JPH08147671A - Magnetic recording medium - Google Patents
Magnetic recording mediumInfo
- Publication number
- JPH08147671A JPH08147671A JP29122094A JP29122094A JPH08147671A JP H08147671 A JPH08147671 A JP H08147671A JP 29122094 A JP29122094 A JP 29122094A JP 29122094 A JP29122094 A JP 29122094A JP H08147671 A JPH08147671 A JP H08147671A
- Authority
- JP
- Japan
- Prior art keywords
- film
- recording medium
- magnetic recording
- magnetic
- magnetic layer
- 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.)
- Pending
Links
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 132
- 239000004760 aramid Substances 0.000 claims abstract description 22
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 239000011164 primary particle Substances 0.000 claims abstract description 19
- 239000004642 Polyimide Substances 0.000 claims abstract description 12
- 229920001721 polyimide Polymers 0.000 claims abstract description 12
- 239000010419 fine particle Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000010408 film Substances 0.000 description 132
- 239000010410 layer Substances 0.000 description 64
- 239000002609 medium Substances 0.000 description 62
- 238000000034 method Methods 0.000 description 43
- 239000002245 particle Substances 0.000 description 43
- 239000000243 solution Substances 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 35
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 230000002776 aggregation Effects 0.000 description 13
- 238000004220 aggregation Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000006247 magnetic powder Substances 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
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 2
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Magnetic Record Carriers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、磁気記録媒体に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic recording medium.
【０００２】[0002]
【従来の技術】従来、磁気記録媒体としては、ポリエス
テルフィルムに酸化物塗布型磁性層やメタル塗布型磁性
層を設けてなる磁気記録媒体が知られている（例えば特
開昭６１−２６９３３号公報、特開昭６０−６６３１９
号公報など）。しかしながら、フィルムの加工工程ある
いは製品としての実施態様の変遷からフィルムの走行速
度は増大する一方であり、耐スクラッチ性、耐削れ性等
の耐久性や走行安定性の確保と同時にドロップアウトの
防止などの電磁変換特性を確保することは非常に困難な
状況である。2. Description of the Related Art Conventionally, as a magnetic recording medium, there is known a magnetic recording medium comprising a polyester film provided with an oxide coating type magnetic layer or a metal coating type magnetic layer (for example, Japanese Patent Laid-Open No. 61-26933). JP-A-60-66319.
Issue Bulletin). However, the traveling speed of the film is increasing due to the transition of the film processing process or the embodiment as a product, and the durability such as scratch resistance and abrasion resistance and the traveling stability are secured, and at the same time the dropout is prevented. It is a very difficult situation to secure the electromagnetic conversion characteristics of.
【０００３】[0003]
【発明が解決しようとする課題】近年、ビデオカメラの
屋外での使用の増加、あるいは小型化、記録時間の長時
間化の要請により、またコンピュータの外部メモリとし
て使用するため、薄膜で、過酷な条件での耐久性に優れ
た磁気記録媒体の要求が強くなってきている。In recent years, due to an increase in the use of video cameras outdoors, a demand for miniaturization and a long recording time, and for use as an external memory of a computer, they are thin and harsh. There is an increasing demand for magnetic recording media having excellent durability under the conditions.
【０００４】しかしながら、上記ポリエステルフィルム
ベースからなる磁気記録媒体では、常温、通常湿度下で
は問題ないが高温、高湿度条件下で使用すると走行性
や、出力特性が悪化したり、また、繰り返し走行におい
てドロップアウトが発生するという問題が出てきてい
る。これは基材フィルムの耐熱性、耐湿性が不十分であ
ったり、表面性、走行性が十分ではないためであると考
えられる。However, the above-mentioned polyester film-based magnetic recording medium has no problem at room temperature and normal humidity, but when used under high temperature and high humidity conditions, the running property and output characteristics are deteriorated, and the magnetic recording medium is repeatedly run. The problem is that dropouts occur. It is considered that this is because the heat resistance and moisture resistance of the base film are insufficient, or the surface properties and running properties are insufficient.
【０００５】また、磁気記録媒体の基材フィルムの表裏
両面に突起を形成することは走行性を高める目的で行わ
れ、通常非磁性面には磁性面よりも大きな突起が形成さ
れる。この時、テープ巻き張力等によって非磁性面の突
起形状が磁性面に転写され、磁性面の損傷からドロップ
アウトの発生等の問題がある。Further, the formation of protrusions on both the front and back surfaces of the base film of the magnetic recording medium is carried out for the purpose of enhancing the running property, and usually the protrusions larger than the magnetic surface are formed on the non-magnetic surface. At this time, the protrusion shape of the non-magnetic surface is transferred to the magnetic surface due to the tape winding tension and the like, and there is a problem that dropout occurs due to damage of the magnetic surface.
【０００６】本発明はかかる問題点を解決し、芳香族ポ
リアミドあるいは芳香族ポリイミドの優れた耐熱性、高
剛性を損なうことなく、かつ含有される粒子の構成、表
面特性を規定することにより高速度、繰り返し走行など
の厳しい条件下でも表面が傷つき難く（以下耐スクラッ
チ性と言う）、走行性、出力特性に優れ、同時に耐久性
に優れた磁気記録媒体を提供することを目的とする。The present invention solves the above problems and provides a high speed by not limiting the excellent heat resistance and high rigidity of aromatic polyamide or aromatic polyimide, and defining the constitution and surface characteristics of the contained particles. It is an object of the present invention to provide a magnetic recording medium that has a surface that is not easily scratched even under severe conditions such as repeated running (hereinafter referred to as scratch resistance), has excellent running properties and output characteristics, and at the same time has excellent durability.
【０００７】[0007]
【課題を解決するための手段】本発明は、芳香族ポリア
ミドあるいは芳香族ポリイミドからなる基材フィルムの
片面に磁性層を設けてなる磁気記録媒体であって、該基
材フィルムには、平均一次粒径が５〜２５０ｎｍ、平均
凝集度が５〜１００、モース硬度が６〜１０の微粒子を
含有し、かつ、非磁性層側には高さ３Ｈ以上の粗大突起
を２〜１００個／１００ｃｍ2 有し、かつ該基材フィル
ムのビッカース硬度が２０以上であることを特徴とする
磁気記録媒体である。The present invention is a magnetic recording medium having a magnetic layer provided on one side of a base film made of aromatic polyamide or aromatic polyimide, wherein the base film has an average primary It contains fine particles having a particle size of 5 to 250 nm, an average degree of aggregation of 5 to 100, and a Mohs hardness of 6 to 10, and 2 to 100 coarse protrusions with a height of 3H or more on the nonmagnetic layer side / 100 cm 2. And a Vickers hardness of the base film of 20 or more.
【０００８】本発明の芳香族ポリアミドとは、次の一般
式（Ｉ）および／または一般式（II）で表される繰り返
し単位を５０モル％以上含むものが好ましく、７０モル
％以上からなるものがより好ましい。The aromatic polyamide of the present invention preferably contains 50 mol% or more of repeating units represented by the following general formula (I) and / or general formula (II), and is composed of 70 mol% or more. Is more preferable.
【０００９】一般式（Ｉ）General formula (I)
【化１】 一般式（II）Embedded image General formula (II)
【化２】 ここで、Ａｒ1 、Ａｒ2 、Ａｒ3 は例えば、Embedded image Here, Ar 1 , Ar 2 and Ar 3 are, for example,
【化３】 などが挙げられ、Ｘ、Ｙは−Ｏ−，−ＣＨ2 −，−ＣＯ
−，−ＳＯ2 −、−Ｓ−，−Ｃ（ＣＨ3 ）2 −等から選
ばれるが、これに限定されるものではない。更にこれら
の芳香環上の水素原子の一部が、ハロゲン基（特に塩
素）、ニトロ基、Ｃ1 〜Ｃ3 のアルキル基（特にメチル
基）、Ｃ1 〜Ｃ3 のアルコキシ基などの置換基で置換さ
れているものも含み、また、重合体を構成するアミド結
合中の水素が他の置換基によって置換されているものも
含む。Embedded image And the like, X, Y is -O -, - CH 2 -, - CO
-, - SO 2 -, - S -, - C (CH 3) 2 - is chosen from such, but is not limited thereto. Further, a part of hydrogen atoms on these aromatic rings is a substituent such as a halogen group (especially chlorine), a nitro group, a C 1 -C 3 alkyl group (especially a methyl group), a C 1 -C 3 alkoxy group and the like. And those in which hydrogen in the amide bond constituting the polymer is replaced by another substituent.
【００１０】特性面からは上記の芳香環がパラ位で結合
されたものが、全芳香環の５０％以上、好ましくは７５
％以上を占める重合体が、フィルムの剛性が高く耐熱性
も良好となるため好ましい。また芳香環上の水素原子の
一部がハロゲン基（特に塩素）で置換された芳香環が全
体の３０％以上であると耐湿性が向上し、吸湿による寸
法変化、剛性低下などの特性が改善されるために好まし
い。From the characteristic point of view, the above-mentioned aromatic ring bonded in the para-position is 50% or more, preferably 75% of the total aromatic ring.
%, A polymer having a high rigidity and a good heat resistance is preferable. If 30% or more of all aromatic rings have hydrogen atoms on the aromatic ring replaced by halogen groups (especially chlorine), moisture resistance is improved, and characteristics such as dimensional change and rigidity reduction due to moisture absorption are improved. Is preferred.
【００１１】本発明の芳香族ポリアミドは、一般式
（Ｉ）および／または一般式（II）で表される繰り返し
単位を５０モル％以上含むものであって、５０モル％未
満は他の繰り返し単位が共重合、またはブレンドされて
いても差し支えない。The aromatic polyamide of the present invention contains 50 mol% or more of the repeating unit represented by the general formula (I) and / or the general formula (II), and less than 50 mol% is another repeating unit. May be copolymerized or blended.
【００１２】本発明における芳香族ポリイミドとは、重
合体の繰り返し単位の中に芳香環とイミド環を１つ以上
含むものであり、一般式（III ）および／または一般式
（IV）で示される繰り返し単位を５０モル％以上含むも
のが好ましく、より好ましくは７０モル％以上である。The aromatic polyimide in the present invention is one containing at least one aromatic ring and one imide ring in the repeating unit of the polymer and is represented by the general formula (III) and / or the general formula (IV). The content of repeating units is preferably 50 mol% or more, more preferably 70 mol% or more.
【００１３】一般式（III ）General formula (III)
【化４】 一般式（IV）[Chemical 4] General formula (IV)
【化５】 ここでＡｒ4 、Ａｒ6 は少なくとも１個の芳香環を含
み、イミド環を形成する２つのカルボニル基は芳香環上
の隣接する炭素原子に結合している。このＡｒ4 は、芳
香族テトラカルボン酸あるいはこの無水物に由来する。
代表例としては次の様なものが挙げられる。Embedded image Here, Ar 4 and Ar 6 include at least one aromatic ring, and two carbonyl groups forming an imide ring are bonded to adjacent carbon atoms on the aromatic ring. This Ar 4 is derived from an aromatic tetracarboxylic acid or its anhydride.
