.6 times in the longitudinal direction (machine direction), and then cooled in the roll stack at 60 ℃.
Subsequently, the longitudinally stretched film was introduced into a tenter while holding both ends thereof with clips, and stretched at 4.0 times in the direction (transverse direction) perpendicular to the longitudinal direction in an atmosphere heated to 150 ℃ at the maximum transverse stretching temperature. Then, the sheet was subjected to heat-setting at 220 ℃ for 5 seconds in a tenter, further subjected to 1% thermal relaxation at 200 ℃, then uniformly cooled slowly, and cooled to room temperature to obtain a biaxially oriented film having a thickness of 5 μm. The Young's modulus of the resulting film was 6.0GPa in the machine direction and 6.5GPa in the transverse direction.
500 angstroms of aluminum was vacuum-deposited on one side of the obtained biaxially oriented film, and the biaxially oriented film was wound into a 4.5mm wide tape to form a tape roll (リ - ル). The obtained coils were stacked and wound to obtain a wound body, which was then pressed at 150 ℃ and 1MPa for 5 minutes, both end surfaces were flame sprayed with a metal coating to form external electrodes, and leads were welded to the sprayed metal coating to form a wound film capacitor.
Table 2 shows the properties of the aromatic polyester (a) and the polyolefin (b) used and the properties of the obtained biaxially oriented film and capacitor.
< example 9>
The same operation as in example 8 was repeated except that a thermoplastic resin composition (c8) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 10% by weight to 30% by weight was used instead of the thermoplastic resin composition (c 7).
Table 2 shows the characteristics of the obtained biaxially oriented film and the film capacitor.
< example 10>
Instead of the thermoplastic resin composition (c7), a thermoplastic resin composition (c9) obtained by changing PEN to polyethylene terephthalate (PET) was used, dried at 170 ℃ for 3 hours, supplied to an extruder heated to 280 ℃, and molded into a sheet shape with a die at 290 ℃. The sheet was cooled and solidified on a cooling drum having a surface temperature of 20 ℃ to obtain an unstretched film, which was introduced into a roll stack heated to 90 ℃ and stretched 3.6 times in the longitudinal direction (machine direction), and then cooled in the roll stack at 20 ℃.
Subsequently, the longitudinally stretched film was introduced into a tenter while holding both ends thereof with clips, and stretched at 4.0 times in the direction (transverse direction) perpendicular to the longitudinal direction in an atmosphere heated to 120 ℃ at the maximum transverse stretching temperature. Then, the sheet was subjected to heat-setting at 220 ℃ for 5 seconds in a tenter, further subjected to 1% thermal relaxation at 200 ℃, then uniformly cooled slowly, and cooled to room temperature to obtain a biaxially oriented film having a thickness of 5 μm.
Table 2 shows the properties of the aromatic polyester (a) and the polyolefin (b) used and the properties of the obtained biaxially oriented film and film capacitor.
< comparative example 3>
The same operation as in example 8 was repeated except that 100% by weight of PEN was used instead of the syndiotactic polystyrene in the thermoplastic resin composition (c 7).
Table 2 shows the characteristics of the obtained biaxially oriented film and the film capacitor.
< comparative example 4>
The same operation as in example 10 was repeated except that 100% by weight of PET was used instead of the syndiotactic polystyrene in place of the thermoplastic resin composition (c 9).
Table 2 shows the characteristics of the obtained biaxially oriented film and the film capacitor.
< comparative example 5>
The same operation as in example 8 was repeated except that the thermoplastic resin composition (c10) was changed to 90% by weight from 10% by weight of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) in place of the thermoplastic resin composition (c 7).
Table 2 shows the characteristics of the obtained biaxially oriented film and the film capacitor.
TABLE 2
| Unit of | Example 8 | Example 9 | Example 10 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Film thickness | μm | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| Proportion of polyolefin | Wt％ | 10 | 30 | 10 | 90 | ||
| Aromatic polyester (a) type melting point (Tma) glass transition point (Tga) | ℃℃ | PEN270120 | PEN270120 | PET26075 | PEN270120 | PET26075 | PEN270120 |
| Melting point (Tma) glass transition point (Tgb) of polyolefin (b) dielectric constant dielectric loss | ℃℃ | 270932.60.0002 | 270932.60.0002 | 270932.60.0002 | ———— | ———— | 270932.60.0002 |
| Coefficient of thermal expansion | ppm/℃ | 7 | 7 | 7 | 7 | 7 | 8 |
| Coefficient of humidity expansion | ppm/％RH | 11 | 9 | 11 | 12 | 12 | 2 |
| Breakdown voltage of insulation | V/μm | 460 | 480 | 410 | 400 | 450 | 490 |
| Heat resistance | ℃ | 120 | 120 | 95 | 120 | 95 | 120 |
| Voids | - | ○ | ○ | × | － | － | － |
| Film forming property | － | ◎ | ◎ | × | ◎ | ◎ | × |
| Moisture resistance of capacitor | - | ○ | ○ | ○ | × | × | ○ |
< example 11>
The same operation as in example 8 was repeated except that a thermoplastic resin composition (c11) was used in place of the thermoplastic resin composition (c7), the PEN content was changed from 90% by weight to 89% by weight, and 1% by weight of oxazoline group-containing polystyrene (エポクロス RPS-1005, SP value 22.2(Fedor method), manufactured by japan catalyst co., ltd.) was added as a compatibilizing agent, and the film thickness was changed from 5.0 μm to 3.0 μm. Further, the SP value of PEN was 24.8(Fedor method), and the SP value of syndiotactic polystyrene was 20.7(Fedor method).
Table 3 shows the properties of the obtained biaxially oriented film.
< example 12>
The same operation as in example 11 was repeated except that the thermoplastic resin composition (c12) was used in place of the thermoplastic resin composition (c11) except that the PEN content was changed from 89% by weight to 79% by weight and the syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) content was changed from 10% by weight to 20% by weight.
