JPH0224823A - Biaxially oriented polyester film for magnetic recording medium - Google Patents
Biaxially oriented polyester film for magnetic recording mediumInfo
- Publication number
- JPH0224823A JPH0224823A JP63175452A JP17545288A JPH0224823A JP H0224823 A JPH0224823 A JP H0224823A JP 63175452 A JP63175452 A JP 63175452A JP 17545288 A JP17545288 A JP 17545288A JP H0224823 A JPH0224823 A JP H0224823A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- polyester
- film
- precipitated
- magnetic recording
- 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.)
- Granted
Links
- 229920006267 polyester film Polymers 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims abstract description 143
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000010954 inorganic particle Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 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 abstract 1
- 238000006748 scratching Methods 0.000 abstract 1
- 230000002393 scratching effect Effects 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 238000005299 abrasion Methods 0.000 description 16
- 239000000654 additive Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 13
- -1 polyethylene Polymers 0.000 description 11
- 238000005809 transesterification reaction Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229940043430 calcium compound Drugs 0.000 description 4
- 150000001674 calcium compounds Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 150000002642 lithium compounds Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003973 paint 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
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 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
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241001422033 Thestylus Species 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Magnetic Record Carriers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は磁気記録媒体としたとき、優れた走行性、電磁
変換特性及び耐摩耗性を与えるポリエステルフィルムに
関する。更に詳しくはテープ走行時の擦シ傷や摩耗粉の
発生が極めて少なく、ドロップアウトの発生が抑制され
た高密度磁気記録用に適したベースフィルムに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyester film that provides excellent running properties, electromagnetic conversion characteristics, and abrasion resistance when used as a magnetic recording medium. More specifically, the present invention relates to a base film suitable for high-density magnetic recording, which generates extremely few scratches and abrasion particles during tape running, and suppresses the occurrence of dropouts.
〔従来の技術および解決すべき問題点〕ポリエステルフ
ィルムは物理的、化学的特性に優れ産業用基材として広
く用いられている。[Prior Art and Problems to be Solved] Polyester films have excellent physical and chemical properties and are widely used as industrial base materials.
就中、二軸配向ポリエチレンテレ7ターレートフイルム
は特に機械的強度、寸法安定性、平面性等に優れること
から、磁気記録媒体のベースフィルムとして今や必要不
可欠なものとなっている。とζろで、近年磁気記録媒体
の改良が急速な勢いで行なわれておシ、これに伴ないベ
ースフィルムへの要求も一段と厳しいものとなって来て
いる。例えばビデオテープのように高密度の記録を要す
るものでは、磁性層の薄膜化が行なわれるが、この場合
ベースフィルム自体の凹凸が磁性層表面に反映され、そ
の程度が大きい場合には電磁変換特性の低下やドロップ
アウトの多発を招くようになる。従ってベースフィルム
の表面はより平坦であることが望まれるが、一方良く知
られているようにフィルム表面が平坦になるとフィルム
の走行性が悪化するのみならずフィルムと基材、例えば
ガイドビンとの間の摩擦、摩耗が大きくなシ、フィルム
にスリキズか発生したり摩耗粉が生成するようになる。In particular, biaxially oriented polyethylene tele-7 tarlate film is now indispensable as a base film for magnetic recording media because it is particularly excellent in mechanical strength, dimensional stability, flatness, etc. In recent years, improvements in magnetic recording media have been made at a rapid pace, and as a result, demands on base films have become even more stringent. For example, in products that require high-density recording such as videotapes, the magnetic layer is made thinner, but in this case, the unevenness of the base film itself is reflected on the surface of the magnetic layer, and if the degree of unevenness is large, the electromagnetic conversion characteristics This leads to a decrease in performance and frequent dropouts. Therefore, it is desirable that the surface of the base film be as flat as possible, but as is well known, when the film surface becomes flat, it not only deteriorates the runnability of the film, but also causes problems between the film and the base material, such as guide bins. If the friction and abrasion between the parts is large, scratches may occur on the film and abrasion powder may be generated.
即ち、ポリエステルフィルムの耐摩耗性が不充分である
と、磁性層製造工程あるいは製品となった後、フィルム
と各種ロール又はガイドビンとの間に摩耗粉が生成し、
やはシミ磁変換特性やドロップアウトの点において劣る
ようになる。That is, if the abrasion resistance of the polyester film is insufficient, abrasion powder will be generated between the film and various rolls or guide bins during the magnetic layer manufacturing process or after it is made into a product.
Otherwise, it becomes inferior in terms of stain magnetic conversion characteristics and dropout.
また、フィルムの耐擦傷性が不充分であると磁性層塗布
前後においてフィルムにキズか入り易く、それが磁性層
表面に反映されて電磁気的な特性が劣るようKなる。更
に削シ取られた白粉状の物質の存在によってもしばしば
電磁気特性が悪化してしまう。Furthermore, if the scratch resistance of the film is insufficient, the film is likely to be scratched before and after coating the magnetic layer, and this will be reflected on the surface of the magnetic layer, resulting in poor electromagnetic properties. Furthermore, the electromagnetic properties are often deteriorated by the presence of white powder-like substances that have been scraped off.
ポリエステルフィルムの走行性や耐摩耗性などの表面特
性を改良する手段として、従来フィルム中に不活性な微
粒子を存在させフィルム表面を適度に粗らす方法、具体
的にはいわゆる析出粒子法と添加粒子法とが知られてい
る。As a means of improving surface properties such as runnability and abrasion resistance of polyester films, conventional methods include the presence of inert fine particles in the film to appropriately roughen the film surface, specifically the so-called precipitated particle method and addition. The particle method is known.
析出粒子法とはポリエステル製造工程において触媒残渣
等を微細な粒子としてポリエステル中に析出させるもの
であシ、操作が簡単でポリマーを安価に製造することが
でき、しかも製膜時のフィルターの寿命が長いという長
所を有する。更に一般にポリエステルとの親和性に優れ
、フィルムからの粒子の脱離が少なく、耐摩耗性におい
ても比較的優れている。しかしながら、該粒子の主成分
は有機成分であるため耐擦傷性においては劣っている。The precipitated particle method is a method in which catalyst residues are precipitated into polyester as fine particles during the polyester manufacturing process.It is easy to operate and can produce polymers at low cost, and it also shortens the life of the filter during film formation. It has the advantage of being long. Furthermore, it generally has excellent affinity with polyester, has little detachment of particles from the film, and has relatively excellent abrasion resistance. However, since the main component of the particles is an organic component, they are inferior in scratch resistance.
一方、析出粒子法と対比される添加粒子法とは、炭酸カ
ルシウム、カオリン、シリカ等をそのマ′!あるいは微
粒子化したのち、ポリエステル製造時あるいは成型時に
添加する方法であるが、一般にポリエステルとの親和性
に欠は耐摩耗性が不充分な上、しばしば不要な大粒子が
混入し、フィルム表面に粗大な突起を与えてしまいフィ
ルム品質を損ねてしまうO
このように各々単独では達成し得ない効果を得るべく両
者を組み合せて使用する試みもまた為されている。例え
ば、特公昭!S−−〇’ltt号公報あるいは特公昭S
S−90930号公報には析出粒子法と添加粒子法とを
併用することが記載されているが、これらの方法を採用
したとしても走行性、耐摩耗性及び耐擦傷性を高度に満
足させることはこれまで不可能であった。On the other hand, the additive particle method, which is contrasted with the precipitated particle method, uses calcium carbonate, kaolin, silica, etc. Another method is to make it into fine particles and then add it during polyester production or molding. However, it generally lacks compatibility with polyester, has insufficient abrasion resistance, and often contains unnecessary large particles, creating a rough surface on the film surface. Thus, attempts have also been made to use the two in combination in order to obtain effects that cannot be achieved by each alone. For example, Tokko Akira! S--〇'ltt publication or special public show S
Publication S-90930 describes the combined use of the precipitated particle method and the additive particle method, but even if these methods are adopted, running properties, abrasion resistance, and scratch resistance cannot be highly satisfied. has not been possible until now.