The following are typical examples.
【００１４】[0014]
【化６】 ここでＺは−Ｏ−，−ＣＨ2 −，−ＣＯ−，−ＳＯ
2 −、−Ｓ−，−Ｃ（ＣＨ3 ）2 −等から選ばれるが、
これに限定されるものではない。[Chemical 6] Wherein Z is -O -, - CH 2 -, - CO -, - SO
2 -, - S -, - C (CH 3) 2 - is chosen from such,
It is not limited to this.
【００１５】また、Ａｒ6 は無水カルボン酸あるいはこ
のハライドに由来する。Ａｒ5 、Ａｒ7 は例えばAr 6 is derived from carboxylic acid anhydride or its halide. Ar 5 and Ar 7 are, for example,
【化７】 などが挙げられ、Ｘ、Ｙは−Ｏ−，−ＣＨ2 −，−ＣＯ
−，−ＳＯ2 −、−Ｓ−，−Ｃ（ＣＨ3 ）2 −等から選
ばれるが、これに限定されるものではない。更にこれら
の芳香環上の水素原子の一部が、ハロゲン基（特に塩
素）、ニトロ基、Ｃ1 〜Ｃ3 のアルキル基（特にメチル
基）、Ｃ1 〜Ｃ3 のアルコキシ基などの置換基で置換さ
れているものも含み、また、重合体を構成するアミド結
合中の水素が他の置換基によって置換されているものも
含む。[Chemical 7] And the like, X, Y is -O -, - CH 2 -, - CO
-, - SO 2 -, - S -, - C (CH 3) 2 - is chosen from such, but is not limited thereto. Further, a part of hydrogen atoms on these aromatic rings is a substituent such as a halogen group (especially chlorine), a nitro group, a C 1 -C 3 alkyl group (especially a methyl group), a C 1 -C 3 alkoxy group and the like. And those in which hydrogen in the amide bond constituting the polymer is replaced by another substituent.
【００１６】本発明の芳香族ポリイミドは、一般式（II
I ）および／または一般式（IV）で表される繰り返し単
位を５０モル％以上含むものであって、５０モル％未満
は他の繰り返し単位が共重合、またはブレンドされてい
ても差し支えない。The aromatic polyimide of the present invention has the general formula (II
I) and / or the repeating unit represented by the general formula (IV) is contained in an amount of 50 mol% or more, and less than 50 mol% may be copolymerized or blended with other repeating units.
【００１７】また本発明の芳香族ポリアミド、芳香族ポ
リイミドには、フィルムの物性を損なわない程度に滑
剤、酸化防止剤その他の添加剤等がブレンドされていて
もよい。The aromatic polyamide and aromatic polyimide of the present invention may be blended with a lubricant, an antioxidant and other additives to the extent that the physical properties of the film are not impaired.
【００１８】次に、本発明の磁気記録媒体に用いる基材
フィルムの物性を説明する。Next, the physical properties of the base film used in the magnetic recording medium of the present invention will be described.
【００１９】本発明の磁気記録媒体は、該基材フィルム
のビッカース硬度として２０以上、好ましくは２５以
上、より好ましくは３０以上である。ビッカース硬度が
２０未満であれば、該基材フィルム中に含有せしめる粒
子を用いたとき、後述の非磁性面に形成された粗大突起
によって耐スクラッチ性、および耐削れ性を十分に確保
することができず、また、粗大突起の形状が磁性面に転
写されてドロップアウトの原因となったり、該基材フィ
ルムの加工工程上問題となることが多い。The Vickers hardness of the base film of the magnetic recording medium of the present invention is 20 or more, preferably 25 or more, more preferably 30 or more. If the Vickers hardness is less than 20, scratch resistance and abrasion resistance can be sufficiently secured by using coarse projections formed on the non-magnetic surface described below when particles to be contained in the base film are used. In many cases, the shape of the coarse protrusions is transferred to the magnetic surface to cause dropout, which causes a problem in the process of processing the base film.
【００２０】また、本発明の磁気記録媒体は、該基材フ
ィルムの２０℃における少なくとも一方向の引張りヤン
グ率Ｅ20が、Ｅ20≧８００kg／mm2 であることが望まし
く、長手方向にテンシライズまたは幅方向にテンシライ
ズされても差し支えない。テンシライズの度合いは特に
限定されないが、伸度、引き裂き抵抗力等の特性を考慮
に入れると、長手方向の引張りヤング率ＥMDと幅方向の
引張りヤング率ＥTDが、０．５≦ＥMD／ＥTD≦２、の範
囲であるのが実用的である。Further, in the magnetic recording medium of the present invention, the tensile Young's modulus E20 in at least one direction at 20 ° C. of the base film is preferably E20 ≧ 800 kg / mm 2 , and the longitudinal direction is tensified or widthwise. There is no problem even if it is tensified. The degree of tensioning is not particularly limited, but considering the characteristics such as elongation and tear resistance, the tensile Young's modulus EMD in the longitudinal direction and the tensile Young's modulus ETD in the width direction are 0.5 ≦ EMD / ETD ≦ 2. It is practical to be in the range of.
【００２１】また、本発明の磁気記録媒体は、該基材フ
ィルムの２０℃、相対湿度６０％における少なくとも一
方向の引張りヤング率Ｅ20が、Ｅ20≧８００kg／mm2 、
より好ましくはＥ20≧９００kg／mm2 、更に好ましくは
Ｅ20≧１０００kg／mm2 であることが好ましい。本発明
の磁気記録媒体は磁気記録媒体の薄型化の要請に応えて
薄膜で使用されることが多いので、テープ走行中、ある
いはストップ／スタート時にかかるテンションに耐える
ために、高いヤング率（Ｅ20≧８００kg／mm2）を持つ
ことが求められている。ヤング率がこれより低いとテー
プの伸びが起こり記録再生性が低下する。また、基材フ
ィルムが高いヤング率（Ｅ20≧８００kg／mm2 ）を持つ
ことにより塗布層形成、バックコート層形成工程など磁
気記録媒体形成時にかかるテンションにも耐えることが
出来、加工上も有利である。The magnetic recording medium of the present invention has a tensile Young's modulus E20 in at least one direction at 20 ° C. and a relative humidity of 60% of the substrate film of E20 ≧ 800 kg / mm 2 ,
More preferably, E20 ≧ 900 kg / mm 2 , and even more preferably E20 ≧ 1000 kg / mm 2 . Since the magnetic recording medium of the present invention is often used as a thin film in response to the demand for thinning of the magnetic recording medium, it has a high Young's modulus (E20 ≧ 20) in order to withstand tension applied during tape running or during stop / start. It is required to have 800 kg / mm 2 ). If the Young's modulus is lower than this range, the tape is elongated and the recording / reproducing property is deteriorated. Further, since the base material film has a high Young's modulus (E20 ≧ 800 kg / mm 2 ), it can withstand the tension applied during the formation of the magnetic recording medium such as the coating layer forming step and the back coat layer forming step, which is advantageous in processing. is there.
【００２２】次に、本発明の磁気記録媒体に用いる基材
フィルム中に含有される粒子について説明する。Next, the particles contained in the base film used in the magnetic recording medium of the present invention will be described.
【００２３】本発明の磁気記録媒体の基材フィルムに含
有される粒子の平均一次粒径は５〜２５０ｎｍ、好まし
くは５〜１５０ｎｍ、より好ましくは１０〜１００ｎｍ
である。平均一次粒径が上記の範囲より大きいと耐削れ
性が悪くなり、上記範囲より小さいと耐スクラッチ性が
悪くなる。The average primary particle size of the particles contained in the base film of the magnetic recording medium of the present invention is 5-250 nm, preferably 5-150 nm, more preferably 10-100 nm.
Is. If the average primary particle size is larger than the above range, the abrasion resistance is poor, and if it is smaller than the above range, the scratch resistance is poor.
【００２４】さらに、上記の粒子はフィルム中で凝集し
ている必要があり、平均凝集度は５〜１００、好ましく
は１０〜５０、より好ましくは１０〜３０である。この
平均凝集度が上記範囲より小さいときにはフィルムの耐
スクラッチ性が低下し、上記範囲より大きいときには、
耐削れ性を損なうばかりか、粗大突起の形成や削りカス
によるドロップアウトなどの電磁気変換特性を著しく損
なうことになる。Further, the above particles need to be aggregated in the film, and the average degree of aggregation is 5 to 100, preferably 10 to 50, and more preferably 10 to 30. When the average degree of cohesion is less than the above range, the scratch resistance of the film decreases, and when it is more than the above range,
Not only the abrasion resistance is impaired, but also electromagnetic conversion characteristics such as formation of coarse protrusions and dropout due to scraps are significantly impaired.
【００２５】また、上記粒子のモース硬度は６〜１０，
好ましくは６．５〜９の範囲である必要がある。モース
硬度が上記範囲より小さいときにはフィルムの耐スクラ
ッチ性が低下する。The Mohs hardness of the above particles is 6 to 10,
It should preferably be in the range of 6.5 to 9. When the Mohs hardness is less than the above range, the scratch resistance of the film decreases.
【００２６】本発明に用いる粒子の種類としては、特に
限定されないが、例えば、ＳｉＯ2、ＴｉＯ2 、Ｔｉ
Ｎ、Ａｌ2 Ｏ3 、ＺｒＯ2 、その他の金属微粉末などの
無機粒子を挙げることができるが、上記要件を満たす限
り特に制限はないが、非晶性のシリカあるいは結晶形態
がβ，γ，δ型から選ばれた少なくとも一種類のＡｌ2
Ｏ3 、ＺｒＯ2 、ＴｉＮのいずれかは耐スクラッチ性及
び耐削れ性に良好であり好ましく用いることができる。The type of particles used in the present invention is not particularly limited, but for example, SiO 2 , TiO 2 , Ti
Examples thereof include inorganic particles such as N, Al 2 O 3 , ZrO 2 , and other fine metal powders, but there is no particular limitation as long as the above requirements are satisfied, but amorphous silica or a crystalline form of β, γ, At least one type of Al 2 selected from δ type
Any one of O 3 , ZrO 2 and TiN has good scratch resistance and abrasion resistance and can be preferably used.
【００２７】本発明の磁気記録媒体の基材フィルムに含
有される粒子の含有量は０．０１〜５重量％、好ましく
は０．０５〜３重量％である。粒子の含有量が上記の範
囲より少ないと走行性改良に寄与することがなく、多い
とフィルム物性の低下や耐削れ性および電磁変換特性が
悪くなる。The content of particles contained in the base film of the magnetic recording medium of the present invention is 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If the content of the particles is less than the above range, it does not contribute to the improvement of the running property, and if it is more than the above range, the physical properties of the film are deteriorated and the abrasion resistance and the electromagnetic conversion characteristics are deteriorated.