Table 3 shows the properties of the obtained biaxially oriented film.
< example 13>
The same operation as in example 11 was repeated except that a thermoplastic resin composition (c13) in which the type of syndiotactic polystyrene was changed to 10 mol% of a methylstyrene-copolymerized syndiotactic polystyrene was used instead of the thermoplastic resin composition (c11), and a water-soluble coating solution having the following composition was applied to one surface of the uniaxially stretched film as a layer D so that the thickness after stretching and drying was 20 nm.
(composition of coating layer)
Binder resin a: isophthalic acid copolymerized PEN 50 wt%
Binder resin B: hydroxypropyl cellulose (Nippon Caoda corporation HPC-SL) 40% by weight
Surfactant (b): alkyl nonyl phenyl Ether 10% by weight
Table 3 shows the properties of the obtained biaxially oriented film.
Further, a film laminate obtained by depositing aluminum having a thickness of 600 angstroms on one side of the obtained film sample was cut into a square with 1cm on one side, and 2 pieces were stacked and sandwiched between rubber plates with 2cm on one side, and a load of 2kg was applied. In this state, a voltage was applied to the outside of the film laminate to cause dielectric breakdown, and self-repairability was observed.
< example 14>
The same operation as in example 12 was repeated except that the thermoplastic resin composition (c13) in which the PEN content was changed from 79% by weight to 80% by weight and the content of the compatibilizing agent was changed from 1% by weight to 0% by weight was used instead of the thermoplastic resin composition (c 12).
An attempt was made to obtain a biaxially oriented film having a thickness of 3.0 μm, but the film was broken very often during production.
< comparative example 6>
The same operation as in example 11 was repeated except that the content of PEN was changed from 89% by weight to 100% by weight instead of the thermoplastic resin composition (c11) and that syndiotactic polystyrene and a compatibilizing agent were not used.
Table 3 shows the properties of the obtained biaxially oriented film.
TABLE 3
| Unit of | Example 11 | Example 12 | Example 13 | Example 14 | Comparative example 6 | |
| Film thickness | μm | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Proportion of polyolefin | Wt％ | 10 | 20 | 10 | 20 | － |
| Compatibilizing agents | Wt％ | 1 | 1 | 1 | — | － |
| Aromatic polyester (a) type melting point (Tma) glass transition point (Tga) | ℃℃ | PEN270120 | PEN270120 | PEN270120 | PEN270120 | PEN270120 |
| Melting point of polyolefin (b) (Tma) glass transition point (Tgb) dielectric constant dielectric loss | ℃℃ | SPS270932.60.0002 | SPS270932.60.0002 | PMS-SPS247952.60.0002 | SPS270932.60.0002 | ———— |
| Coefficient of thermal expansion | ppm/℃ | 7 | 7 | 7 | 7 | 7 |
| Coefficient of humidity expansion | ppm/％RH | 11 | 10 | 11 | 10 | 12 |
| Breakdown voltage of insulation | V/μm | 460 | 480 | 460 | — | 380 |
| Heat resistance | ℃ | 120 | 120 | 120 | — | 120 |
| Average length of disperse phase | μm | 10 | 15 | 9 | 30 | — |
| Film forming property | — | ◎ | ◎ | ◎ | × | ◎ |
< example 15>
After the transesterification of dimethyl naphthalene-2, 6-dicarboxylate and ethylene glycol in the presence of manganese acetate by conventional methods, triethyl phosphonoacetate was added. Subsequently, antimony trioxide was added and polycondensation was carried out by a conventional method to obtain a polyethylene-2, 6-naphthalate resin (a) (hereinafter abbreviated as PEN (a)). The results of measuring the concentrations of the respective elements in pen (a) by atomic absorption were: mn is 50ppm, Sb is 300ppm, and P is 50 ppm.
A thermoplastic resin composition (c '1) obtained by uniformly blending 25% by weight of PEN (a) (having an intrinsic viscosity (o-chlorophenol, 35 ℃) of 0.62) and 75% by weight of syndiotactic polystyrene (B) (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) and PEN (a) were dried at 180 ℃ for 6 hours, respectively, and then fed to an extruder heated to 300 ℃ to form a film layer A and a film layer B by means of a multi-channel coextrusion die, laminated and extruded in a die, so that the thermoplastic resin composition (c' 1) became the film layer A and the PEN (a) became the film layer B, and then rapidly cooled and solidified on a casting drum having a surface finish of 0.3S and a surface temperature of 60 ℃ to obtain an unstretched film. The film layer A was extruded in contact with a casting drum, and 0.15% by weight of silica particles having an average particle diameter of 0.3 μm and 0.1% by weight of silica particles having an average particle diameter of 0.1 μm were previously added to PEN constituting the film layer B in the polymerization stage based on the weight of the layer, and 0.1% by weight of silica particles having an average particle diameter of 0.1 μm were previously added to the thermoplastic resin composition (c' 1) constituting the film layer A in the polymerization stage based on the weight of the layer.
A biaxially oriented laminate film was obtained by repeating the same operation as in comparative example 1 except that the stretching ratio of the unstretched film was changed. The Young's modulus of the resulting film was 8GPa in the machine direction and 6.5GPa in the transverse direction. The thicknesses of the film layer A and the film layer B in the laminated film were adjusted depending on the discharge amounts, and the film layer A was 4 μm and the film layer B was 2 μm.
The same operation as in comparative example 1 was repeated with respect to the obtained biaxially oriented laminated film to obtain a magnetic tape.
The magnetic coating material is formed on the surface of the film layer a of the biaxially oriented laminated film, and the back coating material is formed on the surface of the film layer B of the biaxially oriented laminated film.