本発明者は上記実情に鑑みて、磁気記録媒体用のポリエ
ステルフィルムについて鋭意検討を行なった結果、析出
粒子法によって得られたある特定の粒子と、ある特定の
粒径、硬度を有する添加粒子とを組み合せて用いるなら
ば、上記の問題点が工業的容易に解決し得ることを知見
し本発明に至った。In view of the above-mentioned circumstances, the present inventor has conducted intensive studies on polyester films for magnetic recording media, and has found that certain particles obtained by the precipitated particle method and additive particles having a certain particle size and hardness. The inventors have found that the above problems can be easily solved industrially by using a combination of the following, and have thus arrived at the present invention.
即ち、本発明の要旨はポリエステル製造工程で析出させ
た平均粒径0. / −5μmの不活性物質粒子0.0
1−/重量%と、平均粒径1μm未満で且つモース硬度
6以上のポリエステルに対し不活性な無機粒子0.01
−3重量%とを含有することを特徴とする磁気記録媒体
用二軸配向ポリエステルフィルムに存スル。That is, the gist of the present invention is that the average particle size precipitated in the polyester manufacturing process is 0. / -5μm inert particles 0.0
1-/wt%, inorganic particles having an average particle diameter of less than 1 μm and inert to polyester having a Mohs hardness of 6 or more.
-3% by weight of a biaxially oriented polyester film for magnetic recording media.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明でいうポリエステルとは、テレフタル酸% 2.
6−fフタレンジカルボン酸の如*芳香族ジカルボン酸
又はそのエステルと、エチレングリコールを主たる出発
原料として得られるポリエステルを指すが他の第三成分
を含有していてもかまわない。この場合、ジカルボン酸
成分としては例えば、イソフタル酸、フタル酸、2.6
−す7タレンジカルボン酸、テレフタル酸、アジピン酸
、セバシン酸、及びオキシカルボン酸成分、例えばp−
オキシエトキシ安息香酸などの一種又は二種以上を用い
ることができる。Polyester as used in the present invention refers to terephthalic acid%2.
It refers to a polyester obtained using an aromatic dicarboxylic acid such as 6-f phthalene dicarboxylic acid or its ester and ethylene glycol as the main starting materials, but it may contain other third components. In this case, the dicarboxylic acid component includes, for example, isophthalic acid, phthalic acid, 2.6
-S7tale dicarboxylic acid, terephthalic acid, adipic acid, sebacic acid, and oxycarboxylic acid components, such as p-
One or more types of oxyethoxybenzoic acid can be used.
グリコール成分としては、ジエチレングリコール、プロ
ピレングリコール、ブタンジオール、へ弘−シクロヘキ
サンジメタツール、ネオペンチルグリコールなどの一種
又は二種以上を用いることができる。いずれKしても、
本発明のポリエステルとは繰シ返し構造単位のざ04以
上がエチレンテレフタレート単位又ハエチレン〜コ、6
−ナフタレン単位を有するポリエステルを指す。As the glycol component, one or more of diethylene glycol, propylene glycol, butanediol, Hehiro-cyclohexane dimetatool, neopentyl glycol, etc. can be used. Even if K eventually,
The polyester of the present invention means that 04 or more of the repeating structural units are ethylene terephthalate units or ethylene to 6
- Refers to polyesters with naphthalene units.
また2本発明のポリエステルフィルムとは、かかるポリ
エステルを出発原料とする二軸忙配向されたポリエステ
ルフィルムを指すが、その製造法としては公知の方法を
用いることができる。例えば通常−70〜J、10℃で
シート状に溶融押出しした後、#0−10℃で冷却固化
し、無定形シートとした後、縦、横方向に逐次二軸延伸
あるbは同時に延伸し、160〜コSO℃で熱処理する
等の方法(例えば特公昭JO−ztst号公報記載の方
法ンを利用することができる。縦及び横方向に延伸する
に際しては各々−段で延伸してもよいし、また必要に応
じ多段で延伸したシ多段延伸の間に配向緩和のための熱
処理区間を設けたシすることもできる。Further, the polyester film of the present invention refers to a biaxially oriented polyester film using such a polyester as a starting material, and known methods can be used for its production. For example, it is usually melt-extruded into a sheet at -70 to 10°C, then cooled and solidified at #0 to 10°C to form an amorphous sheet, and then biaxially stretched sequentially in the longitudinal and transverse directions. , a method such as heat treatment at 160 to 100°C (for example, the method described in Japanese Patent Publication No. Sho JO-ZTST can be used. When stretching in the longitudinal and transverse directions, stretching may be carried out in stages respectively. However, if necessary, it is also possible to perform multi-stage stretching and provide a heat treatment section for orientation relaxation between multi-stage stretching.
また、二軸延伸後、次工程の熱処理工程に供する前に1
再度延伸することも可能である。この再延伸は、縦、横
いずれの方向に行なうこともできるし、また両方向に行
なってもよい。In addition, after biaxial stretching, 1
It is also possible to stretch again. This re-stretching may be performed in either the longitudinal or transverse directions, or in both directions.
本発明において反応系で析出させた不活性物質粒子とは
、例えばエステル交換触媒としてアルカリ金属またはア
ルカリ土類金属化合物を用いた系を常法によシ重合する
ことによシ反応系内に析出するものである。また、エス
テル交換反応あるいは重縮合反応時にテレフタル酸を添
加すること忙よシ析出させてもよい。これらの場合、リ
ン酸、リン酸トリメチル、リン酸トリエチル、リン酸ト
リブチル、酸性リン酸エチル、亜リン酸、亜リン酸トリ
メチル、亜リン酸トリエチル、亜リン酸トリブチル等の
リン化合物の一種以上を存在させておいてもよい。In the present invention, the inert substance particles precipitated in the reaction system are particles precipitated in the reaction system by, for example, polymerizing a system using an alkali metal or alkaline earth metal compound as a transesterification catalyst by a conventional method. It is something to do. Alternatively, terephthalic acid may be added during the transesterification reaction or polycondensation reaction to cause precipitation. In these cases, one or more phosphorus compounds such as phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, acidic ethyl phosphate, phosphorous acid, trimethyl phosphite, triethyl phosphite, and tributyl phosphite are used. It may be left to exist.
また、エステル化工程を経る場合にもこれらの方法で不
活性物質粒子を析出させることができる。例えば、エス
テル化反応終了前または後にアルカリ金属またはアルカ
リ土類金属化合物を存在させ、リン化合物の存在下ある
いは非存在下に重合反応を行なわせる。Furthermore, even when an esterification step is performed, inert material particles can be precipitated by these methods. For example, an alkali metal or alkaline earth metal compound is made to exist before or after the completion of the esterification reaction, and the polymerization reaction is carried out in the presence or absence of a phosphorus compound.