【００２８】次に、本発明の磁気記録媒体に用いる基材
フィルムの表面状態を説明する。Next, the surface condition of the base film used for the magnetic recording medium of the present invention will be described.
【００２９】さらに、本発明の磁気記録媒体に用いる基
材フィルムにおいて、磁性層を設ける面の表面は微細突
起高さが３〜１００ｎｍ、好ましくは５〜７０ｎｍであ
ることが好ましい。上記範囲より小さいときには、耐滑
り性が悪くなり、耐スクラッチ、耐削れ性を低下させ
る。一方、上記範囲より大きいときには、ドロップアウ
トが増加する。更に、これら微細突起は基材フィルム上
に径として、０．０１μｍ以上のものが、１０4 〜１０
8 個／ｍｍ2 存在することが好ましい。微細突起径が
０．０１μｍ未満、あるいは微細突起数が１０4 個／ｍ
ｍ2 未満である時には、耐滑り性が悪くなり、耐スクラ
ッチ、耐削れ性を低下させる。また、微細突起数が１０
8 個／ｍｍ2 を越えると、磁気ヘッドとのあたりが悪く
なり、Ｓ／Ｎ比の低下を起こす。Further, in the substrate film used for the magnetic recording medium of the present invention, the height of the fine projections on the surface on which the magnetic layer is provided is 3 to 100 nm, preferably 5 to 70 nm. When it is less than the above range, the slip resistance is deteriorated and the scratch resistance and the abrasion resistance are deteriorated. On the other hand, when it is larger than the above range, dropout increases. Further, those fine protrusions having a diameter of 0.01 μm or more on the base film are 10 4 to 10
It is preferable that there are 8 pieces / mm 2 . Fine projection diameter is less than 0.01 μm, or the number of fine projections is 10 4 / m
When it is less than m 2 , slip resistance is deteriorated and scratch resistance and abrasion resistance are deteriorated. The number of fine protrusions is 10
If it exceeds 8 pieces / mm 2 , the contact with the magnetic head is deteriorated and the S / N ratio is lowered.
【００３０】また、本発明の磁気記録媒体に用いる基材
フィルム裏面は走行性の確保と言う観点から、特にモー
ス硬度が先述の微粒子よりも小さく、かつ平均粒径が
０．３〜３μｍの範囲にある粒子を０．０１〜５重量％
の範囲で同時に含有すると、走行性が向上し、さらに耐
スクラッチ性、耐削れ性がより一層良好となる。The back surface of the base film used for the magnetic recording medium of the present invention has a Mohs hardness smaller than that of the above-mentioned fine particles and an average particle diameter of 0.3 to 3 μm from the viewpoint of ensuring the running property. 0.01 to 5% by weight of particles in
In the range of 1, the running property is improved, and the scratch resistance and the abrasion resistance are further improved.
【００３１】磁気記録媒体として以上の構成を有する基
材フィルムを用いることにより、磁気ヘッドとのあたり
が円滑にして、ドロップアウトやＳ／Ｎ比の低下による
電磁変換特性の低下を防止できると共に、ガイドローラ
あるいは磁気ヘッド、テープ相互との接触面積は小さく
また、その硬度バランスが適度に保持され、走行性およ
び耐久性はきわめて良好なものとなるのである。By using the substrate film having the above-mentioned structure as the magnetic recording medium, the contact with the magnetic head can be made smooth, and the drop of the electromagnetic conversion characteristics due to the dropout and the drop of the S / N ratio can be prevented, and The contact area between the guide roller, the magnetic head, and the tape is small, and the hardness balance is appropriately maintained, so that the running property and durability are extremely good.
【００３２】また本発明の芳香族ポリアミド、芳香族ポ
リイミドには、フィルムの物性を損なわない程度に滑
剤、酸化防止剤その他の添加剤等がブレンドされていて
もよい。The aromatic polyamide and aromatic polyimide of the present invention may be blended with a lubricant, an antioxidant and other additives so long as the physical properties of the film are not impaired.
【００３３】また、本発明の磁気記録媒体は、該基材フ
ィルムの磁性層が形成される側の表面において高さ２Ｈ
以上の表面粗大突起個数が、５０個／１００ｃｍ2 以
下、より好ましくは３０個／１００ｃｍ2 以下、更に好
ましくは２０個／１００ｃｍ2以下であると良い。５０
個／１００ｃｍ2 を超えると磁気記録媒体としたときの
表面性が悪化し、ドロップアウトが発生し、高密度の磁
気記録媒体として適さなくなる。The magnetic recording medium of the present invention has a height of 2H on the surface of the base film on which the magnetic layer is formed.
More surface large protrusions number, may 50/100 cm 2 or less, more preferably 30/100 cm 2 or less, further preferably is 20/100 cm 2 or less. Fifty
If the number exceeds 100/100 cm 2 , the surface property of the magnetic recording medium deteriorates and dropout occurs, which makes it unsuitable as a high density magnetic recording medium.
【００３４】また本発明の磁気記録媒体は、該基材フィ
ルムの非磁性層側の表面において高さ３Ｈ以上の表面粗
大突起個数が、２〜１００個／１００ｃｍ2 、より好ま
しくは、２〜７０個／１００ｃｍ2 、更に好ましくは２
〜５０個／１００ｃｍ2 である。２個／１００ｃｍ2 未
満であると磁気記録媒体としたときのガイドロールなど
との接触抵抗が大きくなり、走行性が低下する。また１
００個／１００ｃｍ2を超えると塗布工程におけるカレ
ンダー処理時あるいは磁気記録媒体としての使用時に粗
大突起が磁性層側の表面に影響を及ぼすことがあり、ド
ロップアウトの原因となって好ましくない。In the magnetic recording medium of the present invention, the number of surface coarse protrusions having a height of 3H or more on the surface of the non-magnetic layer side of the base film is 2 to 100/100 cm 2 , and more preferably 2 to 70. Pieces / 100 cm 2 , more preferably 2
It is about 50 pieces / 100 cm 2 . When it is less than 2 pieces / 100 cm 2 , the contact resistance with a guide roll or the like when used as a magnetic recording medium becomes large, and the running property is deteriorated. Again 1
If the number exceeds 100/100 cm 2 , coarse protrusions may affect the surface on the magnetic layer side during calendering in the coating process or during use as a magnetic recording medium, which is not preferable because it causes dropout.
【００３５】また、本発明の磁気記録媒体は、該基材フ
ィルムを塩化メチレンで抽出したときの抽出物の量が
０．２％以下、好ましくは０．１％以下であると、長期
に使用したときの走行性が均質に保てるので好ましい。
０．２％を超えるとフィルム表面が粘くなり高速走行に
不利である。Further, the magnetic recording medium of the present invention is used for a long period when the amount of the extract when the base film is extracted with methylene chloride is 0.2% or less, preferably 0.1% or less. It is preferable because the running property can be kept uniform.
If it exceeds 0.2%, the film surface becomes sticky, which is disadvantageous for high-speed running.
【００３６】本発明は、上記基材フィルム上の片面に磁
性層を設けた磁気記録媒体である。磁性層を形成する方
法は、強磁性粉末を各種バインダーを用いて磁性塗料と
し基材フィルム上に塗布する湿式法、蒸着法、スパッタ
リング法、イオンプレーティング法などの乾式法があ
り、特に限定されるものではないが、ここでは湿式法を
例にとって説明する。The present invention is a magnetic recording medium in which a magnetic layer is provided on one surface of the base film. The method for forming the magnetic layer includes a wet method in which a ferromagnetic powder is used as a magnetic paint using various binders and applied on a base film, a vapor deposition method, a sputtering method, a dry method such as an ion plating method, and is not particularly limited. Although not limited to this, the wet method will be described here as an example.
【００３７】磁性体となる磁性粉末の種類は特に限定さ
れないが、強磁性粉末、例えば、酸化鉄、酸化クロム、
Ｆｅ，Ｃｏ、Ｆｅ−Ｃｏ、Ｆｅ−Ｃｏ−Ｎｉ、Ｃｏ−Ｎ
ｉ等が好ましく用いられる。The type of magnetic powder to be a magnetic material is not particularly limited, but ferromagnetic powder such as iron oxide, chromium oxide,
Fe, Co, Fe-Co, Fe-Co-Ni, Co-N
i and the like are preferably used.
【００３８】磁性粉末は各種バインダーを用いて磁性塗
料とすることができるが、熱硬化性樹脂系バインダーお
よび放射線硬化系バインダーが好ましく、その他添加剤
として分散剤、潤滑剤、帯電防止剤等を用いてもよい。
例えば、塩化ビニル・酢酸ビニル・ビニルアルコール共
重合体、ポリウレタンプレポリマおよびポリイソシアネ
ートよりなるバインダーを用いることができる。また、
磁性層面のモース硬度としても２０以上あると本発明の
効果がより一層発揮されるので好ましい。The magnetic powder can be made into a magnetic paint by using various binders, but thermosetting resin binders and radiation curing binders are preferable, and dispersants, lubricants, antistatic agents and the like are used as other additives. May be.
For example, a binder composed of a vinyl chloride / vinyl acetate / vinyl alcohol copolymer, a polyurethane prepolymer and a polyisocyanate can be used. Also,
It is preferable that the Mohs hardness of the surface of the magnetic layer is 20 or more because the effects of the present invention can be further exhibited.
【００３９】また本発明の磁気記録媒体の基材フィルム
はもちろん単層フィルムでも用いられるが、積層フィル
ムであっても良い。積層フィルムとする時は、本発明の
磁気記録媒体の基材フィルムと基層部（積層された本発
明の基材フィルム以外のフィルム構成部分）は同じ種類
でも異なるものでも良い。この基層部を構成する少なく
とも一層にも粒子を含有していてもよく、粒子の種類、
粒子の平均一次粒径、含有量は本発明に望ましく用いら
れるものを、使用することが望ましい。基層部における
粒子の径が積層された本発明の基材フィルム中の粒子の
径よりも大きいと、基材フィルム表面に適度のうねりを
持たせる事ができテ−プ走行性がより一層良好となるの
で望ましい。The magnetic recording medium of the present invention may be used not only as a base film but also as a single layer film, but may be a laminated film. In the case of a laminated film, the base film and the base layer portion (film constituting portion other than the laminated base film of the present invention) of the magnetic recording medium of the present invention may be the same kind or different. The base layer portion may also contain particles in at least one layer, the type of particles,
It is desirable to use the average primary particle diameter and content of the particles that are preferably used in the present invention. When the diameter of the particles in the base layer portion is larger than the diameter of the particles in the laminated base material film of the present invention, it is possible to impart an appropriate waviness to the base material film surface and further improve tape running property. Is desirable.
【００４０】本発明の磁気記録媒体における基材フィル
ムの厚みは好ましくは０．５〜５０μｍ、より好ましく
は１〜２０μｍ、更に好ましくは２〜１０μｍである
と、薄膜の磁気記録媒体として本発明の効果である優れ
た走行性、電磁変換特性が実現されるので望ましい。The thickness of the substrate film in the magnetic recording medium of the present invention is preferably 0.5 to 50 μm, more preferably 1 to 20 μm, and further preferably 2 to 10 μm, as a thin film magnetic recording medium of the present invention. It is desirable because excellent running performance and electromagnetic conversion characteristics that are the effects are realized.