Further, the proportion (% by weight) of the polyolefin is 1.36g/cm from the specific gravity of the PEN film3Syndiotactic polystyrene film specific gravity 1.04g/cm3And (4) obtaining.
Table 4 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 16>
The same operation as in example 15 was repeated except that a thermoplastic resin composition (c '2) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 75% by weight to 10% by weight was used instead of the thermoplastic resin composition (c' 1) and the draw ratio was changed.
Table 4 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< examples 17 to 19>
The same operation as in example 15 was repeated except that a thermoplastic resin composition (c '3) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 75% by weight to 30% by weight was used instead of the thermoplastic resin composition (c' 1) and the draw ratio was changed.
Table 4 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 20>
The same operation as in example 15 was repeated except that 0.1% by weight of silica particles having an average particle diameter of 0.1 μm were previously added to PEN constituting the film layer B in the polymerization stage, and that instead of the thermoplastic resin composition (c '1) constituting the film layer a, a thermoplastic resin composition (c' 4) was used in which the content of PEN (a) was changed from 25% by weight to 24% by weight and 1% by weight of oxazoline group-containing polystyrene (エポクロス RPS-1005, manufactured by japan catalyst corporation) was added as a compatibilizing agent, and that 0.15% by weight of silica particles having an average particle diameter of 0.3 μm and 0.1% by weight of silica particles having an average particle diameter of 0.1 μm were previously added in the polymerization stage.
The magnetic coating material is formed on the surface of the film layer B of the biaxially oriented laminated film, and the back coating material is formed on the surface of the film layer a of the biaxially oriented laminated film.
Table 4 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 21>
The same operation as in example 20 was repeated except that the stretching ratio was changed to use the thermoplastic resin composition (c '5) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 75% by weight to 10% by weight and the kind of the compatibilizing agent was changed to epoxy-containing acrylic copolymerized polystyrene (Toyo Synthesis Co., Ltd., アルフオン UG-4070) instead of the thermoplastic resin composition (c' 4).
Table 4 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 22>
The same operation as in example 20 was repeated except that a thermoplastic resin composition (c '6) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) was changed from 75% by weight to 30% by weight was used instead of the thermoplastic resin composition (c' 4) and the draw ratio was changed.
Table 4 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 23>
The same operation as in example 22 was repeated except that a 3-layer structure of film layer B/film layer a/film layer B was used instead of the 2-layer structure of film layer a/film layer B, the thickness of each film layer after biaxial stretching was changed to 1.0 μm/4.0 μm/1.0 μm, and the stretching ratio was changed.
Table 5 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< comparative example 7>
The same operation as in comparative example 1 was repeated except that a thermoplastic resin composition (c '7) in which the content of syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) in the thermoplastic resin composition (c' 1) was changed from 75% by weight to 70% by weight was used instead of PEN (a).
Table 5 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< comparative example 8>
The unstretched film obtained in example 23 was stretched 5.1 times in the film-forming direction of the film to obtain a uniaxially oriented film stretched only in the film-forming direction.
Table 5 shows the properties of the obtained uniaxially oriented films.
TABLE 4
TABLE 5
< comparative example 9>
The same operation as in comparative example 1 was repeated except that the film thickness after biaxial stretching was changed from 4.5 μm to 6.0. mu.m.
Tables 6 and 7 show the properties of the obtained biaxially oriented films and magnetic tapes.
< example 24>
Polyethylene-2, 6-naphthalate resin (PEN) was prepared as a resin for the film layer B, which was dried at 160 ℃ for 5 hours and had an intrinsic viscosity (o-chlorophenol, 35 ℃) of 0.62 and a melting point (Tm) of 269 ℃ by adding 0.02% by weight of silicone particles having an average particle diameter of 0.5 μm and 0.3% by weight of silica particles having an average particle diameter of 0.1 μm. A thermoplastic resin composition (c' 8) was prepared by adding 0.02% by weight of silicone particles having an average particle size of 0.5 μm and 0.3% by weight of silica particles having an average particle size of 0.1 μm, to a mixture of PEN having an intrinsic viscosity (o-chlorophenol, 35 ℃) of 0.62 and a melting point (Tm) of 269 ℃ dried at 160 ℃ for 5 hours and syndiotactic polystyrene (B) (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) dried at 100 ℃ for 3 hours, in a weight ratio of 50:50, and adding 0.02% by weight of silicone particles having an average particle size of 0.5 μm and 0.3% by weight of silica particles having an average particle size of 0.1 μm, as the resin of the film layer A. The polymers of the film layers a and B were fed to an extruder and melted, the polymer of the film layer B was branched into 25 layers, and the polymer of the film layer a was branched into 24 layers, and then the layers were joined using a multi-layer feed block device in which the layers a and B were alternately stacked, and the resulting mixture was fed into a die while maintaining the stacked state, and cast on a casting drum to prepare a stacked unstretched sheet in which the layers a and B were alternately stacked and the total number of layers was 49. At this time, the extrusion amount ratio of the polymers of the layer B and the layer a was adjusted to 8:2, and the layers were laminated so that both surface layers were the layer B. Further, the laminated unstretched sheet extruded from the die was rapidly cooled and solidified on a casting drum having a surface smoothness of 0.3S and a surface temperature maintained at 60 ℃ to form an unstretched film.
A biaxially oriented laminate film having a young's modulus of 8GPa in the machine direction and 6.5GPa in the transverse direction was obtained by repeating the same operation as in comparative example 1 except that the stretching ratio of the laminate unstretched film was changed. The thicknesses of the film layers A and B in the laminated film were adjusted by the discharge amount, and the thickness of each layer of the film layer B was 0.192. mu.m, 4.8 μm in total, the thickness of each layer of the film layer A was 0.050. mu.m, and the total thickness of the film layer A was 1.2. mu.m.