いずれにしても本発明におけるポリエステル生成反応中
に生成する微細な析出化合物にはカルシウム、リチウム
、アンチモン、リン等の元素が一種以上含まれている。In any case, the fine precipitated compounds produced during the polyester production reaction in the present invention contain one or more elements such as calcium, lithium, antimony, and phosphorus.
例えばエステル交換触媒として酢酸カルシウムを用いた
場合には重合反応中にテレフタル酸カルシウム及びポリ
エステルオリゴマーのカルシウム塩からなる下記組成と
推定されるカルシウム化合物が析出してくる。For example, when calcium acetate is used as a transesterification catalyst, a calcium compound estimated to have the following composition consisting of calcium terephthalate and a calcium salt of a polyester oligomer is precipitated during the polymerization reaction.
る化合物が析出してくるし、
n = 0または1〜3の整数
この系にリン化合物を併用した場合には式■の他に次の
ような化合物が析出してくるものと考えられる。When n = 0 or an integer of 1 to 3 and a phosphorus compound is used in combination with this system, it is thought that the following compounds will precipitate in addition to formula (1).
n=0./、コまたはJ
また、この系にリン化合物を併用した場合には、上式■
の他に下記構造式と推定される化合物が一部析出してく
るものと考えられる・n == 0または1〜Sの整数
m == 0または)
〜
n = 0または/−j−の整数
n = 0またはl
更にカルシウム化合物とリチウム化合物とを併用した場
合には上式■、■及び次式で表わされるような複雑な化
合物が析出してくるものと考えられる。n=0. /, co or J In addition, when a phosphorus compound is used together with this system, the above formula ■
In addition, it is thought that a part of a compound estimated to have the following structural formula will precipitate. ・n = = 0 or an integer from 1 to S m = = 0 or) ~ n = 0 or an integer from /-j- n = 0 or l Furthermore, when a calcium compound and a lithium compound are used together, it is thought that complex compounds represented by the above formulas (1), (2), and the following formula will precipitate.
カルシウム化合物の代シにリチウム化合物を また
、辷の系にリン化合物を併用した場合に用いた場合には
重縮合中に下記構造と推定され は上式■〜■の他に
例えば次式で表わされるような複雑な化合物が析出して
くるものと推定される。If a lithium compound is used instead of a calcium compound, and a phosphorus compound is used in combination with the base system, the following structure is assumed during polycondensation. It is estimated that complex compounds such as those described above will precipitate.
鶴
n=0または1
m = oまたはl
いずれにしても本発明においては、これら析出粒子はポ
リエステルフィルム中Vco、oi〜/、0重量%、好
ましくはO,OS〜o、r重量係官まれている必要があ
る〇
析出粒子含有量が0.0 /重量%未満ではフィルムと
しての滑シ性か不足するようになるし、一方この量がへ
〇重量%t−越えても最早滑シ性かよシ改善されること
は無く、逆に粒子同志の凝集によシ粗大突起が頻発する
ようになる。Tsuru n = 0 or 1 m = o or l In any case, in the present invention, these precipitated particles are Vco, oi ~/, 0% by weight, preferably O, OS ~ o, r weight coefficient in the polyester film. If the precipitated particle content is less than 0.0% by weight, the film will lack lubricity; on the other hand, if this amount exceeds 0.0% by weight, the film will no longer have lubricity. The problem is not improved; on the contrary, coarse protrusions frequently occur due to aggregation of particles.
また該析出粒子の平均粒径は0./−3μmでなければ
ならない。何故なら平均粒径が0. /μm未満では滑
シ性発現効果が不充分で走行性が満足されないし、また
耐摩耗性も悪化するようになる。一方、平均粒径が5μ
mを越えると析出系粒子であるにもかかわらす製膜時の
フィルターの寿命が短くなるし、また磁気記録媒体とし
たときに電磁気特性が悪化するようになる。Further, the average particle size of the precipitated particles is 0. /-3μm. This is because the average particle size is 0. If it is less than /μm, the effect of developing lubricity will be insufficient and the running properties will not be satisfied, and the wear resistance will also deteriorate. On the other hand, the average particle size is 5μ
If the particle size exceeds m, the life of the filter during film formation will be shortened even though it is a precipitated particle, and the electromagnetic properties will deteriorate when used as a magnetic recording medium.
析出粒子の平均粒径としては特に0.3〜3μmが好ま
しい。The average particle size of the precipitated particles is particularly preferably 0.3 to 3 μm.
本発明で用いることのできる析出粒子の製造法は多岐に
わたるので、その全てについて詳述することはできない
が、具体的な例として例えば次のような例を挙げること
ができる。Since there are a wide variety of methods for producing precipitated particles that can be used in the present invention, it is not possible to discuss all of them in detail, but the following examples can be cited as specific examples.
即ち、
■ エステル交換反応触媒としてリチウム化合物をポリ
エステルを構成する全酸成分に対して0./−0,!;
モルチ使用し重縮合反応を完結させた場合には平均粒径
O,S〜λμの析出粒子0.0!−0,3重量%を含む
ポリエステルを得ることができるし、
■ この場合、エステル交換反応終了後リン酸をリチウ
ム化合物に対し0.!−/、r倍モル添加して同様の操
作を行なうと平均粒径0.3〜lμ程度の析出粒子をo
、os〜0.2重量%含むポリエステルが得られる。That is, (1) a lithium compound is used as a transesterification reaction catalyst at a rate of 0.0% relative to the total acid components constituting the polyester; /-0,! ;
When the polycondensation reaction is completed using a mortar, the precipitated particles with an average particle size of O,S~λμ are 0.0! -0.3% by weight of polyester can be obtained, and (1) In this case, after the transesterification reaction, phosphoric acid is added to the lithium compound by 0.3% by weight. ! -/, If the same operation is performed with r times the molar addition, precipitated particles with an average particle size of about 0.3 to lμ are o
, os~0.2% by weight is obtained.
■ また■においてリン酸の代シにリン酸トリメチル、
リン酸トリエチルまたはリン酸トリブチルの如きトリプ
ルキルエステルを用いると析出粒子量が0.1〜O,S
重量%となる。■ Also, in ■, trimethyl phosphate is substituted for phosphoric acid.
When triple-kill esters such as triethyl phosphate or tributyl phosphate are used, the amount of precipitated particles ranges from 0.1 to O,S.
% by weight.
■ エステル交換触媒としてカルシウム化合物をo、o
r〜o、isモルチ用い重縮合反応を完結させた場合に
は平均粒径−〜3μ程度の析出粒子o、o 、t −o
、a重量%を含むポリエステルを得ることができるし、
また■ この操作においてエステル交換反応終了後テレ
フタル酸を添加すれば析出粒子の平均粒径はO,S−λ
μ程度となる。■ Calcium compounds are used as transesterification catalysts.
When the polycondensation reaction is completed using r~o,is morti, precipitated particles o, o, t-o with an average particle size of ~3μ
, a polyester containing % by weight can be obtained, and
In addition, if terephthalic acid is added after the transesterification reaction in this operation, the average particle size of the precipitated particles will be O, S-λ.
It will be about μ.
なお当然の事なから析出粒子の粒径、量は重合条件、特
に温度及び圧力にも左右されるので上に示した例はその
一部の結果である。It should be noted that, as a matter of course, the particle size and amount of the precipitated particles also depend on the polymerization conditions, particularly the temperature and pressure, and the examples shown above are only some of the results.