【００４１】本発明の磁気記録媒体における基材フィル
ムの２００℃、１０分間での熱収縮率は５％以下が好ま
しく、より好ましくは２％以下であると温度変化による
テープの寸法変化が小さく良好な電磁変換特性を保てる
ので望ましい。The heat shrinkage of the substrate film in the magnetic recording medium of the present invention at 200 ° C. for 10 minutes is preferably 5% or less, and more preferably 2% or less, the dimensional change of the tape due to temperature change is small and good. It is desirable because it can maintain excellent electromagnetic conversion characteristics.
【００４２】本発明の磁気記録媒体における基材フィル
ムの伸度は１０％以上、より好ましくは２０％以上、更
に好ましくは３０％以上であるとテープが適度な柔軟性
を持つので望ましい。The elongation of the substrate film in the magnetic recording medium of the present invention is preferably 10% or more, more preferably 20% or more, further preferably 30% or more, since the tape has appropriate flexibility.
【００４３】本発明の磁気記録媒体における基材フィル
ムの吸湿率は、５％以下、より好ましくは３％以下、更
に好ましくは２％以下であると湿度変化によるテープの
寸法変化が小さく良好な電磁変換特性を保てるので望ま
しい。When the moisture absorption rate of the substrate film in the magnetic recording medium of the present invention is 5% or less, more preferably 3% or less, and further preferably 2% or less, the dimensional change of the tape due to humidity change is small and good electromagnetic properties are obtained. It is desirable because the conversion characteristics can be maintained.
【００４４】これらの特性は、積層された場合には積層
フィルムについても満足することが好ましい。It is preferable that these characteristics are also satisfied in the laminated film when laminated.
【００４５】次に本発明の製造方法を説明するが、これ
に限定されるものではない。Next, the manufacturing method of the present invention will be explained, but the present invention is not limited to this.
【００４６】まず芳香族ポリアミドであるが、酸クロリ
ドとジアミンから得る場合には、Ｎ−メチルピロリドン
（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメ
チルホルムアミド（ＤＭＦ）などの非プロトン性有機極
性溶媒中で、溶液重合したり、水系媒体を使用する界面
重合などで合成される。ポリマ溶液は、単量体として酸
クロリドとジアミンを使用すると塩化水素が副生する
が、これを中和する場合には水酸化カルシウム、炭酸カ
ルシウム、炭酸リチウムなどの無機の中和剤、またエチ
レンオキサイド、プロピレンオキサイド、アンモニア、
トリエチルアミン、トリエタノールアミン、ジエタノー
ルアミンなどの有機の中和剤が使用される。また、イソ
シアネートとカルボン酸との反応は、非プロトン性有機
極性溶媒中、触媒の存在下で行なわれる。First, an aromatic polyamide, but when it is obtained from an acid chloride and a diamine, it is used in an aprotic organic polar solvent such as N-methylpyrrolidone (NMP), dimethylacetamide (DMAc) or dimethylformamide (DMF). , Solution polymerization or interfacial polymerization using an aqueous medium. When acid chloride and diamine are used as monomers in the polymer solution, hydrogen chloride is by-produced.When neutralizing this, inorganic neutralizing agents such as calcium hydroxide, calcium carbonate and lithium carbonate, and ethylene Oxide, propylene oxide, ammonia,
Organic neutralizing agents such as triethylamine, triethanolamine, diethanolamine are used. The reaction between isocyanate and carboxylic acid is carried out in the presence of a catalyst in an aprotic organic polar solvent.
【００４７】これらのポリマ溶液はそのまま製膜原液と
して使用してもよく、あるいはポリマを一度単離してか
ら上記の有機溶媒や、硫酸等の無機溶剤に再溶解して製
膜原液を調製してもよい。These polymer solutions may be directly used as a film forming stock solution, or the polymer may be isolated once and then redissolved in the above organic solvent or an inorganic solvent such as sulfuric acid to prepare a film forming stock solution. Good.
【００４８】本発明の芳香族ポリアミドフィルムを得る
ためにはポリマの固有粘度（ポリマ０．５ｇを硫酸中で
１００ｍｌの溶液として３０℃で測定した値）は、０．
５以上であることが好ましい。In order to obtain the aromatic polyamide film of the present invention, the intrinsic viscosity of the polymer (value measured at 30 ° C. in a solution of 0.5 g of the polymer in 100 ml of sulfuric acid) is 0.
It is preferably 5 or more.
【００４９】製膜原液には溶解助剤として無機塩例えば
塩化カルシウム、塩化マグネシム、塩化リチウム、硝酸
リチウムなどを添加する場合もある。製膜原液中のポリ
マ濃度は２〜４０重量％程度が好ましい。Inorganic salts such as calcium chloride, magnesium chloride, lithium chloride and lithium nitrate may be added to the stock solution for film formation as a dissolution aid. The polymer concentration in the stock solution for film formation is preferably about 2 to 40% by weight.
【００５０】一方、芳香族ポリイミドあるいはポリアミ
ド酸の溶液は次のようにして得られる。即ち、ポリアミ
ド酸はＮ−メチルピロリドン（ＮＭＰ）、ジメチルアセ
トアミド（ＤＭＡｃ）、ジメチルホルムアミド（ＤＭ
Ｆ）などの非プロトン性有機極性溶媒中で、テトラカル
ボン酸二水物と芳香族ジアミンを反応させて調製するこ
とができる。また芳香族ポリイミドは前記のポリアミド
酸を含有する溶液を加熱したり、ピリジンなどのイミド
化剤を添加してポリイミドの粉末を得、これを再度溶媒
に溶解して調製できる。製膜原液中のポリマ濃度は５〜
４０重量％程度が好ましい。On the other hand, a solution of aromatic polyimide or polyamic acid is obtained as follows. That is, polyamic acid is N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DM).
It can be prepared by reacting a tetracarboxylic acid dihydrate with an aromatic diamine in an aprotic organic polar solvent such as F). The aromatic polyimide can be prepared by heating a solution containing the above polyamic acid or adding an imidizing agent such as pyridine to obtain a polyimide powder, which is dissolved again in a solvent. Polymer concentration in the film forming solution is 5
About 40% by weight is preferable.
【００５１】粒子の添加方法は、特に制限はないが、凝
集度の調整，粗大突起の出現を抑制するためには、例え
ば、粒子を予め１０ポイズ好ましくは１ポイズ以下の溶
媒中に分散させる方法を挙げることができる。溶媒とし
ては、製膜時に用いるものと同一であることが好ましい
が、特に悪影響が見られないときには、他の溶媒を用い
て差し支えない。また、これら溶媒には分散助剤等の添
加物が分散あるいは物性に悪影響を及ぼさない範囲で用
いられて構わない。粒子の分散には撹拌分散器、ボール
ミル、超音波分散器等を用い、本発明の範囲内に粒子
径、凝集度を調整する。The method of adding particles is not particularly limited, but in order to adjust the degree of coagulation and suppress the appearance of coarse protrusions, for example, the particles are previously dispersed in a solvent of 10 poise or less, preferably 1 poise or less. Can be mentioned. The solvent is preferably the same as that used for film formation, but other solvents may be used unless particularly adverse effects are observed. In addition, additives such as a dispersion aid may be used in these solvents within a range that does not adversely affect dispersion or physical properties. For dispersing the particles, a stirring disperser, a ball mill, an ultrasonic disperser or the like is used, and the particle diameter and the degree of aggregation are adjusted within the scope of the present invention.
【００５２】この分散された粒子は前記ポリマ溶液に混
合するが、混合にあたっては重合前の溶媒に添加あるい
は重合後に添加あるいはポリマ溶液調整時に添加しても
よく、さらにはキャスト直前でも構わないが、原液中に
均一に分散されていることが非常に重要である。The dispersed particles are mixed with the above-mentioned polymer solution. In mixing, they may be added to a solvent before polymerization, added after polymerization, or added at the time of preparing a polymer solution, and further just before casting. It is very important that it is uniformly dispersed in the stock solution.
【００５３】上記のように調製された製膜原液は、いわ
ゆる溶液製膜法によりフィルム化が行なわれる。溶液製
膜法には乾湿式法、乾式法、湿式法などがありいづれの
方法で製膜されても差し支えないが、ここでは乾湿式法
を例にとって説明する。The stock solution for film formation prepared as described above is formed into a film by a so-called solution film forming method. The solution film-forming method may be a dry-wet method, a dry method, a wet method, or the like, and the film may be formed by any method, but here, the dry-wet method will be described as an example.
【００５４】乾湿式法で製膜する場合は該原液を口金か
らドラム、エンドレスベルト等の支持体上に押し出して
薄膜とし、次いでかかる薄膜層から溶媒を飛散させ薄膜
が自己保持性をもつまで乾燥する。乾燥条件は例えば、
室温〜２２０℃、６０分以内の範囲、好ましくは室温〜
２００℃の範囲で行うことができる。またこの乾燥工程
で用いられるドラム、エンドレスベルトの表面欠点頻度
を制御することは粗大突起の制御の観点から好ましく、
例えば、径が３０μｍ以上の表面欠点頻度が０．００１
〜０．０２個／mm2 、好ましくは０．００２〜０．０１
５個／mm2 であればよい。乾式工程を終えたフィルムは
支持体から剥離されて湿式工程に導入され、上記の湿式
法と同様に脱塩、脱溶媒などが行なわれ、さらに延伸、
乾燥、熱処理が行なわれてフィルムとなる。When a film is formed by a dry-wet method, the stock solution is extruded from a spinneret onto a support such as a drum or an endless belt to form a thin film, and then the solvent is scattered from the thin film layer and dried until the thin film has a self-holding property. To do. Drying conditions are, for example:
Room temperature to 220 ° C, within 60 minutes, preferably room temperature to
It can be performed in the range of 200 ° C. Further, it is preferable to control the surface defect frequency of the drum and endless belt used in this drying step from the viewpoint of controlling coarse protrusions,
For example, the frequency of surface defects with a diameter of 30 μm or more is 0.001.
~ 0.02 pieces / mm 2 , preferably 0.002-0.01
It should be 5 pieces / mm 2 . The film after the dry process is peeled from the support and introduced into the wet process, desalting, desolventizing and the like are performed in the same manner as the above-mentioned wet method, and further stretching,
It is dried and heat-treated to form a film.