The same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Further, the proportion (% by weight) of the polyolefin is 1.36g/cm from the specific gravity of the PEN film3Syndiotactic polystyrene film specific gravity 1.04g/cm3And (4) obtaining.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 25>
In example 24, a biaxially oriented laminated film having a young's modulus in the machine direction of 8GPa, a young's modulus in the transverse direction of 6.5GPa, a thickness of each of film layers B of 0.168 μm, a total thickness of film layers B of 4.2 μm, a thickness of each of film layers a of 0.075 μm, and a total thickness of film layers a of 1.8 μm was obtained by repeating the same operations as in example 24 except that the inert particles contained in the resins of film layers a and B were changed to 0.1 wt% of silica particles having an average particle diameter of 0.1 μm, the thermoplastic resin composition (c '8) was changed to a thermoplastic resin composition (c' 9) which is a mixture of PEN and syndiotactic polystyrene in a weight ratio of 40:60, and the stretching ratio and the amounts of each of the layers were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 26>
In example 24, a biaxially oriented laminated film having a young's modulus of 8GPa in the machine direction, a young's modulus of 6.5GPa in the transverse direction, a thickness of 0.120 μm for each layer of the film layer B, a total thickness of 3.0 μm for the film layer B, a thickness of 0.125 μm for each layer of the film layer a, and a total thickness of 3.0 μm for the film layer a was obtained by repeating the same operations as in example 24 except that the thermoplastic resin composition (c '8) was changed to a thermoplastic resin composition (c' 10) which was a mixture of PEN and syndiotactic polystyrene (B) in a weight ratio of 60:40 and that the stretching ratios and the discharge amounts of the respective layers were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 27>
In example 24, a biaxially oriented laminated film having a young's modulus of 8GPa in the machine direction, a young's modulus of 6.5GPa in the transverse direction, a thickness of 0.333 μm for each layer of the film layer B, a total thickness of 3.0 μm for the film layer B, a thickness of 0.375 μm for each layer of the film layer a, and a total thickness of 3.0 μm for the film layer a was obtained by repeating the same operation as in example 24 except that the stretching ratio, the discharge amount of each layer, and the number of layers were changed so that the film layer B was 9 layers, the film layer a was 8 layers, and the film layer B was disposed at both ends.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 28>
In example 24, a biaxially oriented laminated film having a young's modulus of 8GPa in the machine direction, a young's modulus of 6.5GPa in the transverse direction, a thickness of 0.037 μm for each layer of the film layer B, a total thickness of 1.8 μm for the film layer B, a thickness of 0.088 μm for each layer of the film layer a, and a total thickness of 4.2 μm for the film layer a was obtained by repeating the same operation as in example 24 except that the stretching ratio, the discharge amount of each layer, and the number of layers were changed so that the film layer B was 49 layers, the film layer a was 48 layers, and the film layers B were disposed at both ends.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 29>
In example 26, a biaxially oriented laminate film having a young's modulus of 8GPa in the machine direction and 8GPa in the transverse direction was obtained by repeating the same operation as in example 24 except that the stretching ratio and the discharge amount of each layer were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 30>
In example 26, a biaxially oriented laminate film having a young's modulus in the machine direction of 5.5GPa and a young's modulus in the transverse direction of 12GPa was obtained by repeating the same operation as in example 24, except that the stretching ratio and the discharge amount of each layer were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< comparative example 10>
In example 24, the same operations as in example 24 were repeated except that the inert particles contained in the resins of the film layers a and B were changed to 0.02 wt% of silicone particles having an average particle size of 1.2 μm and 0.4 wt% of silica particles having an average particle size of 0.1 μm, the thermoplastic resin composition (c '8) was changed to a thermoplastic resin composition (c' 11) composed of only syndiotactic polystyrene (B), and the stretching ratio and the discharge amount of each layer were changed, to obtain a biaxially oriented laminated film having a young's modulus of 8GPa in the machine direction, a young's modulus of 6.5GPa in the transverse direction, a thickness of each layer of the film layer B of 0.072 μm, a total thickness of the film layer B of 1.8 μm, a thickness of each layer of the film layer a of 0.175 μm, and a total thickness of the film layer a of 4.2 μm.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 6 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
TABLE 6
< example 31>
Polyethylene-2, 6-naphthalate resin (PEN) having an intrinsic viscosity (o-chlorophenol, 35 ℃) of 0.62 and a melting point (Tm) of 269 ℃ to which 0.02% by weight of silicone particles having an average particle diameter of 0.5 μm and 0.3% by weight of silica particles having an average particle diameter of 0.1 μm were added was prepared as the resin of the film layer B. Furthermore, syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) to which 0.02% by weight of silicone particles having an average particle diameter of 0.5 μm and 0.3% by weight of silica particles having an average particle diameter of 0.1 μm were added was prepared as the resin of the film layer C. The polymer of the film layer B was dried at 160 ℃ for 3 hours, the polymer of the film layer C was dried at 100 ℃ for 3 hours, and then supplied to an extruder to be melted, the polymer of the film layer B was branched into 25 layers, and the polymer of the film layer C was branched into 24 layers, and then merged using a multi-layer feed block device in which the layers B and C were alternately stacked, and introduced into a die while keeping the stacked state, and cast onto a casting drum to prepare a stacked unstretched sheet in which the total number of layers of the layers B and C were alternately stacked was 49. At this time, the extrusion amount ratio of the polymers of the B layer and the C layer was adjusted to 9:1, and the layers were laminated so that both surface layers were B layers. Further, the laminated unstretched sheet extruded from the die was rapidly cooled and solidified on a casting drum having a surface smoothness of 0.3S and a surface temperature maintained at 60 ℃ to form an unstretched film.