径、特定硬度の無機粒子とを組み合わせて用いることK
ある。Use in combination with inorganic particles of specific diameter and hardness K
be.
即ち、析出粒子を用いること釦よシ走行性が改善され、
また耐摩耗性の改良もかなシの程度まで達成し得るが、
耐擦傷性は依然として不充分なままである。本発明者は
特忙この点に意を致した結果、該析出粒子に加え平均粒
径/μm未満で且つモース硬度が6以上のポリエステル
に対し不活性な無機粒子′f!:0.01−3重量係用
いるならば析出粒子の特長を活かしたまま耐擦傷性を付
与し得ることを知見し本発明を完成した。In other words, the use of precipitated particles improves the running properties of the button.
It is also possible to improve wear resistance to a modest degree, but
Scratch resistance remains insufficient. The present inventor was very busy and took this into consideration, and found that in addition to the precipitated particles, inorganic particles 'f! :0.01-3 weight ratio, it was found that scratch resistance could be imparted while taking advantage of the characteristics of the precipitated particles, and the present invention was completed.
本発明で用いるモース硬度6以上の粒子としては、例え
ばルチル型二酸化チタン、結晶質シリカ、酸化アルミニ
ウム、チタンカーバイト、チタンブラック、シリコンカ
ーバイド等を挙げることができるが、これらの中でもモ
ース硬度が5以上でしかも工業的に入手が容易な酸化ア
ルミニウム及びシリコンカーバイド、就中酸化アルミニ
ウムが好ましく用いられる。Examples of particles with a Mohs hardness of 6 or more used in the present invention include rutile titanium dioxide, crystalline silica, aluminum oxide, titanium carbide, titanium black, silicon carbide, etc. Among these, particles with a Mohs hardness of 5 Aluminum oxide and silicon carbide, especially aluminum oxide, are preferably used because they are industrially easily available.
モース硬度の高いこれらの粒子がフィルム中に存在する
時耐摩耗性及び耐擦傷性就中、耐擦傷性が著しく改良さ
れる。しかしながら、その量がポリエステルフィルムに
対し0.01重量%未満あるいはモース硬度が6未満の
粒子の場合にはその効果は急激に低下してしまう。なお
モース硬度が6以上の粒子を3重量ts′fr:越えて
存在させたとしても最早耐擦傷性はよシ改善されること
はないし、逆に粗大突起が頻発するようになるので好ま
しくない。特に好ましい量範囲は0.1−コ重量%であ
る。When these particles with high Mohs hardness are present in the film, the abrasion resistance and scratch resistance, especially the scratch resistance, are significantly improved. However, if the amount of particles is less than 0.01% by weight based on the polyester film, or if the Mohs hardness is less than 6, the effect will sharply decrease. Incidentally, even if particles having a Mohs hardness of 6 or more are present in an amount exceeding 3 weight ts'fr:, the scratch resistance will no longer be improved, and on the contrary, coarse protrusions will occur frequently, which is not preferable. A particularly preferred amount range is 0.1-cowt%.
なお、本発明で用いるかかる粒子の平均粒径は1μm未
満でおる必要かめる。この値が1μmを越えるとしばし
ば該粒子がフィルム表面から脱離して耐摩耗性がかえっ
て悪化してしまう。Incidentally, the average particle size of such particles used in the present invention must be less than 1 μm. If this value exceeds 1 .mu.m, the particles often separate from the film surface, resulting in a worsening of the abrasion resistance.
添加粒予め平均粒径は、好ましくはO,Sμm以下、特
lCO,1μm以下が好ましく、同時に析出粒子のそれ
よりも小さいことが望ましい。The preliminarily average particle diameter of the added particles is preferably at most O.S.mu.m, particularly at most 1.mu.m, and at the same time is desirably smaller than that of the precipitated particles.
これらの要件を満たし本発明において特に好適に用いる
ことのできる粒子の一例としては、例えばいわゆる熱分
解法による酸化アルミニウムを挙げることができる。こ
の粒子は通常無水塩化アルミニウムを原料として火焔加
水分解によって製造され、その粒径は1OrrLμから
ioamμ程度である。また本発明においてはアルコキ
シドの加水分解法による酸化アルミニウム粒子も好適に
使用し得る。この場合、通常AI(OQ Hy )
またはA l (0Cd=4e )を出発原料とし、加
水分解の条件を適宜選択するととkよプ1μm以下の微
粒子を得る。勿論この場合、合成したスラリーに酸を添
加して透明なゾルを得、次いでこのゾルをゲル化した後
SOO℃以上に加熱する仁とによシ焼結体とする等の方
法を採用することもできる。また、別の方法即ちアルミ
ン酸ナトリウム溶液に酢酸メチルや酢酸エチルを加え攪
拌し、 A100H′t−得、次いでこれを加熱するこ
とKよって得られた酸化アルミニウム微粉末を用いても
よい。いずれkしても本発明においては平均粒径1μm
未満の酸化アルミニウムがlF#に好ましく用いられる
。本発明においては他の添加粒子と同様かかる酸化アル
ミニウム粒子の場合も一次粒子まで完全に分散させて使
用することが好ましいが、フィルムの表面状態に悪影響
を及ぼさない限シ、多少凝集し2次粒子として挙動して
も差しつかえない。但しこの場合も見かけ上の平均粒径
は1μm未満でなければならない。・この場合、酸化ア
ルミニウムの一部例えばJO重量係未満がS 1 e
T i * Fe * Na及びに等の酸化物で置換さ
れていてもさしつかえない。An example of particles that meet these requirements and can be particularly suitably used in the present invention is aluminum oxide produced by a so-called thermal decomposition method. These particles are usually produced by flame hydrolysis using anhydrous aluminum chloride as a raw material, and have a particle size of about 1 OrrLμ to ioamμ. Further, in the present invention, aluminum oxide particles produced by an alkoxide hydrolysis method can also be suitably used. In this case, usually AI (OQ Hy )
Alternatively, if A 1 (0Cd=4e) is used as a starting material and the hydrolysis conditions are appropriately selected, fine particles with k diameter of 1 μm or less can be obtained. Of course, in this case, a method such as adding an acid to the synthesized slurry to obtain a transparent sol, then gelling the sol, and then heating it to a temperature above SOO°C to form a sintered body may be adopted. You can also do it. Alternatively, aluminum oxide fine powder obtained by another method, namely, adding methyl acetate or ethyl acetate to a sodium aluminate solution and stirring to obtain A100H't-, and then heating this may be used. In any case, in the present invention, the average particle size is 1 μm.
Aluminum oxide less than or equal to 1 F# is preferably used for IF#. In the present invention, as with other additive particles, it is preferable to use such aluminum oxide particles by completely dispersing them to the primary particles. It is okay to behave as such. However, in this case as well, the apparent average particle size must be less than 1 μm. - In this case, a part of the aluminum oxide, for example less than JO weight, is S 1 e
There is no problem even if it is substituted with an oxide such as T i * Fe * Na or .
いずれにしても本発明においては、析出粒子と共に平均
粒径が1μm未満で且つモース硬度が6以上である無機
粒子を特定量用いるととKその特徴を有するが、該無機
粒子の粒度分布は特に制限されるものではない。しかし
ながら本発明においてはよシシャープなもの、具体的に
は粒径の小さい方から積算した場合、重量分率ys%と
25%の粒径の比が一00以下、好ましくは/、j以下
のものが好適に用いられる。In any case, in the present invention, if a specific amount of inorganic particles having an average particle size of less than 1 μm and a Mohs hardness of 6 or more are used together with the precipitated particles, the inorganic particles have the characteristics, but the particle size distribution of the inorganic particles is particularly There are no restrictions. However, in the present invention, the ratio of the particle size of weight fraction ys% to 25% is 100 or less, preferably /, j or less when integrated from the smaller particle size. are preferably used.