【００５５】以上のように形成されるフィルムはその製
膜工程中で延伸が行なわれるが、延伸倍率は面倍率で
０．８〜８．０（面倍率とは延伸後のフィルム面積を延
伸前のフィルムの面積で除した値で定義する。１以下は
リラックスを意味する。）の範囲内にあることが好まし
く、より好ましくは１．１〜５．０である。また延伸あ
るいは熱処理後のフィルムを徐冷する事が有効であり、
５０℃／秒以下の速度で冷却する事が有効である。The film formed as described above is stretched in the film-forming step, and the stretching ratio is 0.8 to 8.0 in terms of areal ratio (the areal ratio means the film area after stretching before stretching). It is defined as a value divided by the area of the film, and 1 or less means relax.), And more preferably 1.1 to 5.0. It is also effective to gradually cool the film after stretching or heat treatment,
Cooling at a rate of 50 ° C / sec or less is effective.
【００５６】なお本発明のフィルムは、積層フィルムで
あってもよい。例えば２層の場合には、重合した芳香族
ポリアミド溶液を二分し、それぞれ異なる粒子を添加し
た後、積層する。さらに３層以上の場合も同様である。
これら積層の方法としては、周知の方法たとえば、口金
内での積層、複合管での積層や、一旦１層を形成してお
いてその上に他の層を形成する方法などがある。The film of the present invention may be a laminated film. For example, in the case of two layers, the polymerized aromatic polyamide solution is divided into two, and different particles are added, respectively, and then laminated. The same applies to the case of three or more layers.
As a method of stacking these, there are known methods such as stacking in a die, stacking in a composite tube, and a method in which one layer is once formed and then another layer is formed thereon.
【００５７】次にこのフィルムに磁性層を形成する。磁
性層を形成する方法は公知の方法で行うことができる
が、湿式法の場合には、グラビアロールを使用する方法
が塗膜の均一性の点ではより好ましい。塗布後の乾燥温
度は９０℃〜１５０℃が好ましい。またカレンダー工程
は２５℃〜１５０℃の範囲で行うのが好ましい。Next, a magnetic layer is formed on this film. The method of forming the magnetic layer can be performed by a known method, but in the case of a wet method, a method using a gravure roll is more preferable from the viewpoint of uniformity of the coating film. The drying temperature after coating is preferably 90 ° C to 150 ° C. The calendering step is preferably performed in the range of 25 ° C to 150 ° C.
【００５８】この後、磁性層と反対側の面に更に走行性
を向上させるために、公知の方法によりバックコート層
を設けてもよい。Thereafter, a back coat layer may be provided on the surface opposite to the magnetic layer by a known method in order to further improve the running property.
【００５９】更に、必要に応じこの磁性層を形成したフ
ィルムをキュアし、後にスリットして本発明の磁気記録
媒体となる。If necessary, the film on which the magnetic layer is formed is cured and then slit to form the magnetic recording medium of the present invention.
【００６０】こうして得られた磁気記録媒体は、小形
化、薄型化が可能なためコンパクトで大容量のデータを
記録することができ、ビデオ、オーデイオ用にはもちろ
ん、なおかつ耐スクラッチ性、走行性、出力特性等に優
れ、特にコンピューターのデータテープ等のデジタル記
録材やビデオカメラ用テープ等として好適である。１Since the magnetic recording medium thus obtained can be made compact and thin, it is compact and capable of recording a large amount of data. It is of course suitable for video and audio applications, and has scratch resistance, running property, and It is excellent in output characteristics and the like, and is particularly suitable as a digital recording material such as a computer data tape and a tape for a video camera. 1
【００６１】[0061]
【実施例】本発明の物性の測定方法、効果の評価方法は
次の方法による。EXAMPLES The methods of measuring physical properties and evaluating effects of the present invention are as follows.
【００６２】（１）平均一次粒径、平均凝集度 粒子を含有させたフィルムを断面方向に厚さ１００ｎｍ
の超薄片とし、日本電子製透過型電子顕微鏡（ＪＥＭ−
１２００ＥＸ）を用いて、約１０万倍の倍率にて断面の
凝集粒子を観察し、これ以上分割できない最小粒径（一
次粒子径）を観察した。また、この凝集粒子が幾つの一
次粒子からなるかを断面写真より数えた。(1) Average primary particle size, average degree of coagulation The film containing the particles has a thickness of 100 nm in the cross-sectional direction.
Of the transmission electron microscope (JEM-
(1200 EX), the agglomerated particles in the cross section were observed at a magnification of about 100,000 times, and the minimum particle size (primary particle size) that could not be further divided was observed. In addition, how many primary particles the agglomerated particles consist of was counted from a cross-sectional photograph.
【００６３】これを５００視野について実施し、平均値
を各々平均一次粒径、平均凝集度とした。This was carried out for 500 fields of view, and the average values were taken as the average primary particle diameter and the average cohesion degree, respectively.
【００６４】（２）微細突起数 電子顕微鏡にて１万倍以上に拡大してフィルム表面上を
観察し、突起の最大径が０．０１μｍのものについてそ
の数を数えた。(2) Number of fine protrusions The surface of the film was observed under an electron microscope at a magnification of 10,000 times or more, and the number of protrusions having a maximum diameter of 0.01 μm was counted.
【００６５】（３）微細突起高さ 小坂研究所社製薄膜段差測定器（ＥＴ−１０）を用い、
触針半径０．５μｍ、荷重４ｍｇ、カットオフ値０．０
８ｍｍの条件で、表面粗さ方向の５０万倍に拡大してチ
ャート紙上に書かせ、断面曲線のフィルム長２５μｍに
相当する部分について一番高い山の高さを求め、同様に
して任意のフィルム長２５μｍに相当する部分について
計１０点測定し、その数値を平均した。(3) Height of fine protrusions Using a thin film step measuring device (ET-10) manufactured by Kosaka Laboratory,
Stylus radius 0.5 μm, load 4 mg, cutoff value 0.0
Under the condition of 8 mm, it is magnified 500,000 times in the surface roughness direction and written on a chart paper, and the highest peak height is obtained for the portion corresponding to the film length of 25 μm of the cross-section curve, and similarly any film A total of 10 points were measured for a portion corresponding to a length of 25 μm, and the numerical values were averaged.
【００６６】（４）粗大突起個数 非磁性層側のフィルム表面１００ｃｍ2 の範囲を実体顕
微鏡により偏光下、異物を観測し、マーキングする。マ
ーキングした異物の高さを波長５４６ｎｍで多重干渉計
を用いて観測し、干渉縞の数でチェックする。二重環以
上のものを２Ｈ、三重環以上のものを３Ｈとして、その
個数を計数した。(4) Number of coarse projections Foreign matter is observed and marked under polarized light in a range of 100 cm 2 of the film surface on the non-magnetic layer side with a stereoscopic microscope. The height of the marked foreign matter is observed at a wavelength of 546 nm using a multiple interferometer and checked by the number of interference fringes. The number of double rings or more was set as 2H and the number of triple rings or more was set as 3H, and the number thereof was counted.
【００６７】（５）ビッカース硬度 ＪＩＳＢ−７７３４に準じ測定した。測定荷重は３５ｇ
とした。(5) Vickers hardness Measured according to JIS B-7734. Measurement load is 35g
And
【００６８】（６）耐久性（耐スクラッチ性、耐削れ
性） ２５℃、５５％ＲＨの環境下、１００回繰り返し走行さ
せた後の磁性面のすり傷や欠落を観察し、次の３段階で
評価した。(6) Durability (Scratch resistance, Scratch resistance) Observed scratches and defects on the magnetic surface after running 100 times in an environment of 25 ° C. and 55% RH. It was evaluated by.
【００６９】◎：まったくすり傷や欠落が見られない。⊚: No scratches or missing are observed.
【００７０】○：極めて弱いすり傷の発生が認められ
る。◯: Generation of extremely weak scratches is recognized.
【００７１】×：きついすり傷や磁性層の欠落が認めら
れる。X: Tight scratches and lack of magnetic layer are recognized.
【００７２】（７）電磁変換特性 磁性層を塗布したフィルムを１／２インチ幅にスリット
し、ＶＴＲカセットに組み込みＶＴＲテ−プとした。こ
のテ−プに家庭用ＶＴＲを用いてテレビ試験波形発生器
により１００％クロマ信号からカラ−ビデオノイズ測定
器でクロマＳ／Ｎを測定した。Ｓ／Ｎ比は次式で示され
る。(7) Electromagnetic conversion characteristics The film coated with the magnetic layer was slit into a 1/2 inch width and incorporated into a VTR cassette to obtain a VTR tape. Chroma S / N was measured from a 100% chroma signal by a television test waveform generator using a household VTR on this tape with a color video noise measuring instrument. The S / N ratio is shown by the following equation.
【００７３】Ｓ／Ｎ＝２０ｌｏｇ（Ｖs ／Ｖn ） ここで、Ｖs ：１００％振幅のカラー信号レベル Ｖn ：リファレンス記録電流で記録・再生し、ＡＭ復調
及びＰＭ復調した１００％レベルにおけるノイズの実効
値電圧 市販テ−プを基準として評価し、−２ｄＢ以上を○、そ
れ未満を×とした。S / N = 20log (Vs / Vn) Where, Vs: Color signal level of 100% amplitude Vn: Effective value of noise at 100% level, which is recorded / reproduced by reference recording current, AM demodulated and PM demodulated. Voltage A commercially available tape was evaluated as a standard, and −2 dB or more was evaluated as ◯ and less than that was evaluated as x.
【００７４】（８）走行性 フィルムを幅１／２インチのテ−プ状にスリットしたも
のを、横浜システム研究所製テ−プ走行性試験機（ＳＦ
Ｔ−７００型）を使用し、４０℃、８０％ＲＨ雰囲気で
走行させ、下式により求めた。(8) Runnability A film slitted into a tape having a width of 1/2 inch was used as a tape runnability testing machine (SF
T-700 type) was used, traveling was carried out at 40 ° C. and 80% RH atmosphere, and the value was calculated by the following formula.
【００７５】μＫ＝０．７３３ｌｏｇ（Ｔ2 ／Ｔ1 ） ここでＴ1 は入側張力、Ｔ2 は出側張力である。ガイド
径は６ｍｍφであり、ガイド材質はポリオキシメチレン
（表面粗さ２０〜４０ｎｍ程度のもの）巻き付け角は９
０。 、走行速度は３．３ｃｍ／秒、繰返しストロ−クは
１５ｃｍである。この測定によって得られる１０パス目
のμＫをμＫ10、１００パス目のμＫをμＫ100 とした
時、μＫ10／μＫ100 が０．８以上１．２以下の場合は
走行性を○、この範囲外は走行性を×と判定した。な
お、測定に当たっては静電気の影響を避けるためフィル
ムを毎回除電して測定した。ΜK = 0.733 log (T2 / T1) where T1 is the inlet tension and T2 is the outlet tension. The guide diameter is 6 mmφ, the guide material is polyoxymethylene (with a surface roughness of about 20-40 nm), and the winding angle is 9
0. The running speed is 3.3 cm / sec and the repeating stroke is 15 cm. When μK of the 10th pass obtained by this measurement is μK10 and μK of the 100th pass is μK100, the runnability is ○ when μK10 / μK100 is 0.8 or more and 1.2 or less, and the runnability is outside this range. Was determined as x. In the measurement, the charge was removed from the film each time to avoid the influence of static electricity.