A biaxially oriented laminate film having a young's modulus of 8GPa in the machine direction and 6.5GPa in the transverse direction was obtained by repeating the same operation as in comparative example 1 except that the stretching ratio of the laminate unstretched film was changed. The thicknesses of the film layers B and C in the laminated film were adjusted by the discharge amount, and the film layer B had a total thickness of 5.4 μm at 0.216 μm, and the film layer C had a total thickness of 0.6 μm at 0.025 μm at each layer.
In addition, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Further, the proportion (% by weight) of the polyolefin is 1.36g/cm from the specific gravity of the PEN film3Syndiotactic polystyrene film specific gravity 1.04g/cm3And (4) obtaining.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 32>
In example 31, a biaxially oriented laminated film having a young's modulus in the machine direction of 8GPa, a young's modulus in the transverse direction of 6.5GPa, a thickness of each layer of the film layer B of 0.168 μm, a total thickness of the film layer B of 4.2 μm, a thickness of each layer of the film layer C of 0.075 μm, and a total thickness of the film layer B of 1.8 μm was obtained by repeating the same operations as in example 31 except that the inert particles contained in the resins of the film layers B and C were changed to 0.1 wt% of silica particles having an average particle diameter of 0.1 μm, and the stretching ratios and the discharge amounts of the respective layers were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 33>
In example 31, a biaxially oriented laminated film having a young's modulus in the machine direction of 8GPa, a young's modulus in the transverse direction of 6.5GPa, a thickness of each of the film layers B of 0.120 μm, a total thickness of the film layers B of 3.0 μm, a thickness of each of the film layers C of 0.125 μm, and a total thickness of the film layers B of 3.0 μm was obtained by repeating the same operations as in example 31 except that the stretching ratio and the discharge amount of each layer were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 34>
In example 31, a biaxially oriented laminated film having a young's modulus of 8GPa in the machine direction, a young's modulus of 6.5GPa in the transverse direction, a thickness of 0.533 μm for each layer of the film layer B, a total thickness of 4.8 μm for the film layer B, a thickness of 0.15 μm for each layer of the film layer C, and a total thickness of 1.2 μm for the film layer C was obtained by repeating the same operation as in example 31 except that the stretching ratio, the discharge amount of each layer, and the number of layers were changed so that the film layer B was 9 layers and the film layer C was 8 layers, and the film layers B were disposed at both ends.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 35>
In example 31, a biaxially oriented laminated film having a young's modulus in the machine direction of 8GPa, a young's modulus in the transverse direction of 6.5GPa, a thickness of each layer of film layer B of 0.073 μm, a total thickness of film layer B of 3.6 μm, a thickness of each layer of film layer C of 0.050 μm, and a total thickness of film layer C of 2.4 μm was obtained by repeating the same operation as in example 31 except that the stretching ratio, the discharge amount of each layer, and the number of layers were changed so that the film layer B was 49 layers, the film layer C was 48 layers, and the film layers B were disposed at both ends.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 36>
A biaxially oriented laminate film having a young's modulus of 8GPa in the machine direction and 8GPa in the transverse direction was obtained by repeating the same operation as in example 32 except that the stretching ratio and the discharge amount of each layer were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< example 37>
A biaxially oriented laminate film having a young's modulus in the machine direction of 5.5GPa and a young's modulus in the transverse direction of 12GPa was obtained by repeating the same operation as in example 32, except that the stretching ratio and the discharge amount of each layer were changed.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
< comparative example 11>
In example 31, a biaxially oriented laminated film having a young's modulus of 8GPa in the machine direction, a young's modulus of 6.5GPa in the transverse direction, a thickness of 0.072 μm for each layer of the film layer B, a total thickness of 1.8 μm for the film layer B, a thickness of 0.175 μm for each layer of the film layer C, and a total thickness of 4.2 μm for the film layer C was obtained by repeating the same operations as in example 31 except that the inert particles contained in the resin of the film layer B were changed to 0.02% by weight of the siloxane particles having an average particle size of 1.2 μm and 0.4% by weight of the silica particles having an average particle size of 0.1 μm.
Further, the same operation as in comparative example 1 was repeated to obtain a magnetic recording medium.
Table 7 shows the properties of the obtained biaxially oriented laminated film and magnetic tape.
TABLE 7
| Unit of | Example 31 | Example 32 | Example 33 | Example 34 | Example 35 | Example 36 | Example 37 | Comparative example 9 | Comparative example 11 | |
| Layer structure | － | Multiple layers | Multiple layers | Multiple layers | Multiple layers | Multiple layers | Multiple layers | Multiple layers | Single layer | Multiple layers |
| Film thickness | μm | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 |
| Each layer of layer B | μm | 0.216 | 0.168 | 0.120 | 0.533 | 0.073 | 0.168 | 0.168 | － | 0.072 |
| Layer B in total | μm | 5.4 | 4.2 | 3.0 | 4.8 | 3.6 | 4.2 | 4.2 | 6.0 | 1.8 |
| Each layer of C | μm | 0.025 | 0.075 | 0.125 | 0.150 | 0.050 | 0.075 | 0.075 | － | 0.175 |
| Layer C in total | μm | 0.6 | 1.8 | 3.0 | 1.2 | 2.4 | 1.8 | 1.8 | － | 4.2 |
| Number of layers | － | |||||||||
| Layer B | － | 25 | 25 | 25 | 9 | 49 | 25 | 25 | － | 25 |
| Layer C | － | 24 | 24 | 24 | 8 | 48 | 24 | 24 | － | 24 |
| All layers of | － | 49 | 49 | 49 | 17 | 97 | 49 | 49 | － | 49 |
| Proportion of polyolefin | By weight% | 8 | 25 | 43 | 16 | 34 | 25 | 25 | 0 | 64 |
| Young's modulus | ||||||||||
| Direction of film formation | GPa | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 5.5 | 8.0 | 8.0 |
| Width direction of the sheet | GPa | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 8.0 | 12 | 6.5 | 6.5 |
| Coefficient of thermal expansion | ppm/℃ | 7 | 7 | 8 | 7 | 7 | -2 | -8 | 7 | 8 |
| Coefficient of humidity expansion | ppm/％RH | 11 | 9 | 6 | 10 | 7 | 6 | 4 | 12 | 4 |
| Track skew | ppm | 862 | 705 | 548 | 783 | 626 | 367 | 100 | 940 | 391 |
| Film forming property | － | ◎ | ◎ | ○ | ◎ | ◎ | ○ | ◎ | ◎ | × |
< example 38>
Polyethylene-2, 6-naphthalate resin (PEN) was obtained in the same manner as in comparative example 1 except that the inert particles were changed to 0.1% by weight of spherical silica having an average particle diameter of 0.3. mu.m. The obtained PEN (intrinsic viscosity 0.62) was dried at 180 ℃ for 6 hours and then fed to an extruder heated to 300 ℃ while syndiotactic polystyrene (grade: 130ZC, manufactured by gloss petrochemical Co., Ltd.) as the polyolefin (B) was fed to another extruder heated to 280 ℃, and the PEN layer B and the syndiotactic polystyrene layer C were alternately laminated in a molten state in a mold into 49 layers represented by B/C/B … B/C/B, respectively, and molded into a sheet shape while maintaining the laminated structure. The sheet was cooled and solidified by a cooling drum having a surface temperature of 60 ℃, and the thus-obtained unstretched film was introduced into a roll stack heated to 140 ℃, stretched 3.6 times in the longitudinal direction (machine direction), and then cooled by the roll stack at 60 ℃.