また、これらの粒子の形状についても特に制限はないが
、通常よシ塊状もしくは球に近いものが好ましく用いら
れる。具体的忙は、例えば特公昭33−/ダSざ3号公
報に定義しである体積形状が0.1〜π/6、好ましく
はO,コ〜π/6であるような粒子が好ましい。Further, there are no particular restrictions on the shape of these particles, but those that are generally clumpy or nearly spherical are preferably used. Specifically, it is preferable to use particles having a volume shape of 0.1 to π/6, preferably 0,0 to π/6, as defined in, for example, Japanese Patent Publication No. 33/1983/DaSza No. 3.
また、用いる粒子の比表面積においても特に制限はない
。例えば、平均粒径0.3μ、密度−f/dの真球の粒
子は、67Fl″/を程度の比表面積を有するが、!r
00 @ / f程度のポーラスなものまで好適に使
用できる。Furthermore, there is no particular restriction on the specific surface area of the particles used. For example, a perfectly spherical particle with an average particle diameter of 0.3μ and a density of −f/d has a specific surface area of about 67Fl″/, but!r
Porous materials up to about 00 @ / f can be suitably used.
なお、これらの粒子は各種の表面処理剤でその表面が変
性されていてもよい。通常エチレングリコールやポリエ
ステルとの親和性を改良する目的で用いられるこれらの
表面処理剤、例えばいわゆるシランカップリング剤やチ
タンカップリング剤は一般に粒子に対して3重量係以下
の量適用される。Note that the surfaces of these particles may be modified with various surface treatment agents. These surface treatment agents, such as so-called silane coupling agents and titanium coupling agents, which are normally used for the purpose of improving the affinity with ethylene glycol and polyester, are generally applied in an amount of 3 weight percent or less to the particles.
本発明において使用するこれら無機粒子は必要に応じ粉
砕、分級及びr過等の操作を経てポリエステルに配合さ
れる。粉砕処理には例えばロッドミル、ボールミル、振
動ロッドミル、振動ホールミル、パンミル、ローラーミ
ル、インパクトミル、攪拌摩砕ミル、流体エネルギーミ
ル等を使用することができるし、また分級処理には例え
ば半自由うず式、強制うず式、ハイドロサイクロン式、
遠心分離法等を採用することができる。These inorganic particles used in the present invention are blended into polyester after operations such as pulverization, classification, and filtration, as required. For the crushing process, for example, a rod mill, ball mill, vibrating rod mill, vibrating hall mill, pan mill, roller mill, impact mill, stirring mill, fluid energy mill, etc. can be used, and for the classification process, for example, a semi-free spiral mill can be used. , forced whirlpool type, hydrocyclone type,
A centrifugation method etc. can be adopted.
粒子をポリエステルに配合させる方法としては、通常核
粒子をエチレングリコールスラリーとしてポリエステル
展進の初期段階で反応系忙添加する方法か分散性の点か
ら好ましく採用されるが、もちろん製膜前ポリエステル
に直接ブレンドする方法を用いてもよい。The method of blending the particles into the polyester is usually to add the core particles as an ethylene glycol slurry to the reaction system at the initial stage of polyester expansion, which is preferred from the viewpoint of dispersibility, but of course it is preferable to mix the core particles with the polyester directly before film formation. A blending method may also be used.
以上述べたように本発明釦おいては性状の異なる一種類
の粒子、即ち析出粒子と添加粒子を用いるが、これらを
ポリエステルフィルムに配合するためには例えば次のよ
うな方法を採る。As described above, the button of the present invention uses one type of particles having different properties, that is, precipitated particles and additive particles, and in order to blend these into the polyester film, for example, the following method is adopted.
■ 析出粒子を含むポリエステルと添加粒子を含むポリ
エステルとをブレンドした後製膜する。■ Polyester containing precipitated particles and polyester containing additive particles are blended and then a film is formed.
■ 析出粒子と添加粒子を同時に含むポリエステルを得
、これを用いて製膜する。(2) Obtain a polyester containing both precipitated particles and additive particles, and use this to form a film.
■ 析出粒子を含むポリエステルと無機粒子とをブレン
ドした後、製膜する。■ After blending polyester containing precipitated particles and inorganic particles, a film is formed.
なお本発明においては、その趣旨を損なわない限シ本発
明で必須とする2種類の粒子以外の粒子あるいはその他
の配合剤を含んでいてもよい。例えば表面粗度や滑)性
を微調節する目的で、モース硬度6未満の添加粒子例え
ばカオリン、タルク、炭酸カルシウム、フッ化すチウム
、モルデナイト、フッ化カルシウム、酸化亜鉛、ケイ酸
カルシウム、ゼオライト、リン酸カルシウム等を併用し
ても構わない。また、耐候剤、耐光剤、帯電防止剤、潤
滑剤、遮光剤、抗酸化剤、熱安定剤等を配合した系にお
いても本発明の効果は充分に発揮される。In addition, in the present invention, particles other than the two types of particles essential to the present invention or other compounding agents may be included as long as the purpose is not impaired. For example, for the purpose of finely adjusting surface roughness and lubricity, additive particles with a Mohs hardness of less than 6 are used, such as kaolin, talc, calcium carbonate, sulfur fluoride, mordenite, calcium fluoride, zinc oxide, calcium silicate, zeolite, and calcium phosphate. etc. may be used together. Further, the effects of the present invention are fully exhibited even in systems containing weathering agents, light stabilizers, antistatic agents, lubricants, light shielding agents, antioxidants, heat stabilizers, and the like.
以上述べたように、本発明はある特定の析出粒子と平均
粒径が1μm未満で且つモース硬度が6以上の無機粒子
を併用することによシ、走行性、耐摩耗性及び耐擦傷性
を高度に且つ簡便に達成し得たものであシ、本発明にな
るポリエステルフィルムを用いる仁とによ)最終的に電
磁気的特性にも優れた磁気記録媒体を得ることが可能と
なる。As described above, the present invention improves runnability, wear resistance, and scratch resistance by using certain precipitated particles together with inorganic particles having an average particle size of less than 1 μm and a Mohs hardness of 6 or more. This has been achieved to a high degree and easily, and by using the polyester film of the present invention, it is finally possible to obtain a magnetic recording medium with excellent electromagnetic properties.
以下本発明を実施例によシ更に詳細に説明するが、本発
明はその要旨を越えない限シ、以下の実施例に限定され
るものではない。なお実施例及び比較例中「部」とめる
は「重量部」を示す。The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the Examples and Comparative Examples, "parts" indicate "parts by weight."
また、本発明で用いた測定法は次の通シである。Furthermore, the measurement method used in the present invention is as follows.
(1) 平均粒径
析出粒子の場合は該粒子を含むポリエステルをプレパラ
ートにはさみ溶融、冷却後、顕微鏡にて測定した。本発
明においては平均粒径とは、その形状の如何にかかわら
ず等制球換算値の体積分率jOチの点の粒径(直径〕を
指す。(1) Average particle size In the case of precipitated particles, the polyester containing the particles was sandwiched between slides, melted, cooled, and then measured using a microscope. In the present invention, the average particle size refers to the particle size (diameter) at a point where the volume fraction is jO in terms of an isostatic sphere, regardless of its shape.