【００７６】以下に実施例に基づいて本発明を説明する
が、これらに限定されるものではない。The present invention is described below based on examples, but the invention is not limited thereto.
【００７７】実施例１ Ｎ−メチルピロリドン（ＮＭＰ）に芳香族ジアミン成分
として８０モル％に相当する２−クロルパラフェニレン
ジアミンと、２０モル％に相当する４、４’−ジアミノ
ジフェニルエ−テルとを溶解させ、これに１００モル％
に相当する２−クロルテレフタル酸クロリドを添加し、
２時間撹拌して重合を完了した。これを水酸化リチウム
で中和して、ポリマ濃度１０重量％、粘度３０００ポイ
ズの芳香族ポリアミド溶液を得た。ついで、この溶液
に、平均一次粒径１６ｎｍ、モース硬度が７．５である
アルミナ粒子をポリマ当たり２重量％添加し、撹拌し
た。Example 1 N-methylpyrrolidone (NMP) was added with 2-chloroparaphenylenediamine corresponding to 80 mol% as an aromatic diamine component and 4,4'-diaminodiphenyl ether corresponding to 20 mol%. To 100% by mol
2-chloroterephthalic acid chloride corresponding to
Polymerization was completed by stirring for 2 hours. This was neutralized with lithium hydroxide to obtain an aromatic polyamide solution having a polymer concentration of 10% by weight and a viscosity of 3000 poise. Then, 2% by weight of alumina particles having an average primary particle size of 16 nm and a Mohs hardness of 7.5 was added to this solution per polymer, and the mixture was stirred.
【００７８】このポリマ溶液を５μｍカットのフィルタ
−を通した後、ＳＵＳ製ベルト上に流延し、１８０℃の
熱風で２分間加熱して溶媒を蒸発させ、自己保持性を得
たフィルムをベルトから連続的に剥離した。次にＮＭＰ
の濃度勾配をつけた水槽内へフィルムを導入して残存溶
媒と中和で生じた無機塩の水抽出を行ない、テンタ−で
水分の乾燥と熱処理を行なって厚さ６μｍの芳香族ポリ
アミドフィルムを得た。この間にフィルム長手方向と幅
方向に各々１．２倍、１．３倍延伸を行ない、２８０℃
で１．５分間乾燥と熱処理を行なった後、２０℃／秒の
速度で徐冷した。This polymer solution was passed through a 5 μm-cut filter, cast on a SUS belt, heated with hot air at 180 ° C. for 2 minutes to evaporate the solvent, and a film having self-supporting property was obtained. Was continuously peeled off. Next is NMP
The film was introduced into a water tank having a concentration gradient of 1. to extract the residual solvent and the inorganic salt generated by the neutralization with water, and the water was dried and heat-treated with a tenter to obtain an aromatic polyamide film with a thickness of 6 μm. Obtained. In the meantime, the film was stretched 1.2 times and 1.3 times in the longitudinal direction and the width direction, respectively, and was drawn at 280 ° C.
After 1.5 minutes of drying and heat treatment, it was slowly cooled at a rate of 20 ° C./sec.
【００７９】このフィルムのビッカース硬度は３２、微
細突起高さは４８ｎｍ，密度は、８×１０6 個／ｍ
ｍ2 、フィルム中に含有されているアルミナ粒子の平均
凝集度は２５であった。また、磁性層面での高さ２Ｈ以
上の粗大突起の密度は、２８個／１００ｃｍ2 、非磁性
層面での高さ３Ｈ以上の粗大突起の密度は、６個／１０
０ｃｍ2 であった。The Vickers hardness of this film is 32, the height of fine projections is 48 nm, and the density is 8 × 10 6 pieces / m 2.
m 2, the average degree of aggregation of the alumina particles contained in the film was 25. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 28/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the non-magnetic layer surface is 6/10.
It was 0 cm 2 .
【００８０】次にこのフィルムの製膜時の金属ベルトと
接しない側の表面に、次の組成からなる磁性塗料を調製
し、グラビアロールで磁性層の厚みが２μｍとなるよう
に塗布し、硬化した後カレンダ処理を行った。Next, a magnetic coating material having the following composition was prepared on the surface of this film that was not in contact with the metal belt during film formation, and was coated with a gravure roll so that the thickness of the magnetic layer was 2 μm, and then cured. After that, calendar processing was performed.
【００８１】 磁性粉( メタル粉) ８０重量部 塩ビ系共重合体 １０重量部 ポリウレタン １０重量部 硬化剤 ５重量部 研磨剤 ５重量部 トルエン １００重量部 メチルエチルケトン １００重量部 次にこれをスリットし、磁気記録媒体とした。Magnetic powder (metal powder) 80 parts by weight PVC copolymer 10 parts by weight Polyurethane 10 parts by weight Curing agent 5 parts by weight Abrasive 5 parts by weight Toluene 100 parts by weight Methyl ethyl ketone 100 parts by weight Next, this is slit and magnetic It was used as a recording medium.
【００８２】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定すると共に良
好であった。Next, the durability, electromagnetic conversion characteristics, and runnability of this magnetic recording medium were measured by the above-mentioned methods, and the results were good.
【００８３】実施例２ 実施例１と同様の方法で得たポリマー溶液に対し、別に
Ｎ−メチルピロリドン中に分散した平均一次粒径４０ｎ
ｍ、モース硬度７．５のアルミナ粒子をポリマあたり
１．０重量％となるように添加し製膜溶液を調整した。
この製膜溶液を５μｍカットのフィルタ−を通した後、
ＳＵＳ製ベルト上に流延し、２００℃の熱風で２分間加
熱して溶媒を蒸発させ、自己保持性を得たフィルムをベ
ルトから連続的に剥離した。以下実施例１と同様な方法
で厚さ５μｍの芳香族ポリアミドフィルムを得た。Example 2 A polymer solution obtained by the same method as in Example 1 was separately dispersed in N-methylpyrrolidone to have an average primary particle size of 40 n.
Alumina particles having m and a Mohs hardness of 7.5 were added so as to be 1.0% by weight per polymer to prepare a film forming solution.
After passing this membrane forming solution through a 5 μm-cut filter,
The film was cast on a SUS belt, heated with hot air at 200 ° C. for 2 minutes to evaporate the solvent, and the film having self-holding property was continuously peeled from the belt. Then, an aromatic polyamide film having a thickness of 5 μm was obtained in the same manner as in Example 1.
【００８４】このフィルムのビッカース硬度は３３、微
細突起高さは３６ｎｍ，密度は、４×１０6 個／ｍ
ｍ2 、フィルム中に含有されているアルミナ粒子の平均
凝集度は１５であった。また、磁性層面での高さ２Ｈ以
上の粗大突起の密度は、２０個／１００ｃｍ2 、非磁性
層面での高さ３Ｈ以上の粗大突起の密度は、５個／１０
０ｃｍ2 であった。The Vickers hardness of this film is 33, the height of fine projections is 36 nm, and the density is 4 × 10 6 pieces / m 2.
m 2, the average degree of aggregation of the alumina particles contained in the film was 15. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 20/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the non-magnetic layer surface is 5/10.
It was 0 cm 2 .
【００８５】このフィルムに磁性層を形成後、実施例１
と同様に磁気記録媒体とした。After forming a magnetic layer on this film, Example 1
A magnetic recording medium was prepared in the same manner as in.
【００８６】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定すると共に良
好であった。Next, the durability, electromagnetic conversion characteristics, and runnability of this magnetic recording medium were measured by the methods described above, and the results were good.
【００８７】実施例３ 実施例１と同様の方法で得たポリマー溶液に対し、別に
Ｎ−メチルピロリドン中に分散した平均一次粒径１６ｎ
ｍ、モース硬度７のシリカ粒子をポリマあたり４．０重
量％となるように添加し製膜溶液を調整した。この製膜
溶液を５μｍカットのフィルタ−を通した後、ＳＵＳ製
のベルト上に流延し、２００℃の熱風で２分間加熱して
溶媒を蒸発させ、自己保持性を得たフィルムをベルトか
ら連続的に剥離した。以下実施例１と同様な方法で厚さ
５μｍの芳香族ポリアミドフィルムを得た。Example 3 A polymer solution obtained by the same method as in Example 1 was dispersed in N-methylpyrrolidone, and the average primary particle size was 16 n.
Silica particles having m and Mohs hardness of 7 were added to the polymer so as to be 4.0% by weight to prepare a film forming solution. This film-forming solution was passed through a 5 μm-cut filter, cast on a SUS belt, heated with hot air at 200 ° C. for 2 minutes to evaporate the solvent, and a film having self-holding property was removed from the belt. It peeled continuously. Then, an aromatic polyamide film having a thickness of 5 μm was obtained in the same manner as in Example 1.
【００８８】このフィルムのビッカース硬度は３５、微
細突起高さは８０ｎｍ，密度は、５×１０7 個／ｍ
ｍ2 、フィルム中に含有されているシリカ粒子の平均凝
集度は２０であった。また、磁性層面での高さ２Ｈ以上
の粗大突起の密度は、５０個／１００ｃｍ2 、非磁性層
面での高さ３Ｈ以上の粗大突起の密度は、１２個／１０
０ｃｍ2 であった。The Vickers hardness of this film is 35, the height of fine projections is 80 nm, and the density is 5 × 10 7 pieces / m 2.
m 2 , the average degree of aggregation of silica particles contained in the film was 20. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 50/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the nonmagnetic layer surface is 12/10.
It was 0 cm 2 .
【００８９】このフィルムを実施例１と同様に磁性層を
形成し、さらにこの磁性層面の反対側に０．５μｍのバ
ック層を設けた。バックコート層用塗料の組成は次の通
りである。A magnetic layer was formed on this film in the same manner as in Example 1, and a back layer of 0.5 μm was provided on the side opposite to the magnetic layer surface. The composition of the coating material for the back coat layer is as follows.
【００９０】 カーボンブラック １００重量部 塩ビ系共重合体 ２０重量部 ポリウレタン ５０重量部 トルエン ２００重量部 メチルエチルケトン ４００重量部 ついでこれをスリットし、磁気記録媒体とした。Carbon black 100 parts by weight PVC copolymer 20 parts by weight Polyurethane 50 parts by weight Toluene 200 parts by weight Methyl ethyl ketone 400 parts by weight Then, this was slit to obtain a magnetic recording medium.
【００９１】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定すると共に良
好であった。Next, the durability, electromagnetic conversion characteristics, and runnability of this magnetic recording medium were measured by the above-mentioned methods and were good.