Subsequently, the longitudinally stretched film was introduced into a tenter while holding both ends thereof with clips, and stretched at 4.0 times in the direction (transverse direction) perpendicular to the longitudinal direction in an atmosphere heated to 150 ℃ at the maximum transverse stretching temperature. Then, the sheet was subjected to heat-setting at 220 ℃ for 5 seconds in a tenter, further subjected to 1% heat relaxation at 200 ℃, then uniformly cooled slowly, and cooled to room temperature to obtain a biaxially oriented laminate film having a thickness of 5 μm. The average thickness of each layer was 0.1 μm.
The proportion (% by weight) of the polyolefin is determined from the specific gravity of the PEN film of 1.36g/cm3Syndiotactic polystyrene film specific gravity 1.04g/cm3And (4) obtaining.
Table 8 shows the properties of the aromatic polyester (a) and the polyolefin (b) used and the properties of the obtained biaxially oriented laminate film.
< example 39>
A biaxially oriented laminate film having a thickness of 5 μm was obtained by repeating the same operation as in example 38 except that the laminate structure was changed from 49 layers to a 5-layer structure represented by B/C/B. The average thickness of each layer was 1 μm.
Table 8 shows the properties of the obtained biaxially oriented laminate film.
< example 40>
A biaxially oriented laminate film having a thickness of 5 μm was obtained by repeating the same operations as in example 38, except that the laminate structure of the PEN layer B and the syndiotactic polystyrene layer C was changed from 49 layers to 2 layers represented by B/C. Average thickness of each layer, layer B was 3 μm and layer C was 2 μm.
Table 8 shows the properties of the obtained biaxially oriented laminate film. The film of the present example satisfied heat resistance and dielectric breakdown voltage, but curled and interlayer peeling was observed.
< comparative example 12>
A biaxially oriented laminate film having a thickness of 5 μm was obtained by repeating the same operation as in example 38 except that the laminate structure was changed to1 layer of PEN layer B and the syndiotactic polystyrene layer C was not laminated.
Table 8 shows the properties of the obtained biaxially oriented laminate film.
< comparative example 13>
The polyethylene 2, 6-naphthalate resin of comparative example 12 was changed to polyethylene terephthalate resin, and after drying at 170 ℃ for 3 hours, it was supplied to an extruder heated to 280 ℃ and molded into a sheet from a die at 290 ℃. The sheet was cooled and solidified by a cooling drum having a surface temperature of 20 ℃, and the thus-obtained unstretched film was introduced into a roll set heated to 90 ℃, stretched 3.6 times in the longitudinal direction (machine direction), and then cooled by a roll set at 20 ℃.
Subsequently, the longitudinally stretched film was introduced into a tenter while holding both ends thereof with clips, and stretched at 4.0 times in the direction (transverse direction) perpendicular to the longitudinal direction in an atmosphere heated to 120 ℃ at the maximum transverse stretching temperature. Then, the sheet was subjected to heat-setting at 220 ℃ for 5 seconds in a tenter, further subjected to 1% thermal relaxation at 200 ℃, then uniformly cooled slowly, and cooled to room temperature to obtain a biaxially oriented film having a thickness of 5 μm.
Table 8 shows the properties of the aromatic polyester (a) used and the properties of the obtained biaxially oriented film.
TABLE 8
| Unit of | Example 38 | Example 39 | Example 40 | Comparative example 12 | Comparative example 13 | |
| Film thickness | μm | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| Proportion of polyolefin | Wt％ | 43 | 34 | 34 | － | － |
| Aromatic polyester (a) type melting Point (Tma) | 。℃ | PEN270 | PEN270 | PEN270 | PEN270 | PET260 |
| Polyolefin (b) melting Point (Tmb) dielectric constant dielectric loss | ℃ | 2702.60.0002 | 2702.60.0002 | 2702.60.0002 | ——— | ——— |
| Coefficient of thermal expansion | ppm/℃ | 7 | 7 | 7 | 7 | 7 |
| Coefficient of humidity expansion | ppm/％RH | 6 | 7 | 7 | 12 | 12 |
| Breakdown voltage of insulation | V/μm | 500 | 480 | 460 | 400 | 450 |
| Heat resistance | ℃ | 120 | 120 | 120 | 120 | 95 |
| Film curling property | ○ | ○ | × | ○ | ○ |
Claims (23)
1. A biaxially oriented film which is a single-layer or laminated biaxially oriented film formed of an aromatic polyester (a) and a polyolefin (b) having a melting point of 230-280 ℃, characterized in that:
the aromatic polyester (a) is polyethylene terephthalate or polyethylene 2, 6-naphthalate;
the polyolefin (b) is a syndiotactic styrene polymer, and accounts for 2-60 wt% of the total weight of the film;
the film thickness is in the range of 1-10 μm.