添加粒子の場合も顕微鏡にて粒径を測定し、析出粒子と
同様に平均粒径を算出する。In the case of added particles, the particle size is also measured using a microscope, and the average particle size is calculated in the same way as for precipitated particles.
なお、析出粒子と添加粒子が同時忙含まれている場合は
、特公昭5S−201794号公報記載の方法により析
出粒子のみを解重合、分離する方法を採用するととによ
シ各々の平均粒径を算出する。If the precipitated particles and additive particles are present at the same time, it is best to depolymerize and separate only the precipitated particles using the method described in Japanese Patent Publication No. 5S-201794 to reduce the average particle size of each. Calculate.
(2) 析出粒子量の測定
ポリエステルi o Of K: o −クロルフェノ
ール/、O1を加え720℃で3時間加熱した後、ベッ
クマン製超遠心機り、7−kOft用いj O,000
rpmでlIo分間遠心分離を行い得られた粒子を10
0℃で真空乾燥する。該粒子を走査型差動熱量計にて測
定した時、ポリマーに相当する融解ピークが認められる
場合は該粒子に0−クロルフェノールを加え加熱冷却後
再び遠心分離操作を行う。融解ピークが認められなくな
った時読粒子を析出粒子とする。通常遠心分離操作は2
回で足りる。(2) Measurement of amount of precipitated particles Polyester ioOf K: o-chlorophenol/, After adding O1 and heating at 720°C for 3 hours, centrifugation was performed using a Beckman ultracentrifuge with a 7-kOft jO,000
The resulting particles were centrifuged for 10 min at rpm.
Vacuum dry at 0°C. When the particles are measured using a scanning differential calorimeter, if a melting peak corresponding to the polymer is observed, 0-chlorophenol is added to the particles, and after heating and cooling, centrifugation is performed again. Particles whose melting peak is no longer observed are defined as precipitated particles. Normally centrifugation operation is 2
times is enough.
(3) フィルムの表面粗度
中心線平均粗さ(Ra)Kより表わし、この値は小板研
究所社製表面粗さ測定器(SE−JFK)によって次の
よグに求めた。触針の先端半径は一μm5荷重はJO■
である。(3) Surface roughness of film Center line average roughness (Ra) K is expressed as K, and this value was determined using a surface roughness meter (SE-JFK) manufactured by Koita Research Institute as follows. The radius of the tip of the stylus is 1 μm5 The load is JO■
It is.
フィルム断面曲線からその中心線の方向に基準長さL(
コ、!xaa)の部分を抜き取#)、この抜き取シ部分
の中心線をX軸、縦倍率の方向をY軸として、粗さ曲線
y=f(x)で表わした時、次の式で与えられた値をμ
mで表わす。A reference length L (
Ko,! The roughness curve y=f(x) is given by the following formula: μ
Represented by m.
Ra=ff、” If(xi ldX なおりットオフ値はo、otrμmである。Ra=ff,” If(xi ldX The cut-off value is o, otrμm.
(4) 耐摩耗性
第2図に示す装置を用いて、フィルムを一〇〇m走行さ
せ、固定ビンに付着する白粉量の多寡を目視判定し、耐
摩耗性のランクをA(付着量が極めて少なく優れている
)〜C(付着量が多く実用性に乏しい)の3ランクに分
けた。(4) Abrasion resistance Using the device shown in Figure 2, the film was run for 100 meters, and the amount of white powder adhering to the fixed bottle was visually judged, and the abrasion resistance was ranked A (the amount of adhesion was It was divided into three ranks: extremely small (excellent) to C (poorly practical due to large amount of adhesion).
(5)走行性
フィルムの滑シ性によシ評価した。滑)性は第、1図の
装置を用いて測定した。即ち固定した硬質クロムメツキ
金属ロール(直径6關〕にフィルムを巻き付は角/ j
j’ すなわちコ、J s t、 rad(ので接
触させ、s J f (Tt)の荷重を一端にかけて/
?Fl / 311mの速度でこれを走行させ、他端
の抵抗力CT1−t)’に測定し、次式によシ走行中の
摩擦係数(μd)を求めた。(5) Running properties The film was evaluated for its lubricity. The lubricity was measured using the apparatus shown in FIG. In other words, the film is wrapped around a fixed hard chrome-plated metal roll (diameter 6 mm).
j', that is, J s t, rad (so contact, and apply a load of s J f (Tt) on one end /
? This was run at a speed of Fl/311 m, the resistance force CT1-t)' at the other end was measured, and the coefficient of friction (μd) during running was determined using the following equation.
/T T
μd=−Fl!n幇=0.ダJ I Jn a(6)耐
擦傷性
まず磁気テープを製造した。即ち次に示す磁性塗料をポ
リエステルフィルムに塗布し、乾燥後の膜厚が一μmと
なるよう磁性層を形成した。即ち磁性微粉末200部、
ポリウレタン樹脂JO部%ニトロセルロースIO部、塩
化ビニル−酢酸ビニル共重合体io部、レシチンS部、
シクロヘキサノン100部、メチルイソブチルケトン7
00部およびメチルエチルケトン、100部をボールミ
ルにてダざ時間混合分散後ポリイソシアネート化合物j
部を加えて磁性塗料とし、これをポリエステルフィルム
に塗布した後、塗料が十分乾燥固化する前に磁気配向さ
せ、その後乾燥した。/T T μd=-Fl! n = 0. (6) Scratch resistance First, a magnetic tape was manufactured. That is, the following magnetic paint was applied to a polyester film to form a magnetic layer so that the film thickness after drying was 1 μm. That is, 200 parts of magnetic fine powder,
Polyurethane resin JO part% Nitrocellulose IO part, vinyl chloride-vinyl acetate copolymer io part, lecithin S part,
100 parts of cyclohexanone, 7 parts of methyl isobutyl ketone
00 parts and methyl ethyl ketone, 100 parts were mixed and dispersed in a ball mill for several hours, and then polyisocyanate compound j
This was applied to a polyester film, magnetically oriented before the paint was fully dried and solidified, and then dried.
更忙この塗布フィルムをスーパーカレンダーにて表面処
理を施こし、5インチ幅にスリットしてビデオテープと
した。This coated film was surface-treated using a supercalender, and slit into 5-inch widths to make a videotape.
次に該磁気テープを硬質クロムメツキ金属ピン(直径4
11%表面粗さJS)IfC巻き付は角/Jl°、張力
!fOfで接触させ走行速度97717秒で擦過させた
。Next, attach the magnetic tape to a hard chrome-plated metal pin (diameter 4
11% surface roughness JS) IfC wrapping is angle/Jl°, tension! It was contacted at fOf and rubbed at a running speed of 97,717 seconds.
次いで磁気テープ擦過面にアルミニウムを蒸着し、傷の
程度を目視判定し次の5ランクに分けた。Next, aluminum was vapor-deposited on the scratched surface of the magnetic tape, and the degree of scratches was visually judged and divided into the following five ranks.
ランクl 傷の量が多く又しばしば深いキズがある。Rank L: There are many scratches and often deep scratches.
ランクコ 傷の量が比較的多く所々深いキズかある。Rank Co. The amount of scratches is relatively large, with some deep scratches here and there.