【００９２】実施例４ ＮＭＰに芳香族ジアミン成分として６０モル％に相当す
るパラフェニレンジアミンと、４０モル％に相当する
４、４’−ジアミノジフェニルエ−テルとを溶解させ、
これに１００モル％に相当する２−クロルテレフタル酸
クロリドを添加し、２時間撹拌して重合を完了した。こ
れを水酸化リチウムで中和して、ポリマ濃度１０重量
％、粘度３０００ポイズの芳香族ポリアミド溶液を得
た。ついで、この溶液に、平均一次粒径１６ｎｍ、モー
ス硬度が７．５であるアルミナ粒子をポリマ当たり２．
５重量％添加し、撹拌した。Example 4 Paraphenylenediamine corresponding to 60 mol% as an aromatic diamine component and 4,4′-diaminodiphenyl ether corresponding to 40 mol% were dissolved in NMP,
To this, 100 mol% of 2-chloroterephthalic acid chloride was added and stirred for 2 hours to complete the polymerization. This was neutralized with lithium hydroxide to obtain an aromatic polyamide solution having a polymer concentration of 10% by weight and a viscosity of 3000 poise. Then, alumina particles having an average primary particle size of 16 nm and a Mohs hardness of 7.5 were added to the solution in an amount of 2.
5 wt% was added and stirred.
【００９３】このポリマ溶液を５μｍカットのフィルタ
−を通した後、ＳＵＳ製のベルト上に流延し、１８０℃
の熱風で２分間加熱して溶媒を蒸発させ、自己保持性を
得たフィルムをベルトから連続的に剥離した。以下実施
例１と同様な方法で厚さ５μｍの芳香族ポリアミドフィ
ルムを得た。This polymer solution was passed through a 5 μm-cut filter and then cast on a SUS belt at 180 ° C.
The film was heated for 2 minutes with hot air to evaporate the solvent, and the self-supporting film was continuously peeled from the belt. Then, an aromatic polyamide film having a thickness of 5 μm was obtained in the same manner as in Example 1.
【００９４】このフィルムのビッカース硬度は２７、微
細突起高さは４５ｎｍ，密度は、３×１０7 個／ｍ
ｍ2 、フィルム中に含有されているアルミナ粒子の平均
凝集度は２５であった。また、磁性層面での高さ２Ｈ以
上の粗大突起の密度は、４６個／１００ｃｍ2 、非磁性
層面での高さ３Ｈ以上の粗大突起の密度は、９個／１０
０ｃｍ2 であった。The Vickers hardness of this film is 27, the height of fine projections is 45 nm, and the density is 3 × 10 7 pieces / m 2.
m 2, the average degree of aggregation of the alumina particles contained in the film was 25. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 46/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the nonmagnetic layer surface is 9/10.
It was 0 cm 2 .
【００９５】このフィルムを実施例１と同様に磁性層を
形成後、磁気記録媒体とした。A magnetic layer was formed on this film in the same manner as in Example 1 and used as a magnetic recording medium.
【００９６】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定すると共に良
好であった。Next, the durability, electromagnetic conversion characteristics, and runnability of this magnetic recording medium were measured by the above-mentioned methods and were good.
【００９７】実施例５ ＮＭＰに芳香族ジアミン成分として１００モル％に相当
する２−クロルパラフェニレンジアミンを溶解させ、こ
れに１００モル％に相当する３，３’，４，４’−ビフ
ェニルテトラカルボン酸二無水物を添加し重合してポリ
アミド酸溶液を得た。この溶液に、別にＮ−メチルピロ
リドン中に分散した平均一次粒径１６ｎｍ、モース硬度
７のシリカ粒子をポリマあたり３．０重量％となるよう
に添加し製膜溶液を調整した。Example 5 As an aromatic diamine component, 100 mol% of 2-chloroparaphenylenediamine was dissolved in NMP, and 100 mol% of 3,3 ', 4,4'-biphenyltetracarboxylic acid was dissolved in the solution. An acid dianhydride was added and polymerized to obtain a polyamic acid solution. To this solution, silica particles having an average primary particle size of 16 nm and a Mohs hardness of 7 dispersed in N-methylpyrrolidone were separately added so as to be 3.0% by weight per polymer to prepare a film forming solution.
【００９８】このポリマ溶液を５μｍカットのフィルタ
−を通した後、ＳＵＳ製のベルト上に流延し、１５０℃
の熱風で自己保持性を持つまで乾燥し、ベルトから連続
的に剥離した。次に４２０℃のテンタ−で熱処理を行な
った後、２０℃／秒の速度で徐冷した。延伸倍率はＭ
Ｄ、ＴＤともに１．１倍、厚みは６μｍであった。This polymer solution was passed through a 5 μm-cut filter and then cast on a SUS belt at 150 ° C.
It was dried with hot air until it was self-retaining and continuously peeled from the belt. Next, after heat treatment with a tenter at 420 ° C., it was gradually cooled at a rate of 20 ° C./sec. Draw ratio is M
Both D and TD were 1.1 times and the thickness was 6 μm.
【００９９】このフィルムのビッカース硬度は３５、微
細突起高さは６３ｎｍ，密度は、６×１０7 個／ｍ
ｍ2 、フィルム中に含有されているシリカ粒子の平均凝
集度は２０であった。また、磁性層面での高さ２Ｈ以上
の粗大突起の密度は、６０個／１００ｃｍ2 、非磁性層
面での高さ３Ｈ以上の粗大突起の密度は、１０個／１０
０ｃｍ2 であった。The Vickers hardness of this film is 35, the height of fine protrusions is 63 nm, and the density is 6 × 10 7 pieces / m 2.
m 2 , the average degree of aggregation of silica particles contained in the film was 20. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 60/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the nonmagnetic layer surface is 10/10.
It was 0 cm 2 .
【０１００】このフィルムを実施例１と同様に磁性層を
形成後、磁気記録媒体とした。A magnetic layer was formed on this film in the same manner as in Example 1 and used as a magnetic recording medium.
【０１０１】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定すると共に良
好であった。Next, with respect to this magnetic recording medium, the durability, electromagnetic conversion characteristics, and runnability were measured by the above-mentioned methods, and the results were good.
【０１０２】比較例１ 実施例１と同様の方法で得たポリマ溶液に対し、平均一
次粒径１６ｎｍ、モース硬度が７．５であるアルミナ粒
子をポリマ当たり０．０５重量％添加し、撹拌した。こ
の溶液を５μｍカットのフィルタ−を通した後、ＳＵＳ
製のベルト上に流延し、２３０℃の熱風で溶媒を蒸発さ
せ、自己保持性を得たフィルムをベルトから連続的に剥
離した。以下実施例１と同様な方法で厚さ５μｍの芳香
族ポリアミドフィルムを得た。Comparative Example 1 Alumina particles having an average primary particle size of 16 nm and a Mohs hardness of 7.5 were added to a polymer solution obtained by the same method as in Example 1 in an amount of 0.05% by weight with respect to the polymer, and the mixture was stirred. . After passing this solution through a 5 μm-cut filter, SUS
The film was cast on a belt made of resin and the solvent was evaporated with hot air at 230 ° C., and the film having self-holding property was continuously peeled from the belt. Then, an aromatic polyamide film having a thickness of 5 μm was obtained in the same manner as in Example 1.
【０１０３】このフィルムのビッカース硬度は３０、微
細突起高さは１８ｎｍ，密度は、３×１０3 個／ｍ
ｍ2 、フィルム中に含有されているアルミナ粒子の平均
凝集度は６であった。また、磁性層面での高さ２Ｈ以上
の粗大突起の密度は、１１個／１００ｃｍ2 、非磁性層
面での高さ３Ｈ以上の粗大突起の密度は、１個／１００
ｃｍ2 であった。The Vickers hardness of this film is 30, the height of fine projections is 18 nm, and the density is 3 × 10 3 pieces / m 2.
m 2, the average degree of aggregation of the alumina particles contained in the film was 6. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 11/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the nonmagnetic layer surface is 1/100.
cm 2 .
【０１０４】このフィルムを実施例１と同様に磁性層を
形成後、磁気記録媒体とした。A magnetic layer was formed on this film in the same manner as in Example 1 and used as a magnetic recording medium.
【０１０５】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定を行ったが、
走行性、耐スクラッチ性が非常に悪かった。Next, with respect to this magnetic recording medium, the durability, electromagnetic conversion characteristics and running property were measured by the above-mentioned methods.
The runnability and scratch resistance were very poor.
【０１０６】比較例２ 実施例１と同様の方法で得たポリマ溶液に対し、平均一
次粒径１６ｎｍ、モース硬度が７であるシリカ粒子をポ
リマ当たり６．０重量％添加し、撹拌した。ついでこの
溶液を５μｍカットのフィルタ−を通した後、ＳＵＳ製
のベルト上に流延し、実施例１と同様な方法で厚さ５μ
ｍの芳香族ポリアミドフィルムを得た。このフィルムの
ビッカース硬度は３６、微細突起高さは１２０ｎｍ，密
度は、３×１０9 個／ｍｍ2 、フィルム中に含有されて
いるシリカ粒子の平均凝集度は１２０であった。また、
磁性層面での高さ２Ｈ以上の粗大突起の密度は、１２３
０個／１００ｃｍ2 、非磁性層面での高さ３Ｈ以上の粗
大突起の密度は、４２５個／１００ｃｍ2 であった。Comparative Example 2 To a polymer solution obtained by the same method as in Example 1, silica particles having an average primary particle size of 16 nm and a Mohs hardness of 7 were added in an amount of 6.0% by weight based on the polymer and stirred. Then, this solution was passed through a 5 μm-cut filter, then cast on a SUS belt, and the thickness was 5 μm in the same manner as in Example 1.
m aromatic polyamide film was obtained. The Vickers hardness of this film was 36, the height of fine projections was 120 nm, the density was 3 × 10 9 particles / mm 2 , and the average degree of aggregation of silica particles contained in the film was 120. Also,
The density of coarse protrusions having a height of 2H or more on the magnetic layer surface is 123
0/100 cm 2, the density of the higher height 3H large protrusions of a non-magnetic layer surface was 425/100 cm 2.
【０１０７】このフィルムを、実施例１と同様に磁性層
を形成後、磁気記録媒体とした。This film was used as a magnetic recording medium after forming a magnetic layer in the same manner as in Example 1.
【０１０８】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定を行ったが、
走行性は良好なものの、発生した粗大突起によるドロッ
プアウトが著しく、また磁性層面には削れ傷が見られ、
実用には供せないものであった。Next, the durability, electromagnetic conversion characteristics, and running property of this magnetic recording medium were measured by the above-mentioned methods.
Although the running property is good, the dropout due to the generated large protrusions is remarkable, and the magnetic layer surface is scratched and scratched.
It was not suitable for practical use.
【０１０９】比較例３ 実施例１と同様の方法で得たポリマ溶液に平均一次粒径
３００ｎｍ、モース硬度が７．５であるアルミナ粒子を
ポリマ当たり２重量％添加し、撹拌した。ついでこの溶
液を、５μｍカットのフィルタ−を通した後、ＳＵＳ製
のベルト上に流延し、実施例１と同様な方法で厚さ５μ
ｍの芳香族ポリアミドフィルムを得た。このフィルムの
ビッカース硬度は３１、微細突起高さは２５０ｎｍ，密
度は、５×１０4 個／ｍｍ2 、フィルム中に含有されて
いるアルミナ粒子の平均凝集度は２０であった。また、
磁性層面での高さ２Ｈ以上の粗大突起の密度は、７２５
個／１００ｃｍ2 、非磁性層面での高さ３Ｈ以上の粗大
突起の密度は、２８４個／１００ｃｍ2 であった。Comparative Example 3 To a polymer solution obtained by the same method as in Example 1, 2% by weight of alumina particles having an average primary particle size of 300 nm and a Mohs hardness of 7.5 were added per polymer and stirred. Then, this solution was passed through a 5 μm-cut filter, cast on a SUS belt, and treated in the same manner as in Example 1 to give a thickness of 5 μm.
m aromatic polyamide film was obtained. The Vickers hardness of this film was 31, the height of fine protrusions was 250 nm, the density was 5 × 10 4 particles / mm 2 , and the average degree of aggregation of the alumina particles contained in the film was 20. Also,
The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 725.
Pieces / 100 cm 2, the density of the higher height 3H large protrusions of a non-magnetic layer surface was 284/100 cm 2.
【０１１０】このフィルムを実施例１と同様に磁性層を
形成後、磁気記録媒体とした。A magnetic layer was formed on this film in the same manner as in Example 1 and used as a magnetic recording medium.
【０１１１】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定を行ったが、
磁性層には欠落がみられ、また、発生した粗大突起によ
るドロップアウトが著しく、実用には供せないものであ
った。Next, with respect to this magnetic recording medium, the durability, electromagnetic conversion characteristics and running property were measured by the above-mentioned methods.
The magnetic layer was found to be lacking, and the large protrusions caused significant dropout, which was not practical.
【０１１２】比較例４ 実施例１と同様の方法で得たポリマ溶液に、別にＮ−メ
チルピロリドン中に分散した平均一次粒径１６ｎｍ、モ
ース硬度３．０の炭酸カルシウム粒子をポリマあたり
０．５重量％となるように添加し製膜溶液を調整した。
ついで、この製膜溶液を５μｍカットのフィルタ−を通
した後、ＳＵＳ製のベルト上に流延し、実施例１と同様
な方法で厚さ５μｍの芳香族ポリアミドフィルムを得
た。Comparative Example 4 Calcium carbonate particles having an average primary particle size of 16 nm and a Mohs hardness of 3.0 dispersed in N-methylpyrrolidone were added to a polymer solution obtained by the same method as in Example 1 in an amount of 0.5 per polymer. A film-forming solution was prepared by adding it so that the amount of the solution would be wt%.
Then, this film-forming solution was passed through a 5 μm-cut filter and then cast on a SUS belt to obtain a 5 μm-thick aromatic polyamide film in the same manner as in Example 1.
【０１１３】このフィルムのビッカース硬度は３０、微
細突起高さは４０ｎｍ，密度は、２×１０5 個／ｍ
ｍ2 、フィルム中に含有されている炭酸カルシウム粒子
の平均凝集度は２０であった。また、磁性層面での高さ
２Ｈ以上の粗大突起の密度は、３０個／１００ｃｍ2 、
非磁性層面での高さ３Ｈ以上の粗大突起の密度は、４個
／１００ｃｍ2 であった。The Vickers hardness of this film is 30, the height of fine projections is 40 nm, and the density is 2 × 10 5 pieces / m 2.
m 2, the average degree of aggregation of the calcium carbonate particles contained in the film was 20. Further, the density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 30/100 cm 2 ,
The density of coarse protrusions having a height of 3H or more on the surface of the non-magnetic layer was 4/100 cm 2 .
【０１１４】このフィルムを実施例１と同様に磁性層を
形成後、磁気記録媒体とした。A magnetic layer was formed on this film in the same manner as in Example 1 and used as a magnetic recording medium.
【０１１５】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定を行ったが、
走行性、耐スクラッチ性、耐削れ性共に悪く使いものに
ならないものであった。Next, with respect to this magnetic recording medium, the durability, electromagnetic conversion characteristics and running property were measured by the above-mentioned methods.
The runnability, scratch resistance, and abrasion resistance were poor and unusable.
【０１１６】比較例５ ＮＭＰに芳香族ジアミン成分として５０モル％に相当す
るメタフェニレンジアミンと、５０モル％に相当する
４，４’−ジアミノジフェニルエ−テルとを溶解させ、
これに１００モル％に相当するイソフタル酸クロリドを
添加し重合してポリマ溶液を得た。この溶液に、平均一
次粒径１６ｎｍ、モース硬度が７．５であるアルミナ粒
子をポリマ当たり２重量％添加し、撹拌した。Comparative Example 5 Metaphenylene diamine corresponding to 50 mol% as an aromatic diamine component and 4,4'-diaminodiphenyl ether corresponding to 50 mol% were dissolved in NMP,
Isophthalic chloride corresponding to 100 mol% was added thereto and polymerized to obtain a polymer solution. Alumina particles having an average primary particle size of 16 nm and a Mohs hardness of 7.5 were added to this solution in an amount of 2% by weight with respect to the polymer, and the mixture was stirred.
【０１１７】ついで、このポリマ溶液を５μｍカットの
フィルタ−を通した後、ＳＵＳ製のベルト上に流延し、
１８０℃の熱風で自己保持性を持つまで乾燥し、ベルト
から連続的に剥離した。次に４２０℃のテンタ−で熱処
理を行なった後、２０℃／秒の速度で徐冷した。延伸倍
率はＭＤ、ＴＤともに１．１倍、厚みは８μｍであっ
た。Then, this polymer solution was passed through a 5 μm-cut filter and then cast on a SUS belt,
It was dried with hot air at 180 ° C. until it had self-holding property, and continuously peeled from the belt. Next, after heat treatment with a tenter at 420 ° C., it was gradually cooled at a rate of 20 ° C./sec. The draw ratio was 1.1 times for both MD and TD, and the thickness was 8 μm.
【０１１８】このフィルムのビッカース硬度は１８、微
細突起高さは４３ｎｍ，密度は、８×１０6 個／ｍ
ｍ2 、フィルム中に含有されているアルミナ粒子の平均
凝集度は２５であった。また、磁性層面での高さ２Ｈ以
上の粗大突起の密度は、３７個／１００ｃｍ2 、非磁性
層面での高さ３Ｈ以上の粗大突起の密度は、５個／１０
０ｃｍ2 であった。The Vickers hardness of this film is 18, the fine protrusion height is 43 nm, and the density is 8 × 10 6 pieces / m 2.
m 2, the average degree of aggregation of the alumina particles contained in the film was 25. The density of coarse protrusions with a height of 2H or more on the magnetic layer surface is 37/100 cm 2 , and the density of coarse protrusions with a height of 3H or more on the non-magnetic layer surface is 5/10.
It was 0 cm 2 .
【０１１９】このフィルムを、実施例１と磁性層を形成
後、磁気記録媒体とした。This film was used as a magnetic recording medium after forming the magnetic layer in Example 1.
【０１２０】次にこの磁気記録媒体について、前記の方
法で耐久性、電磁変換特性、走行性を測定を行ったが、
耐スクラッチ性、耐削れ性が非常に悪く使いものになら
ないものであった。また、電磁変換特性はこの評価では
良好であったが、モニター中ドロップアウトと思われる
現象が多数認められた。Next, with respect to this magnetic recording medium, the durability, electromagnetic conversion characteristics and running property were measured by the above-mentioned methods.
The scratch resistance and abrasion resistance were very poor and it was unusable. In addition, although the electromagnetic conversion characteristics were good in this evaluation, many phenomena that seemed to be dropouts during monitoring were observed.
【０１２１】このため、磁気記録媒体作製後にテープロ
ールの中心部分と辺周部分から磁気テープをサンプリン
グし、表面の微細突起高さを測定すると、巻張力に起因
する磁気テープ裏面の突起の転写によって、微細突起高
さに１５ｎｍの差が生じていた。Therefore, when the magnetic tape is sampled from the central portion and the peripheral portion of the tape roll after the magnetic recording medium is manufactured and the height of the fine protrusions on the surface is measured, the protrusion on the back surface of the magnetic tape due to winding tension is transferred. The difference in height of the fine protrusions was 15 nm.
【０１２２】[0122]
【表１】 [Table 1]
【表２】 [Table 2]
【０１２３】[0123]
【発明の効果】本発明は、耐熱性、機械特性に優れた芳
香族ポリアミドあるいは芳香族ポリイミドからなる基材
フィルムを使用し、含有される粒子の構成、表面特性を
規定することにより高速度、繰り返し走行などの厳しい
条件下でも表面が傷ついたり削れたりし難く、走行性、
出力特性に優れ、同時に耐久性に優れた磁気記録媒体が
得られたものである。また、これらの優れた特性により
磁気記録媒体製造時においても走行性、耐熱性が向上し
加工生産性の向上も可能である。INDUSTRIAL APPLICABILITY The present invention uses a base film made of an aromatic polyamide or an aromatic polyimide having excellent heat resistance and mechanical properties. Even under severe conditions such as repeated running, the surface is difficult to be scratched or scraped, running performance,
A magnetic recording medium having excellent output characteristics and, at the same time, excellent durability was obtained. Further, due to these excellent characteristics, the running property and heat resistance are improved even during the production of the magnetic recording medium, and the processing productivity can be improved.
Claims (1)
ミドからなる基材フィルムの片面に磁性層を設けてなる
磁気記録媒体であって、該基材フィルムには、平均一次
粒径が５〜２５０ｎｍ、平均凝集度が５〜１００、モー
ス硬度が６〜１０の微粒子を０．１〜５重量％含有し、
かつ非磁性層側には高さ３Ｈ以上の粗大突起を２〜１０
０個／１００ｃｍ2 有し、かつ該基材フィルムのビッカ
ース硬度が２０以上であることを特徴とする磁気記録媒
体。1. A magnetic recording medium comprising a base film made of aromatic polyamide or aromatic polyimide and a magnetic layer provided on one side thereof, wherein the base film has an average primary particle size of 5 to 250 nm, Contains 0.1 to 5% by weight of fine particles having a cohesion of 5 to 100 and a Mohs hardness of 6 to 10,
In addition, 2 to 10 coarse protrusions with a height of 3H or more are provided on the nonmagnetic layer side.
A magnetic recording medium having 0 pieces / 100 cm 2 and having a Vickers hardness of 20 or more in the base film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29122094A JPH08147671A (en) | 1994-11-25 | 1994-11-25 | Magnetic recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29122094A JPH08147671A (en) | 1994-11-25 | 1994-11-25 | Magnetic recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08147671A true JPH08147671A (en) | 1996-06-07 |
Family
ID=17766033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29122094A Pending JPH08147671A (en) | 1994-11-25 | 1994-11-25 | Magnetic recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08147671A (en) |
-
1994
- 1994-11-25 JP JP29122094A patent/JPH08147671A/en active Pending
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