2. The biaxially oriented film according to claim 1, which is a single layer film formed of a thermoplastic resin composition (c) of an aromatic polyester (a) and a polyolefin (b).
3. The biaxially oriented film according to claim 1, which is a laminate film comprising at least 1 layer of a film layer A comprising a thermoplastic resin composition (c) of an aromatic polyester (a) and a polyolefin (B), and at least one surface of the film layer A being laminated with a film layer B comprising an aromatic polyester (a).
4. The biaxially oriented film according to claim 3, wherein the film layer A is formed of a thermoplastic resin composition (c') comprising 5 to 95% by weight of the aromatic polyester (a) and 5 to 95% by weight of the polyolefin (b), and the thickness of the film layer A is in the range of 5 to 95% with respect to the thickness of the laminate film.
5. The biaxially oriented film according to claim 1, which is a laminate film, at least 1 layer of which is a film layer C comprising a polyolefin (B), and at least one side of which is laminated a film layer B comprising an aromatic polyester (a).
6. The biaxially oriented film of claim 1, wherein the aromatic polyester (a) is polyethylene 2, 6-naphthalate.
7. The biaxially oriented film of claim 1, wherein polyolefin (b) has at least any 1 characteristic of a dielectric constant of less than 3.0 and a dielectric loss of less than 0.001.
8. The biaxially oriented film according to claim 2 or 3, wherein the polyolefin (b) in the film layer formed of the thermoplastic resin composition (c) is dispersed in islands, and the average length in the MD direction thereof is 20 μm or less.
9. The biaxially oriented film of claim 8, wherein the thermoplastic resin composition (c) further comprises 0.1 to 10% by weight, based on the weight of the thermoplastic resin composition, of a thermoplastic amorphous resin (d) having a solubility parameter between the aromatic polyester (a) and the polyolefin (b).
10. The biaxially oriented film according to claim 9, wherein the thermoplastic amorphous resin (d) is an acrylic copolymerized polyolefin or a vinyl oxazoline copolymerized polyolefin-based resin.
11. The biaxially oriented film according to claim 3, wherein the film comprises 3 layers each comprising a film layer A and a film layer B laminated on both sides thereof.
12. A biaxially oriented film according to claim 3, which film laminates a film layer a and a film layer B having a total number of layers of at least 4.
13. A biaxially oriented film according to claim 5, which comprises 3 layers each comprising a film layer B laminated on both sides of a film layer C.
14. The biaxially oriented film of claim 5, which film laminates film layer C and film layer B having a total number of layers of at least 4.
15. The biaxially oriented film of claim 1, wherein the moisture expansion coefficient in the width direction of the film is 0.1 x 10-6～13×10-6Range of%/RH%.
16. The biaxially oriented film of claim 1, wherein the film has a temperature expansion coefficient in the width direction of-5 x 10-6～15×10-6Range of%/° c.
17. The biaxially oriented film according to claim 1, wherein the Young's modulus in both the film formation direction and the width direction of the film is 5GPa or more, and the total of both is at most 22 GPa.
18. A biaxially oriented film according to any one of claims 1 or 15 to 17, which is used as a base film for a magnetic recording medium.
19. A magnetic recording medium comprising the biaxially oriented film according to claim 1 or any one of claims 15 to 17 and a magnetic layer provided on one side thereof.
20. The biaxially oriented film according to claim 1, wherein the dielectric breakdown voltage is more than 400V/μm, and the heat resistance temperature is 110 ℃ or more.
21. The biaxially oriented film according to any one of claim 1, 15 or 20, which is used as a base film of a film capacitor.