ランクJ 傷の程度は比較的少なく深いキズはわずかで
ある。Rank J: The degree of scratches is relatively small and there are only a few deep scratches.
ランクダ 少し傷が認められるが、満足すべきレベル。Ranked: There are some scratches, but the level is satisfactory.
ランクS はとんど傷が2いていない。Rank S rarely has 2 wounds.
(7) 電磁気特−性
上記磁気テープの電磁気特性を、松下電器製NV−37
00型ビデオデツキを用いて測定した。(7) Electromagnetic characteristics The electromagnetic characteristics of the above magnetic tape were measured using Matsushita Electric's NV-37.
Measurements were made using a 00 type video deck.
oVTRヘッド出力
シンクロスコープによシ測定周波数が弘メガヘルツにお
けるVTRヘッド出力を測定し、フランクをθデシベル
としその相対値をデシベルで表示した。The VTR head output was measured using a VTR head output synchroscope at a measurement frequency of 100 MHz, and the relative value was expressed in decibels with the flank set to θ decibels.
0ドロツプアウト数
#、lメガヘルツの信号を記録したビデオテープを再生
し、大金インダストリー■ドロップアウトカウンターで
ドロップアウト数を約−0分間測定し、1分間当シのド
ロップアウト数に換算した。A videotape recording a signal of #0 dropout and 1 megahertz was played back, and the number of dropouts was measured for about -0 minutes using a Daikin Industry ■ dropout counter, and was converted to the number of dropouts per minute.
実施例1
ジメチルテレフタレート100部、エチレングリコール
70部、酢酸カルシウム−水塩o、i。Example 1 100 parts of dimethyl terephthalate, 70 parts of ethylene glycol, calcium acetate hydrate o, i.
部及び酢酸リテクムニ水塩061j部を反応器釦とシ加
熱昇湛すると共にメタノールを留去させエステル交換反
応を行い、反応開始後約7時間を要して230℃に達せ
しめ、実質的にエステル交換反応を終了した。1 part and 061j part of acetic acid lytecum dihydrate were heated to boiling point with the reactor button, methanol was distilled off, and a transesterification reaction was carried out. It took about 7 hours after the start of the reaction to reach 230°C, and the ester was substantially converted into ester. The exchange reaction was completed.
次にこの反応混合物にリン酸トリエチル0.37部を添
加し更に三酸化アンチモン0”1部tm加した後常法に
従って重合し、グ時間後固有粘度o、b6のポリエチレ
ンテレフタレートを得た。Next, 0.37 part of triethyl phosphate was added to the reaction mixture, and 0.1 part tm of antimony trioxide was added thereto, followed by polymerization according to a conventional method to obtain polyethylene terephthalate having an intrinsic viscosity of o and b6 after 3 hours.
(ポリエステル(A))
該ポリエステル中には均一で微細な析出粒子が多数認め
られその粒径はo、 trμmであった。(Polyester (A)) A large number of uniform and fine precipitated particles were observed in the polyester, and the particle size was 0.05 μm.
本文中記載の方法に従ってその析出粒子量を測定したと
ころポリエステルに対し0.37重量俤であった。When the amount of precipitated particles was measured according to the method described in the text, it was found to be 0.37 weight relative to polyester.
一方、ジメチルテレフタレート100部とエチレングリ
コール70部及び酢酸マグネシウム四水塩0.09部を
反応器にとシ、加熱昇温すると共にメタノールを留去さ
せ、反応開始後約9時間を要してコJ0℃に達せしめエ
ステル交換反応を終了し丸。On the other hand, 100 parts of dimethyl terephthalate, 70 parts of ethylene glycol, and 0.09 parts of magnesium acetate tetrahydrate were placed in a reactor, and the temperature was raised while methanol was distilled off. The temperature was reached to 0°C to complete the transesterification reaction.
次いで熱分解法により得られた平均粒径θ、0λμmの
酸化アルミニウムをi、o部添加した後、更にリン酸ト
リエチルo、oq部及び三酸化アンチモン0.09部を
添加して常法にょシ重縮合反応を行ない固有粘度0.6
6のポリエチレンテレフタレートを得た。(ポリエステ
ル(B))酸化アルミニウムは該ポリエステル中に極め
て均一に分散しておシ、凝集粒子は実質的に認められな
かった。Next, i and o parts of aluminum oxide having an average particle diameter of θ and 0λ μm obtained by pyrolysis were added, and then o and oq parts of triethyl phosphate and 0.09 parts of antimony trioxide were added, and the mixture was processed using a conventional method. Performs polycondensation reaction and has an intrinsic viscosity of 0.6
Polyethylene terephthalate No. 6 was obtained. (Polyester (B)) Aluminum oxide was dispersed extremely uniformly in the polyester, and substantially no aggregated particles were observed.
次にポリエステル(A)とポリエステル(B) 、!:
を70:30重量比に混合し、乾燥した後コタ。Next, polyester (A) and polyester (B),! :
were mixed at a weight ratio of 70:30, dried, and then kettled.
℃で押出機よシシート状に押し出し無定形シートを得た
。この時シートに静電荷を付与するいわゆる静電印加冷
却法を採用した。次いで該シートを縦方向に3.3倍、
横方向に3.弘倍延伸してココ3℃で熱処理を行ない厚
み15μmの二軸延伸フィルムを得た。The mixture was extruded into a sheet using an extruder at ℃ to obtain an amorphous sheet. At this time, we adopted a so-called electrostatic cooling method that applies an electrostatic charge to the sheet. Then, the sheet was stretched 3.3 times in the vertical direction.
3. Laterally. The film was stretched in Hiroshima and then heat-treated at 3° C. to obtain a biaxially stretched film with a thickness of 15 μm.
次いで該ポリエステルフィルムに磁性層を塗布し、耐擦
傷性及び電磁気特性を評価した。A magnetic layer was then applied to the polyester film, and scratch resistance and electromagnetic properties were evaluated.
実施例λ
実施例1においてポリエステルフィルム中の析出粒子の
量及び添加粒子の平均粒径及び配合量を表−7のように
変える他は実施例/と同様にしてポリエチレンテレフタ
レートフィルム及び該フィルムを用いて磁気テープを得
た。Example λ A polyethylene terephthalate film and the film were used in the same manner as in Example 1, except that the amount of precipitated particles in the polyester film and the average particle size and blending amount of added particles were changed as shown in Table 7. A magnetic tape was obtained.
実施例3
実施例1のポリエステル(A)の製造においてリン酸ト
リエチル0.31部の代シにリン酸トリエチル0.26
部及び酸性リン酸エチル0,03部を用いる他は実施例
1と同様にして平均粒径O,Sμmの析出粒子を含むポ
リエステルを得た。Example 3 In the production of polyester (A) in Example 1, 0.26 parts of triethyl phosphate was substituted for 0.31 part of triethyl phosphate.
A polyester containing precipitated particles with an average particle diameter of O.S .mu.m was obtained in the same manner as in Example 1, except that 0.03 parts and 0.03 parts of acidic ethyl phosphate were used.
該ポリエステルと酸化アルミニウム粒子を含むポリエス
テルとを混合することにより表−7に示す粒子を含有す
るポリエチレンテレフタレートフィルムを得、次いで磁
気テープとしての評価を行なった。A polyethylene terephthalate film containing particles shown in Table 7 was obtained by mixing the polyester and a polyester containing aluminum oxide particles, and then evaluated as a magnetic tape.
実施例ダ
実施例3で得られた析出粒子とシリコンカーバイド粒子
とを併用することによυ表−/に示す粒子を含有するポ
リエチレンテレフタレートフィルムを得、次いで磁気テ
ープとしての評価を行なった。Example 2 A polyethylene terephthalate film containing the particles shown in Table υ was obtained by using the precipitated particles obtained in Example 3 in combination with silicon carbide particles, and then evaluated as a magnetic tape.
比較例/ −&
表−1に示すようにポリエチレンテレフタレートフィル
ム中に含まれる粒子を変える他は実施例/と同様に製膜
して厚み15μmの二軸配向フィルムを得、次いで磁気
テープ化し特性を評価した。Comparative Example/-& As shown in Table 1, a biaxially oriented film with a thickness of 15 μm was obtained by forming a film in the same manner as in Example/, except that the particles contained in the polyethylene terephthalate film were changed, and then it was made into a magnetic tape and its properties were evaluated. evaluated.
以上、得られた結果をまとめて表−/に示す。The results obtained above are summarized in Table-/.
本発明の要件を満たす実施例1−ダのフィルムはいずれ
も滑シ性、耐摩耗性に優れ、また特に耐擦傷性に優れる
ので電磁気特性において高度に満足すべきレベルにある
。All of the films of Example 1-da that meet the requirements of the present invention have excellent lubricity and abrasion resistance, and are particularly excellent in scratch resistance, so that their electromagnetic properties are at a highly satisfactory level.
これに対し比較例1は析出粒子のみを用い本願発明で特
定した添加粒子を併用しない場合の例であるが、耐擦傷
性が悪く、その結果、電磁気特性に劣るものしか得られ
ない。On the other hand, Comparative Example 1 is an example in which only precipitated particles are used without the additive particles specified in the present invention, but the scratch resistance is poor, and as a result, only a product with poor electromagnetic properties can be obtained.
比較例−祉添加粒子としてモース硬度Jの炭酸カルシク
ム粒子を用いた場合の例であるが、やはシ耐擦傷性は全
く改良されず磁気テープとしての特性は劣っている。ま
た比較例3は析出粒子と併用する添加粒子のモース硬度
が6以上であってもその平均粒径が1μm以上の場合の
例であるが、この場合フィルムの表面粗度が大きくなシ
すぎると共に添加した粒子が脱離して磁気テープ特性に
悪影譬を与えてしまり。Comparative Example - This is an example in which calcium carbonate particles having a Mohs' hardness of J were used as additive particles, but the scratch resistance was not improved at all and the properties as a magnetic tape were poor. Comparative Example 3 is an example in which the Mohs hardness of the additive particles used together with the precipitated particles is 6 or more, but the average particle size is 1 μm or more, but in this case, the surface roughness of the film is too large and The added particles detach and adversely affect the characteristics of the magnetic tape.
また、比較例ダは酸化アルミニウムの微粒子のみを用い
た例であるが、この場合フィルムの滑シ性が極めて悪く
、また摩耗粉が多量に生じ電磁気特性が悪化してしまう
。Further, Comparative Example D is an example in which only fine particles of aluminum oxide are used, but in this case, the film has extremely poor lubricity, and a large amount of abrasion powder is produced, deteriorating the electromagnetic properties.
以上詳述したように1本発明はある特定の析出粒子と添
加粒子とを組み合わせて使用することKよシ、磁気記録
媒体として必要な緒特性、特に近年その改良が要望され
ている耐擦傷性の改良を成し遂げたものであってその工
業的価値は高い。As described in detail above, the present invention uses a combination of specific precipitated particles and additive particles. It has achieved an improvement over the conventional method, and its industrial value is high.
第1図は金属との動摩擦係数を評価する装置の走行系を
示す概略図であシ、図中、(I〕は6tmlsUs−u
aO−JJ固定ビン、(II) Id 入ロfンシ目ン
メーター (■)は出口テンシロンメーターを示し、巻
き付は角(θ)は133°である。
第2図は耐摩耗性を評価する装置の走行系を示す概略図
であシ、図中で(■ンは6tmflSUS−ダコ0−J
コ固定ビン、(V)はテンションメーターを示し巻き付
は角(θ)は/ 、? !’である。
出 願 人 ダイアホイル株式会社Figure 1 is a schematic diagram showing the running system of the device for evaluating the coefficient of dynamic friction with metal.
aO-JJ fixed bottle, (II) Id Input tension meter (■) indicates the exit tensilon meter, and the winding angle (θ) is 133°. Figure 2 is a schematic diagram showing the running system of the device for evaluating wear resistance.
(V) indicates the tension meter, and the angle (θ) of the winding is /? ! 'is. Applicant Diafoil Co., Ltd.
Claims (1)
1〜5μmの不活性物質粒子0.01〜1重量%と、平
均粒径1μm未満で且つモース硬度6以上のポリエステ
ルに対し不活性な無機粒子0.01〜3重量%とを含有
することを特徴とする磁気記録媒体用二軸配向ポリエス
テルフィルム。(1) The average particle size precipitated in the polyester manufacturing process is 0.
Containing 0.01 to 1% by weight of inert material particles of 1 to 5 μm and 0.01 to 3% by weight of inorganic particles having an average particle size of less than 1 μm and inert to polyester having a Mohs hardness of 6 or more. Biaxially oriented polyester film for magnetic recording media.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63175452A JPH0224823A (en) | 1988-07-14 | 1988-07-14 | Biaxially oriented polyester film for magnetic recording medium |
DE198989109937T DE345644T1 (en) | 1988-06-04 | 1989-06-01 | POLYESTER FILM FOR MAGNETIC RECORDING CARRIERS. |
DE68919130T DE68919130T2 (en) | 1988-06-04 | 1989-06-01 | Polyester film for magnetic recording media. |
EP89109937A EP0345644B1 (en) | 1988-06-04 | 1989-06-01 | Polyester film for magnetic recording media |
US07/360,781 US5006589A (en) | 1988-06-04 | 1989-06-02 | Polyester film for magnetic recording media |
KR1019890007723A KR960008598B1 (en) | 1988-06-04 | 1989-06-03 | Polyester film for magnetic recording media |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63175452A JPH0224823A (en) | 1988-07-14 | 1988-07-14 | Biaxially oriented polyester film for magnetic recording medium |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0224823A true JPH0224823A (en) | 1990-01-26 |
JPH0514327B2 JPH0514327B2 (en) | 1993-02-24 |
Family
ID=15996320
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63175452A Granted JPH0224823A (en) | 1988-06-04 | 1988-07-14 | Biaxially oriented polyester film for magnetic recording medium |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0224823A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02286721A (en) * | 1989-04-28 | 1990-11-26 | Toray Ind Inc | Biaxially oriented polyester film |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62158726A (en) * | 1985-12-29 | 1987-07-14 | Toray Ind Inc | Biaxially oriented polyester film for magnetic tape |
-
1988
- 1988-07-14 JP JP63175452A patent/JPH0224823A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62158726A (en) * | 1985-12-29 | 1987-07-14 | Toray Ind Inc | Biaxially oriented polyester film for magnetic tape |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02286721A (en) * | 1989-04-28 | 1990-11-26 | Toray Ind Inc | Biaxially oriented polyester film |
Also Published As
Publication number | Publication date |
---|---|
JPH0514327B2 (en) | 1993-02-24 |
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