22. A film capacitor comprising the biaxially oriented film according to claim 1, 15 or 20 and a layer D containing an oxygen atom-containing compound provided on at least one surface of the biaxially oriented film, wherein the thickness of the layer D is 30% or less of the total thickness of the film, the ratio of oxygen atoms to carbon atoms on the surface of the layer D as measured by X-ray photoelectron spectroscopy is 10% or more,
23. a film capacitor comprising the biaxially oriented film according to claim 1, 15 or 20 and a metal layer provided on at least one side thereof.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004021049A JP4220910B2 (en) | 2004-01-29 | 2004-01-29 | Biaxially stretched laminated polyester film for capacitors and film capacitors comprising the same |
| JP021045/2004 | 2004-01-29 | ||
| JP021049/2004 | 2004-01-29 | ||
| JP146247/2004 | 2004-05-17 | ||
| JP146245/2004 | 2004-05-17 | ||
| JP146244/2004 | 2004-05-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1914275A CN1914275A (en) | 2007-02-14 |
| CN100473691C true CN100473691C (en) | 2009-04-01 |
Family
ID=34904804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800037132A Active CN100473691C (en) | 2004-01-29 | 2005-01-28 | Biaxially oriented film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4220910B2 (en) |
| CN (1) | CN100473691C (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2108673A1 (en) * | 2008-04-11 | 2009-10-14 | DuPont Teijin Films U.S. Limited Partnership | Plastic film having a high breakdown voltage |
| JP5193705B2 (en) * | 2008-07-02 | 2013-05-08 | 帝人株式会社 | Biaxially oriented laminated film |
| KR20120096952A (en) * | 2009-05-15 | 2012-08-31 | 도레이 카부시키가이샤 | Blaxially oriented polyester film and magnetic recording medium |
| JP2012097163A (en) * | 2010-10-29 | 2012-05-24 | Dainippon Printing Co Ltd | Polyester resin composition |
| CN103648776B (en) * | 2011-06-30 | 2016-05-04 | 杜邦帝人薄膜美国有限公司 | The multilayer polester film of dimensionally stable |
| CN103630472B (en) * | 2013-11-28 | 2015-12-30 | 南京大学 | A kind of method of quantitative description carbon nano tube suspension gathering and settling behavior |
| CN105415843A (en) * | 2015-12-24 | 2016-03-23 | 上海联净复合材料技术有限公司 | Iron-covering film and film-covered iron therewith |
| JP6765816B2 (en) * | 2016-01-21 | 2020-10-07 | 宇部エクシモ株式会社 | Flexible metal laminate and manufacturing method of flexible metal laminate |
| CN106166882B (en) * | 2016-04-25 | 2017-12-19 | 中国科学院化学研究所 | A kind of biaxial tension thin polymer film and preparation method and application |
| KR102386485B1 (en) * | 2016-06-24 | 2022-04-14 | 도레이 카부시키가이샤 | Biaxially Oriented Thermoplastic Resin Film |
| JP6691512B2 (en) | 2017-06-23 | 2020-04-28 | 富士フイルム株式会社 | Magnetic recording medium |
| WO2019065199A1 (en) | 2017-09-29 | 2019-04-04 | 富士フイルム株式会社 | Magnetic tape and magnetic recording/reproducing apparatus |
| JP6884220B2 (en) | 2017-09-29 | 2021-06-09 | 富士フイルム株式会社 | Magnetic tape and magnetic recording / playback device |
| US11361792B2 (en) | 2018-03-23 | 2022-06-14 | Fujifilm Corporation | Magnetic tape having characterized magnetic layer and magnetic recording and reproducing device |
| US11514943B2 (en) | 2018-03-23 | 2022-11-29 | Fujifilm Corporation | Magnetic tape and magnetic tape device |
| US11361793B2 (en) | 2018-03-23 | 2022-06-14 | Fujifilm Corporation | Magnetic tape having characterized magnetic layer and magnetic recording and reproducing device |
| US11514944B2 (en) | 2018-03-23 | 2022-11-29 | Fujifilm Corporation | Magnetic tape and magnetic tape device |
| JP6830931B2 (en) | 2018-07-27 | 2021-02-17 | 富士フイルム株式会社 | Magnetic tapes, magnetic tape cartridges and magnetic tape devices |
| JP6784738B2 (en) | 2018-10-22 | 2020-11-11 | 富士フイルム株式会社 | Magnetic tapes, magnetic tape cartridges and magnetic tape devices |
| JP7042737B2 (en) | 2018-12-28 | 2022-03-28 | 富士フイルム株式会社 | Magnetic tape, magnetic tape cartridge and magnetic tape device |
| JP6830945B2 (en) | 2018-12-28 | 2021-02-17 | 富士フイルム株式会社 | Magnetic tapes, magnetic tape cartridges and magnetic tape devices |
| JP7003073B2 (en) | 2019-01-31 | 2022-01-20 | 富士フイルム株式会社 | Magnetic tapes, magnetic tape cartridges and magnetic tape devices |
| JP6778804B1 (en) | 2019-09-17 | 2020-11-04 | 富士フイルム株式会社 | Magnetic recording medium and magnetic recording / playback device |
| CN114290782A (en) * | 2022-01-13 | 2022-04-08 | 广东德冠包装材料有限公司 | Biaxially oriented polypropylene film for epoxy resin curing and preparation method thereof |
-
2004
- 2004-01-29 JP JP2004021049A patent/JP4220910B2/en not_active Expired - Fee Related
-
2005
- 2005-01-28 CN CNB2005800037132A patent/CN100473691C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005212248A (en) | 2005-08-11 |
| JP4220910B2 (en) | 2009-02-04 |
| CN1914275A (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100473691C (en) | Biaxially oriented film | |
| KR101153758B1 (en) | Biaxially oriented film | |
| JP4723296B2 (en) | Biaxially oriented film for film capacitor and film capacitor comprising the same | |
| JP6153927B2 (en) | Dimensionally stable multilayer polyester film | |
| JP4805608B2 (en) | Biaxially oriented laminated film and magnetic recording medium | |
| JP4907903B2 (en) | Biaxially oriented film, biaxially oriented laminated film and magnetic recording medium | |
| JP5763456B2 (en) | Biaxially oriented film | |
| JP4624850B2 (en) | Biaxially oriented laminated film and magnetic recording medium | |
| JP4220933B2 (en) | Biaxially oriented laminated film and magnetic recording medium | |
| KR101011290B1 (en) | Biaxially oriented polyester film | |
| JP4076758B2 (en) | Conductive film | |
| JP2011243240A (en) | Biaxially-oriented laminated film | |
| JP5226597B2 (en) | Biaxially oriented laminated film | |
| KR102333059B1 (en) | Release film for ceramic green sheet manufacturing | |
| JP5542253B2 (en) | Laminated polyester film | |
| JP2012229367A (en) | Biaxially oriented film | |
| JPH04345634A (en) | Double-coated polyester film and its production | |
| JP5193705B2 (en) | Biaxially oriented laminated film | |
| JP2010001390A (en) | Biaxially oriented film | |
| JP2004202701A (en) | Polyester film | |
| JP2003251777A (en) | Laminated polyester film | |
| JP2010030116A (en) | Biaxially oriented laminated film and magnetic recording medium using the same | |
| JP2004188621A (en) | Laminated polyester film | |
| JP2009203399A (en) | Polyester film for in-mold transfer foil | |
| JPH0848008A (en) | Laminated film and condenser using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |