JPH0346121A - Magnetic recording medium - Google Patents
Magnetic recording mediumInfo
- Publication number
- JPH0346121A JPH0346121A JP18213389A JP18213389A JPH0346121A JP H0346121 A JPH0346121 A JP H0346121A JP 18213389 A JP18213389 A JP 18213389A JP 18213389 A JP18213389 A JP 18213389A JP H0346121 A JPH0346121 A JP H0346121A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic layer
- magnetic
- parts
- recording medium
- 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
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 146
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 150000004715 keto acids Chemical class 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- -1 sulfuric acid ester Chemical class 0.000 claims description 51
- 150000002430 hydrocarbons Chemical group 0.000 claims description 40
- 230000005294 ferromagnetic effect Effects 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000010409 thin film Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 72
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- 238000000576 coating method Methods 0.000 description 51
- 150000001875 compounds Chemical class 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
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- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 11
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- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
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- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000005496 phosphonium group Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OXCMYAYHXIHQOA-UHFFFAOYSA-N potassium;[2-butyl-5-chloro-3-[[4-[2-(1,2,4-triaza-3-azanidacyclopenta-1,4-dien-5-yl)phenyl]phenyl]methyl]imidazol-4-yl]methanol Chemical compound [K+].CCCCC1=NC(Cl)=C(CO)N1CC1=CC=C(C=2C(=CC=CC=2)C2=N[N-]N=N2)C=C1 OXCMYAYHXIHQOA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical class [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/71—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the lubricant
Landscapes
- Paints Or Removers (AREA)
- Magnetic Record Carriers (AREA)
- Lubricants (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、非磁性支持体上に強磁性粉末を結合剤樹脂に
分散してなる磁性層を有する磁気記録媒体に関し、特に
広範囲の温湿度条件において走行性及び耐久性に優れた
磁気記録媒体に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a magnetic recording medium having a magnetic layer formed by dispersing ferromagnetic powder in a binder resin on a non-magnetic support, and particularly relates to a magnetic recording medium that can be used over a wide range of temperature and humidity. The present invention relates to a magnetic recording medium that has excellent running properties and durability under various conditions.
（従来技術及びその問題点）
近年、磁気記録媒体に対しては、高密度記録への要求が
高まりその対応手段として、磁性層の表面を平滑にする
ことが試みられている
磁性層の表面を平滑にすると、磁気記録媒体を走行させ
たときに磁性層と装置系との摩擦係数が増大してその結
果、使用しているうちに走行に支障をきたしたり、磁性
層が損傷を受け、ドロップアウトが増大したり、さらに
は磁性層が剥離するようなこともあった。(Prior art and its problems) In recent years, there has been an increasing demand for high-density recording in magnetic recording media, and as a means to meet this demand, attempts have been made to smooth the surface of the magnetic layer. If it is made smooth, the coefficient of friction between the magnetic layer and the device system will increase when the magnetic recording medium is run, resulting in problems with running or damage to the magnetic layer, resulting in drops. In some cases, the out-of-out ratio increased, and even the magnetic layer peeled off.
特に、高密度記録用媒体として期待され近年その開発実
用化が促進されている強磁性金属薄膜を磁性層とするい
わゆる金属薄膜型磁気記録媒体は、磁性層の表面は非常
に平滑であるので前記の問題はより一層大きなものとな
る。In particular, so-called metal thin film magnetic recording media, which have a magnetic layer made of a ferromagnetic metal thin film, which is expected to be a high-density recording medium and whose development and practical application have been promoted in recent years, have a very smooth surface. The problem becomes even bigger.
以上の問題に対処するために、磁性層の表面もしくは内
部に、脂肪酸、脂肪酸エステル、炭化水素、シリコーン
化合物等の潤滑剤を含有させることが試みられている。In order to deal with the above problems, attempts have been made to incorporate lubricants such as fatty acids, fatty acid esters, hydrocarbons, and silicone compounds into the surface or inside of the magnetic layer.
また、最近ＶＴＲやパーソナルコンピューターワードプ
ロセッサーの普及にともない、民生用にフロッピーディ
スクドライブ装置が一般化するにいたり、磁気記録媒体
の使用条件も低温下での使用、高温高湿度下での使用と
広きにわたるようになってきた。In addition, with the recent spread of VTRs and personal computer word processors, floppy disk drive devices have become commonplace for consumer use, and the usage conditions for magnetic recording media have widened from use at low temperatures to use at high temperatures and high humidity. It's starting to look like this.
従って、磁気記録媒体は幅広い環境条件下でその走行耐
久性が変動することがないようにすることが重要になっ
てきた。Therefore, it has become important to ensure that the running durability of magnetic recording media does not change under a wide range of environmental conditions.
金属薄膜型磁気記録媒体においても、フッ素オイルのひ
とつであるパーフルオロポリエーテルを利用することが
、種々検討されており、例えば、米国特許公報４２６７
２３８号、同４２６８５５６号、西ドイツ特許公報３０
００５８３号、特公昭６０−１０３６８号公報等には、
分子末端を極性基で変性することにより磁性層の表面に
対する固着性を高めたパーフルオロポリエーテルが開示
されている。Various studies have been conducted on the use of perfluoropolyether, which is a type of fluorine oil, in metal thin film magnetic recording media. For example, U.S. Pat. No. 4,267
No. 238, No. 4268556, West German Patent Publication 30
No. 00583, Special Publication No. 60-10368, etc.,
A perfluoropolyether has been disclosed that has improved adhesion to the surface of a magnetic layer by modifying the molecular terminal with a polar group.
また、特開昭６１−１１３１２６号公報、米国特許公報
４６８２３７８号に開示されているように極性基を有す
るパーフルオロポリエーテルと極性基を有しないパーフ
ルオロポリエーテルとを併用することにより磁性層への
固着性と良好な潤滑性を両立させる試みもなされている
。Furthermore, as disclosed in JP-A-61-113126 and US Pat. No. 4,682,378, it is possible to form a magnetic layer by using a perfluoropolyether having a polar group and a perfluoropolyether having no polar group together. Attempts have also been made to achieve both adhesion and good lubricity.
しかしながら、前記従来の潤滑剤では、このような要求
に十分対処できなかった。However, the conventional lubricants have not been able to adequately meet these demands.
（発明が解決しようとする問題点）
本発明は、前記従来技術の問題点にかんがみなされたも
のであり、特に、低温から高温高温までの幅広い環境条
件下での走行耐久性に優れた磁気記録媒体を提供するこ
とを目的としている。(Problems to be Solved by the Invention) The present invention has been made in view of the problems of the prior art described above, and is particularly directed to magnetic recording that has excellent running durability under a wide range of environmental conditions from low temperatures to high temperatures. The purpose is to provide a medium.
〈問題点を解決する手段）
前記本発明の目的は、非磁性支持体上に磁性層を有する
磁気記録媒体において、炭化水素基を有するオキソ酸ま
たはその塩とフッ素化ポリエーテルとが該磁性層表面も
しくは内部に保持されていることを特徴とする磁気記録
媒体により連成される。<Means for Solving the Problems> An object of the present invention is to provide a magnetic recording medium having a magnetic layer on a non-magnetic support, in which an oxo acid having a hydrocarbon group or a salt thereof and a fluorinated polyether are bonded to the magnetic layer. It is coupled by a magnetic recording medium, which is characterized by being held on the surface or inside.
本発明の磁気記録媒体の磁性層表面もしくは内部に保持
されている炭化水素基を有するオキソ酸またはその塩は
、磁性層に対する固着性が高く、かつ磁性層の摩擦低減
効果も大きい、そして、フッ素化ポリエーテルは、広い
温度範囲で流動性があり、かつ磁性層表面との親和性が
適度であるため良好な潤滑性を示す。The oxoacid or its salt having a hydrocarbon group retained on or inside the magnetic layer of the magnetic recording medium of the present invention has high adhesion to the magnetic layer and has a large friction reduction effect on the magnetic layer, and Chemical polyether exhibits good lubricity because it has fluidity over a wide temperature range and has appropriate affinity with the surface of the magnetic layer.
従って、本発明の磁気記録媒体では、その磁性層表面に
前記の特徴を有する２種の化合物を保持させたことによ
り従来の磁気記録媒体では見られなかった、広い環境条
件下においてその走行耐久性を良好なものとすることが
できた。Therefore, the magnetic recording medium of the present invention has running durability under a wide range of environmental conditions, which has not been seen in conventional magnetic recording media, by retaining two types of compounds having the above-mentioned characteristics on the surface of the magnetic layer. I was able to make it a good one.
本発明の磁気記録媒体において、前記２種の化合物を磁
性層に保持させる場合、磁性層表面に保持させる場合と
、磁性層内部に保持させる場合とがあるが、磁気記録媒
体が強磁性粉末と結合剤樹脂とを主体とした磁性層を有
するいわゆる塗布型である時は、磁性層の表面に保持さ
せてまた内部に保持させてもよい、磁気記録媒体が、強
磁性金属１１１１Ｉｌの磁性層を有するいわゆる金属薄
膜型磁気記録媒体である場合は、通常、その磁性層内部
に保持させる。In the magnetic recording medium of the present invention, when the two types of compounds are held in the magnetic layer, there are cases where they are held on the surface of the magnetic layer and cases where they are held inside the magnetic layer. When the magnetic recording medium is a so-called coating type having a magnetic layer mainly composed of a binder resin, the magnetic recording medium has a magnetic layer made of ferromagnetic metal 1111Il, which may be held on the surface of the magnetic layer or held inside the magnetic layer. In the case of a so-called metal thin film type magnetic recording medium, it is usually held within its magnetic layer.
本発明の磁気記録媒体の前記特徴は、前記炭化水素基を
有するオキソ酸またはその塩が、炭化水素置換ａ酸エス
テルもしくは炭化水素系スルホン酸またはこれらの塩で
ある場合特に顕著である。The above characteristics of the magnetic recording medium of the present invention are particularly remarkable when the hydrocarbon group-containing oxoacid or its salt is a hydrocarbon-substituted a-acid ester, a hydrocarbon-based sulfonic acid, or a salt thereof.
更に、磁性層が強磁性金属薄膜である場合特に効果的で
ある。Furthermore, it is particularly effective when the magnetic layer is a ferromagnetic metal thin film.
本発明の磁気記録媒体に使用される前記炭化水素基を有
するオキソ酸またはその塩としては、ＲＣＯＯＨ、ＲＣ
ＯＯＭ 、ＲＯＣＯＯＨ，ＲＯＣＯＯｌｌ、Ｒ５０ｓＨ
。The hydrocarbon group-containing oxoacid or its salt used in the magnetic recording medium of the present invention includes RCOOH, RC
OOM, ROCOOH, ROCOOll, R50sH
.
Ｒ３０５Ｍ 、 ＲＯ５ＯｓＨＳＲＯ３ＯｓＦＩＳＲＰ
ＯＪｘ、ＲＰＯＪｚ、ＲＰＯ３ＨＭ、ＲＯＰＯＪ富、Ｒ
ＯＰＯＪ＊ 、ＲＯＰＯ３ＨＭ 、 Ｒ５０Ｊ、Ｒ５０
Ｊ 、ＲＯ３ＯＪ、 ＲＯ３Ｏ，Ｍ、Ｒ５ＪＭ 、ＲＰ
Ｏ２Ｈｚ、ＲＰ０２Ｍｇ、ＲＦｅ５肝、ＲＯＰＯ２Ｈｘ
、 ＲＯＰ０２Ｍｉ 、ＲＯＰＯ２１１Ｍ、ＲＢＯＪ
＊、ＲＢＯ＊Ｍｔ、ＲＢＯ，ｆｌＭ、ＲＯＢＯｘＭｚ
、ＲＯＢＯｘＭｚ、ＲＯＢＯ！ＩＮ等が挙げられる。こ
こでＲは炭化水素基、Ｍは水素以外では、例えばＩ’Ｊ
ａ 、Ｋ 、、Ｌ ｓ ＳＮＨ４ＺｎＬ＋ｙＲ）
％ Ｂ ｅ （１／ｌ） 、 Ｍｇ
Ｈ／１） ｓ Ｃａ （ｔ／ｚ）Ｓ ｒ
＜Ｉｉ畳ｒ ％ 、ＣＯｈｉｔ＞〜Ｎ ｉ ｕｚｔ＋
、 Ｃｕ ＜＋／ｎ等の原子及び−級アンモニウム、二
級アンモニウム、三級アンモニウム、四級アンモニウム
等の原子団である。R305M, RO5OsHSRO3OsFISRP
OJx, RPOJz, RPO3HM, ROPOJ Tomi, R
OPOJ*, ROPO3HM, R50J, R50
J, RO3OJ, RO3O,M, R5JM, RP
O2Hz, RP02Mg, RFe5 liver, ROPO2Hx
, ROP02Mi, ROPO211M, RBOJ
*, RBO*Mt, RBO, flM, ROBOxMz
, ROBOxMz, ROBO! IN etc. are mentioned. Here, R is a hydrocarbon group, M is other than hydrogen, for example, I'J
a , K , , L s SNH4ZnL+yR)
% B e (1/l), Mg
H/1) s Ca (t/z) S r
<Ii tatami r%, COhit>~N i uzt+
, Cu <+/n, and atomic groups such as −-class ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium.
そして、更に具体的には、以下の化学式（１）〜（３５
）の化合物等が使用できる。すなわち、ＣＨｚ（ＣＨｉ
）＋ｏＣＯＯＨ（１） 、ＣＨｓ（ＣＦｌｇ）＋ｚＣＯ
Ｏ）！ （２）、ＣＨｚ（ＣＨｇ）ｚｃＯＯＨ（３）
、ＣＨｉ（ＣＬ）＋ｈＣＯＯＨ（４）、Ｃｔｌｓ（ＣＩ
ｌｚ） ＋１ＣＯＯＮａ（５） 、Ｃ）Ｉｆｆ（ＣＨｚ
） ＋６０ｃＯＯＨ（６）、ＣＨｆｆ（ＣＨｚ） ＋１
ＯＯＮａ （７） 、ＣＩ’１３（ＣＴｏ） ＋１ＳＯ
ｉｌｌ （８）、ＣＨｓ（ＣＨｚ）ＩｈｓＯ，Ｎａ（９
） 、ＣＨｚ（ＣＦＩｇ）＋１０ＳＯＪ（１０）、Ｃｔ
ｈ （ＣＨｚ） ＋ ｂＯ８ＯｓＮａ （１１）、ＣＨ
ｄＣＨり＋１ＰＯＪｚ（１２）、ＣＨ３（Ｃｌｌｘ）
＋ ｂＰＯＪａｚ （１３）、ＣＨｓ （ＣＨｚ） ＋
＊ＰＯ３ＨＮａ （１４）、ＣＨｓ（ＣＨｚ） ＋１
ＳＯｉｌｌｚ（１５）、ＣＨｉ（ＣＨｚ） ＋１０ＢＯ
ＪＮａｚ（１６）、ＣＨｓ（ＣＬ）＋１ＯＯＮａ（１７
） 、Ｃ１１ｓ（ＣＬ）＋ａＳＯＪ（１Ｂ）、Ｃｔｌｓ
（ＣＨｚ）＋１ＳＯｚＮａ（１９） 、ＣＨｓ（ＣＨｇ
）＋＊０５Ｏｚｌｌ（２０）、Ｃ１１３（ＣＨｚ） ｒ
１Ｏ５ＯＪａ （２１）、Ｃ１１３（ＣＨｚ） ｒ
ｈｓＯＪａ （２２）、ＣＦＩｓ（Ｃｔｌｚ）＋１ＰＯ
Ｊｚ（２３） 、ＣＨｚ（ＣＨｚ）＋１ＳＯｚＮａｚ（
２４）、Ｃ）！３ （Ｃ１ｈ） ＋ １ＰＯＪＮａ （
２５）、ＣＨｆｆ（ＣＨｚ） ＋ ｈＯＰ（ｈＨ友（２
６）、ＣＨｚ（Ｃｕｔ）＋１ＯＯＮａｚ（２８） 、Ｃ
）Ｉｓ（ＣＨｚ）＋１０ＰＯｔＨＮａ（２９）、ＣＨ３
（Ｃ）Ｉｔ）＋ＪＯＪｘ（３０） 、Ｃ）ｌｚ（ＣＨｚ
）＋１ＯｚＮａｚ（３１）、ＣＨｓ（ＣＨｚ） ＋ＪＯ
ＪＮａ（３２）、ＣＨｉ（ＣＨｚ） １６０ＢＯＸＨ１
（３３）、ＣＨｓ（ＣＬ）＋１０ＢＯＪａｔ（３４）
、ＣＨｉ（ＣＬ）＋１０ＢＯＪＮａ（３５）等である。More specifically, the following chemical formulas (1) to (35
) can be used. That is, CHz(CHi
)+oCOOH(1), CHs(CFlg)+zCO
O)! (2), CHz (CHg)zcOOH (3)
, CHi(CL)+hCOOH(4), Ctls(CI
lz) +1COONa(5) ,C)Iff(CHz
) +60cOOH(6), CHff(CHz) +1
OONa (7), CI'13 (CTo) +1SO
ill (8), CHs(CHz)IhsO,Na(9
), CHz(CFIg)+10SOJ(10), Ct
h (CHz) + bO8OsNa (11), CH
dCHri+1POJz(12), CH3(Cllx)
+ bPOJaz (13), CHs (CHz) +
*PO3HNa (14), CHs (CHz) +1
SOillz (15), CHi (CHz) +10BO
JNaz (16), CHs (CL) + 1OONa (17
), C11s (CL) + aSOJ (1B), Ctls
(CHz)+1SOzNa(19), CHs(CHg
)+*05Ozll(20), C113(CHz) r
1O5OJa (21), C113 (CHz) r
hsOJa (22), CFIs (Ctlz) + 1PO
Jz(23), CHz(CHz)+1SOzNaz(
24), C)! 3 (C1h) + 1POJNa (
25), CHff (CHz) + hOP (hH friend (2
6), CHz (Cut) + 1OONaz (28), C
)Is(CHz)+10POtHNa(29), CH3
(C) It) + JOJx (30), C) lz (CHz
)+1OzNaz(31), CHs(CHz) +JO
JNa (32), CHi (CHz) 160BOXH1
(33), CHs(CL)+10BOJat(34)
, CHi(CL)+10BOJNa(35), etc.
これらの中でも硫黄に由来するオキソ酸が表面への固着
性、滑り性ともに特に優れるので、本発明の磁気記録媒
体に使用することが望ましい。Among these, oxoacids derived from sulfur have particularly excellent adhesion to the surface and slipperiness, and are therefore preferably used in the magnetic recording medium of the present invention.
本発明の磁気記録媒体には、フッ素化ポリエーテルとし
て末端変性タイプと未変性タイプが使用できる。In the magnetic recording medium of the present invention, terminally modified type and unmodified type can be used as the fluorinated polyether.
前記末端変性タイプの末端変性基としては、ＣＨ３０Ｇ
Ｏ−１Ｃ，Ｈ５ＣＯＣＯ−１ＣＩ□ｕｚｓｏｃｏ＝、１
（ＣＯＯ−Ｃ１１，ＣＯＯ−１Ｃ１Ｈ，ＣＯＯ−１Ｃ＋
ｖｆｈｓＣＯＯ−１Ｃ，■５ＯＣＯｃ、ｏ、ｃｏｏ−２
ＯＨ，のほかＣ００ＩＩ、 ５０３１１等のオキソ酸型
末端基等が挙げられる。As the terminal modified group of the terminal modified type, CH30G
O-1C, H5COCO-1CI□uzsoco=,1
(COO-C11, COO-1C1H, COO-1C+
vfhsCOO-1C,■5OCOc,o,coo-2
In addition to OH, oxoacid type terminal groups such as C00II and 50311 can be mentioned.
前記末端変性タイプの具体例としては、以下の化学式（
３６）〜（４２）の化合物等が使用できる。As a specific example of the terminal-modified type, the following chemical formula (
Compounds 36) to (42) can be used.
ＣＪｓＯＣＯＣＦｚ−０（ＣＦｔＯ）＋ｗ−（ＣＦｚＣ
ＦｚＯ）ｎ−ＣＦｚＣＯＯＣａＨｓＣＰｚ−０（ＣＦｚ
Ｏ） ｍ−（ＣＦｚＣＦｚＯ） ｎ−ＣＦｚＣＯＯＣＨ
ｚＣＦｔ−０（ＣＦｘＯ）ｍ−（ＣＦｘＣＦｚＯ）ｎ−
ＣＦｔＯＨＨＯＣＯＣＦｇ−０（ＣＦｔＯ）１１− （
ＣＦｚＣＦｚＯ）ｎ−ＣＦｚＣＯＯＨＣＨ３０ＣＯＣＦ
ｘ−０（ＣＦｚＣＦＪ） ｎ−ＣＦｚＣＯＯｌ：Ｊｌｆ
ｆ（３６）
（３７）
（３８）
（３９）
（４０）
ＨＯＣＦｚ−０（ＣＦｚＯ）ｍ−（ＣＦｚＣＦｘＯ）ｎ
−ＣＦｚＯＨ（４１）／ Ｃ＋ ＋ Ｈｉ＊Ｃ００（：
ＨｚＣＦｚ−０（ＣＦＩＯ） ｌＩ−（ＣＦｚＣＦｚＯ
） ｎ−ＣＦｚＣＨ＊０ＣＯＣ＋ ＋ Ｈｇ３（４２）
さらに、末端変性されていないパーフルオロポリエーテ
ルとしては、以下の化学式（４３）〜（４５）の化合物
等が使用できる。CJsOCOCFz-0(CFtO)+w-(CFzC
FzO)n-CFzCOOCaHsCPz-0(CFz
O) m-(CFzCFzO) n-CFzCOOCH
zCFt-0(CFxO)m-(CFxCFzO)n-
CFtOHHOCOCFg-0(CFtO)11- (
CFzCFzO)n-CFzCOOHCH30COCF
x-0(CFzCFJ) n-CFzCOOl:Jlf
f(36) (37) (38) (39) (40) HOCFz-0(CFzO)m-(CFzCFxO)n
-CFzOH(41)/C+ + Hi*C00(:
HzCFz-0(CFIO) lI-(CFzCFzO
) n-CFzCH*0COC+ + Hg3 (42) Furthermore, as the perfluoropolyether that is not terminally modified, compounds of the following chemical formulas (43) to (45) can be used.
（：Ｆ３−０（ＣＦｚＯ）ｅ＋−（ＣＦｚＣＦｚＯ）ｎ
−ＣＦｓＣＦｓ−０（ＣＦｚＣＦ（ＣＦｓ）Ｏ）ｎ−Ｃ
Ｆ３ＣＦｓ−０（ＣＦｘＣＦｚＣＰｉＯ）ｎ−ＣＦｚ本
発明の磁気記録媒体の磁性層の表面もしくは内部に保持
される前記炭化水素基を有するオキソ酸またはその塩と
フッ素化ポリエーテルの使用量としては、磁性層の内部
に保持される場合は、強磁性粉末１００重量部当り０，
５〜ＩＯ重量部である。磁性層表面上に保持する場合は
、１〜１１００Ｉ１／ボが望ましい。(:F3-0(CFzO)e+-(CFzCFzO)n
-CFsCFs-0(CFzCF(CFs)O)n-C
F3CFs-0(CFxCFzCPiO)n-CFzThe amount of the oxo acid having a hydrocarbon group or its salt and the fluorinated polyether held on the surface or inside of the magnetic layer of the magnetic recording medium of the present invention is as follows: per 100 parts by weight of ferromagnetic powder.
5 to IO parts by weight. When it is held on the surface of the magnetic layer, it is preferably 1 to 1100 I1/bo.
使用量が少ないと、本発明の効果が十分に得られず、ま
た多すぎると、走行中貼付きを起こしたり、磁性層内部
に保持されている場合には、磁性層中の結合剤樹脂と分
離してしみだす結果、かえ（４３〉
（４４）
（４５）
って走行耐久性が添加してしまう。If the amount used is too small, the effect of the present invention cannot be obtained sufficiently, and if it is too large, it may cause sticking during running, or if it is retained inside the magnetic layer, the binder resin in the magnetic layer may As a result of separation and seepage, running durability is increased by (43) (44) (45).
本発明の磁気記録媒体の磁性層に保持させる前記炭化水
素基を有するオキソ酸またはその塩とフッ素化ポリエー
テルとの混合比率は、１：１０乃至１０：１であり、望
ましくは１：５乃至５：１である。前記炭化水素基を有
するオキソ酸またはその塩乃至混合比率が余り少ないと
摩擦係数が高くなり、またフッ素化ポリエーテルの混合
比率が余り少ないと耐久性が低下するので問題となる。The mixing ratio of the hydrocarbon group-containing oxoacid or its salt and the fluorinated polyether to be retained in the magnetic layer of the magnetic recording medium of the present invention is 1:10 to 10:1, preferably 1:5 to 1:5. The ratio is 5:1. If the oxo acid having a hydrocarbon group or its salt or the mixing ratio is too small, the coefficient of friction will increase, and if the mixing ratio of the fluorinated polyether is too small, the durability will decrease, which poses a problem.
本発明の磁気記録媒体においては、その他の潤滑剤を併
用することもできる。In the magnetic recording medium of the present invention, other lubricants can also be used in combination.
併用できるその他の潤滑剤としては、ミリスチン酸、ス
テアリン酸、オレイン酸等の飽和もしくは不飽和の脂肪
酸、金属石鹸、他の脂肪酸アミド、各種モノエステル、
ソルビタン、グリセリン等の多価エステルの脂肪酸エス
テル、多塩基酸のエステル化物等の脂肪酸、高級脂肪族
アルコール、モノアルキルフォスフェート、トリアルキ
ルフォスフェート、パラフィン類、シリコーンオイル、
動植物油、鉱油、高級脂肪族アミン等の有機化合物、グ
ラファイト、シリカ、二硫化モリブデン、二硫化タング
ステン、等の無機粉末、ポリエチレン、ポリプロピレン
、ポリ塩化ビニル、エチレン塩化ビニル強重合体、ポリ
テトラフルオロエチレン等の樹脂粉末、αオレフイン重
合物、常温で液体の不飽和炭化水素、フルオロカーボン
、等が挙げられる。Other lubricants that can be used in combination include saturated or unsaturated fatty acids such as myristic acid, stearic acid, and oleic acid, metal soaps, other fatty acid amides, various monoesters,
Fatty acid esters of polyvalent esters such as sorbitan and glycerin, fatty acids such as esters of polybasic acids, higher aliphatic alcohols, monoalkyl phosphates, trialkyl phosphates, paraffins, silicone oils,
Animal and vegetable oils, mineral oils, organic compounds such as higher aliphatic amines, inorganic powders such as graphite, silica, molybdenum disulfide, tungsten disulfide, etc., polyethylene, polypropylene, polyvinyl chloride, ethylene vinyl chloride strong polymer, polytetrafluoroethylene Examples include resin powders such as, α-olefin polymers, unsaturated hydrocarbons that are liquid at room temperature, fluorocarbons, and the like.
前記の併用できる潤滑剤の使用量は、その使用層様によ
り異なるが、本発明で使用する前記エステル化合物の１
／１０乃至２倍量（重量）であることが望ましい。The amount of the above-mentioned lubricant that can be used in combination varies depending on the type of layer in which it is used.
/10 to 2 times the amount (by weight).
本発明の磁気記録媒体で使用する前記炭化水素系のオキ
ソ酸またはその塩とパーフルオロポリエーテルとは磁性
層表面もしくは磁性層内部に保持される。Ｍｉ磁性層表
面保持させる方法には、有機溶剤に溶解した溶液の状態
で基板に塗布あるいは噴霧した後乾燥する方法、溶融し
て基板に塗着させる方法、基板を溶液中に浸せきして表
面に吸着させる方法、ラングニュアープロジェット法等
を使用することができる。The hydrocarbon-based oxo acid or its salt and perfluoropolyether used in the magnetic recording medium of the present invention are retained on the surface of the magnetic layer or inside the magnetic layer. Methods for retaining the surface of the Mi magnetic layer include coating or spraying it on the substrate in the form of a solution dissolved in an organic solvent and then drying it, melting it and coating it on the substrate, and dipping the substrate in the solution and applying it to the surface. An adsorption method, the Langure-Projet method, etc. can be used.
塗布型の磁気記録媒体の場合は、使用する強磁性粉末の
粒子サイズや形状に特に制限はないが、通常は、針状、
粒状、サイコロ状、米粒状もしくは板状のものが使用さ
れ、大きさとしては、Ｘ線回折法で測定したときの結晶
子サイズは４５０Å以下であることが電磁変換特性上好
ましい。In the case of coating-type magnetic recording media, there are no particular restrictions on the particle size or shape of the ferromagnetic powder used, but it is usually acicular,
A granular, dice-like, rice-grain-like or plate-like material is used, and from the viewpoint of electromagnetic conversion characteristics, it is preferable that the crystallite size is 450 Å or less when measured by X-ray diffraction.
本発明の磁気記録媒体が塗布型である場合の磁性層中の
結合剤樹脂としては、特に制限はな〈従来から知られて
いる各種の樹脂が使用できる。When the magnetic recording medium of the present invention is a coating type, the binder resin in the magnetic layer is not particularly limited; various conventionally known resins can be used.
例えば、塩化ビニル・酢酸ビニル共重合体、塩化ビニル
、酢酸ビニル・ビニルアルコール共重合体、塩化ビニル
とマレイン酸、アクリル酸との共重合体、塩化ビニル・
塩化ビニリデン共重合体、塩化ビニル・アクリロニトリ
ル共重合体、エチレン・酢酸ビニル共重合体、ニトロセ
ルロース等のセルロース誘導体、アクリル樹脂、ポリビ
ニルアセタール樹脂、ポリビニルブチラール樹脂、エポ
キシ樹脂、フェノキシ樹脂、ポリウレタン樹脂、ポリカ
ーボネートポリウレタン樹脂等の各種の熱可塑性、熱硬
化性の樹脂が使用できる。For example, vinyl chloride/vinyl acetate copolymer, vinyl chloride, vinyl acetate/vinyl alcohol copolymer, copolymer of vinyl chloride with maleic acid or acrylic acid, vinyl chloride/vinyl alcohol copolymer,
Vinylidene chloride copolymer, vinyl chloride/acrylonitrile copolymer, ethylene/vinyl acetate copolymer, cellulose derivatives such as nitrocellulose, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, epoxy resin, phenoxy resin, polyurethane resin, polycarbonate Various thermoplastic and thermosetting resins such as polyurethane resin can be used.
強磁性粉末の分散性を高め、磁性層の耐久性を高めるた
めに、結合剤樹脂の分子中に、エポキシ基、カルボキシ
ル基、ヒドロキシル基、アミノ基、Ｓ０３ Ｍ、
０３Ｏｓ Ｍ、 ＰＯｓ Ｍ＊ （但し、Ｍは、
水素、アルカリ金属、アンモニウムであり、ひとつの基
の中に複数のＭがあってもまたＭが互いに異なっていて
もよい、）などの極性基を導入することもできる。その
際の極性基の導入量としては、ポリマー１グラム当り１
Ｏ−７〜１０−”当量が望ましく、特に望ましくは１０
−−〜１０−’当量である。In order to improve the dispersibility of the ferromagnetic powder and the durability of the magnetic layer, epoxy groups, carboxyl groups, hydroxyl groups, amino groups, S03 M,
03Os M, POs M* (However, M is
It is also possible to introduce polar groups such as hydrogen, alkali metals, ammonium, and one group may have a plurality of M's or the M's may be different from each other. In this case, the amount of polar group introduced is 1 per gram of polymer.
O-7 to 10-” equivalents are desirable, particularly preferably 10
--~10-' equivalent.
また、前記の結合剤樹脂にポリイソシアネート系の化合
物を硬化剤として使用して磁気記録媒体の膜物性を更に
向上させることもできる。Furthermore, the film properties of the magnetic recording medium can be further improved by using a polyisocyanate-based compound as a curing agent in the binder resin.
また、アクリル酸エステル系のオリゴマーとモノマーを
結合剤樹脂として使用して放射線を照射することにより
硬化処理をすることもできる。Furthermore, curing treatment can be performed by using an acrylic ester oligomer and monomer as a binder resin and irradiating it with radiation.
非磁性支持体の素材としては、ポリエチレンテレフタレ
ート、ポリエチレン２．６ナフタレートなどのポリエス
テル類、ポリエチレン、ポリプロピレン等のポリオレフ
ィン類、セルローストリトリアセテート等のセルロース
誘導体、ポリカーボネート、ポリイミド、ポリアミトイ
【ド等の樹脂を使用することもでき、アルミニウムなど
の金属で表面がメタライズ化されていてもよい。As materials for the nonmagnetic support, polyesters such as polyethylene terephthalate and polyethylene 2.6 naphthalate, polyolefins such as polyethylene and polypropylene, cellulose derivatives such as cellulose tritriacetate, and resins such as polycarbonate, polyimide, and polyamide are used. The surface may be metallized with metal such as aluminum.
前記非磁性支持体の厚みは３〜１００５ｍ、磁気テープ
としては好ましくは３〜２０μｍ５磁気デイスクとして
は２０〜！００μｍが通常使用される範囲である。The thickness of the non-magnetic support is 3 to 1005 m, preferably 3 to 20 m for a magnetic tape, and 20 to 20 m for a magnetic disk! 00 μm is the commonly used range.
本発明の磁気記録媒体の磁性層中の全結合剤の含有量は
、通常は強磁性粉末１００重量部に対して１０〜１００
重量部であり、好ましくは２０〜４０重量部である。The total binder content in the magnetic layer of the magnetic recording medium of the present invention is usually 10 to 100 parts by weight per 100 parts by weight of the ferromagnetic powder.
Parts by weight, preferably 20 to 40 parts by weight.
本発明の磁気記録媒体の磁性層には、さらにモース硬度
５以上の無機質粒子を含有することが好ましい。The magnetic layer of the magnetic recording medium of the present invention preferably further contains inorganic particles having a Mohs hardness of 5 or more.
使用される無機質粒子は、モース硬度が５以上であれば
特に制限はない、モース硬度が５以上の無機質粒子の例
としては、Ａ１＊Ｏｓ （モース硬度９）ＴｉＯ（同
５ ） 、ＴｉＯ□（同６．５） 、Ｓｉｎｇ （同７
）、ＳｎＯ，（同６．５）、ＣｒｚＯｓ （同９）、
およびα−Ｆｅｚｅｓ （同５．５）を挙げることが
でき、これらを単独あるいは混合して用いることができ
る。The inorganic particles used are not particularly limited as long as they have a Mohs hardness of 5 or more. Examples of inorganic particles with a Mohs hardness of 5 or more include A1*Os (Mohs hardness 9), TiO (Mohs hardness 5), TiO□ ( 6.5), Sing (7)
), SnO, (6.5), CrzOs (9),
and α-Fezes (5.5), which can be used alone or in combination.
とくに好ましいのはモース硬度が８以上の無機質粒子で
ある。モース硬度が５よりも低い無ｉ質粒子を用いた場
合には、磁性層から無ｍ質粒子が脱落しやすく、またヘ
ッドの研磨作用も殆どないため、へ・７ド目詰まりを発
生しやす（、また走行耐久性も乏しくなる。Particularly preferred are inorganic particles having a Mohs hardness of 8 or more. When amorphous particles with a Mohs hardness of less than 5 are used, the amorphous particles tend to fall off from the magnetic layer and have almost no abrasive action on the head, making it easy for the head to become clogged. (Also, running durability becomes poor.
無機質粒子の含有量は、通常、強磁性粉末１００重量部
に対して０．１〜２０重量部の範囲であり、好ましくは
１〜１０重量部の範囲である。The content of the inorganic particles is usually in the range of 0.1 to 20 parts by weight, preferably in the range of 1 to 10 parts by weight, based on 100 parts by weight of the ferromagnetic powder.
また磁性層には前記無機質粒子以外にも、カーボンブラ
ック（特に、平均粒径がｌＯ〜３００ｎ−（ナノメート
ル； １０−’ｍ）のもの）などを含有させることが望
ましい。In addition to the above-mentioned inorganic particles, the magnetic layer preferably contains carbon black (particularly one having an average particle size of lO to 300n-(nanometers; 10-'m)).
つぎに本発明の磁気記録媒体を製造する方法の例を述べ
る。Next, an example of a method for manufacturing the magnetic recording medium of the present invention will be described.
塗布型磁気記録媒体である場合、まず、強磁性粉末と結
合剤樹脂、前記オキソ酸又はオキソ酸の塩及び前記フン
素化ポリエーテル、そして必要に応して、他の充填材、
添加剤などを溶剤と混練し、磁性塗料を調整する。混練
の際に使用する溶剤としては、磁性塗料の調整に通常使
用されている溶剤を使用することができる。In the case of a coated magnetic recording medium, first, the ferromagnetic powder, the binder resin, the oxo acid or the salt of the oxo acid, and the fluorinated polyether, and if necessary, other fillers,
Additives are mixed with a solvent to prepare magnetic paint. As the solvent used during kneading, solvents commonly used for preparing magnetic paints can be used.
混練の方法にも特に制限はなく、また各成分の添加順序
などは適宜設定することができる。There is no particular restriction on the kneading method, and the order of addition of each component can be set as appropriate.
前記磁性塗料を調整する際には、分散剤、帯電防止剤、
潤滑剤等の公知の添加剤を併せて使用することもできる
。When preparing the magnetic paint, dispersants, antistatic agents,
Known additives such as lubricants may also be used.
分散剤の例としては、炭素数１２〜２２の脂肪酸、その
塩またはエステル化物およびその化合物の水素の一部あ
るいは全部をフッ素原子で置換した化合物、上記の脂肪
酸のアミド、脂肪族ア哉ン、高級アルコール、ポリアル
キレンオキサイドアルキル燐酸エステル、アルキル燐酸
エステル、アルキルホウ酸エステル、サルコシネート類
、アルキルエーテルエステル類、トリアルキルポリオレ
フィン、オキシ第４級アンモニウム塩およびレシチンな
どの公知の分散剤を挙げることができる。Examples of dispersants include fatty acids having 12 to 22 carbon atoms, salts or esters thereof, compounds in which part or all of the hydrogen atoms of these compounds are replaced with fluorine atoms, amides of the above fatty acids, aliphatic amines, Known dispersants such as higher alcohols, polyalkylene oxide alkyl phosphates, alkyl phosphates, alkyl borates, sarcosinates, alkyl ether esters, trialkyl polyolefins, oxyquaternary ammonium salts and lecithin can be mentioned.
前記分散剤を使用する場合は、通常は使用する強磁性粉
末１００重量部に対し、０．１〜１０重量部の範囲で使
用される。When the dispersant is used, it is usually used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the ferromagnetic powder used.
帯電防止剤の例としては、カーボンブラック、カーポン
ブランクトボリマーなどの導電性微粉末；サポニンなど
の天然界面活性剤；アルキレンオキサイド系、グリセリ
ン系およびグリシドール系などのノニオン系界面活性剤
；高級アルキルアミン類、第４級アンモニウム塩類、ピ
リジンその他の複素環化合物の塩類、ホスホニウムまた
はスルホニウム類などのカチオン性界面活性剤；カルボ
ン酸、燐酸、硫酸エステル基等の酸性基を含むアニオン
性界面活性剤；アミノ酸類、ア稟ノスルホン酸類、ア稟
ノアルコールの硫酸または燐酸エステル類等の両性界面
活性剤等を挙げることができる。帯電防止剤として上記
の導電性微粉末を使用する場合には、例えば強磁性粉末
１００重量部に対し０．１〜１０重量部の範囲で使用さ
れ、界面活性剤を使用する場合にも同様に０．１２〜１
０重量部の範囲で使用される。Examples of antistatic agents include conductive fine powders such as carbon black and carbon blank polymers; natural surfactants such as saponin; nonionic surfactants such as alkylene oxides, glycerin and glycidol; higher alkyl amines. Cationic surfactants such as quaternary ammonium salts, salts of pyridine and other heterocyclic compounds, phosphoniums or sulfoniums; Anionic surfactants containing acidic groups such as carboxylic acid, phosphoric acid, and sulfuric acid ester groups; Amino acids Examples include amphoteric surfactants such as atomosulfonic acids, sulfuric acid or phosphoric acid esters of anomalous alcohols, and the like. When using the above-mentioned conductive fine powder as an antistatic agent, for example, it is used in a range of 0.1 to 10 parts by weight per 100 parts by weight of ferromagnetic powder, and the same applies when using a surfactant. 0.12~1
It is used in a range of 0 parts by weight.
なお、上述した分散剤、帯電防止剤、潤滑剤などの添加
剤は、厳密に上述した作用効果のみを有するものである
との限定の下に記！ｉ！シたものではなく、例えば、分
散剤が潤滑剤あるいは帯電防止剤として作用することも
有りうる。従って、上記分類により例示した化合物など
の効果作用が、上記分類に記載された事項に限定されな
いことは勿論であり、また複数の作用効果を奏する物質
を使用する場合には、添加量は、その作用効果を考慮し
て決定することが好ましい。In addition, the additives such as the dispersant, antistatic agent, and lubricant mentioned above are described with the limitation that they have strictly only the effects mentioned above! i! For example, the dispersant may act as a lubricant or an antistatic agent. Therefore, it goes without saying that the effects of the compounds exemplified by the above classifications are not limited to those listed in the above classifications, and when using a substance that has multiple effects, the amount added should be It is preferable to decide in consideration of the action and effect.
このようにして調製された前記磁性塗料は前記の非磁性
支持体上に塗布される。塗布は、前記非磁性支持体上に
直接行なうことも可能であるが、また、接着剤層などの
中間層を介して前記非磁性支持体上に塗布することもで
きる。ここでいう中間層とは接着剤単独の層または結合
剤中にカーボン等の非磁性微粒子を分散してなる複合膜
層等である。The magnetic paint thus prepared is applied onto the non-magnetic support. Coating can be performed directly onto the non-magnetic support, but it can also be applied onto the non-magnetic support via an intermediate layer such as an adhesive layer. The intermediate layer herein refers to a layer of adhesive alone or a composite film layer formed by dispersing non-magnetic fine particles such as carbon in a binder.
カーボンを含有する中間層は結合剤樹脂として磁性層に
用いられる種々の結合剤のなかから任意に選ぶことがで
きる。カーボンの粒径は１０〜５０ｎｍ（ナノメートル
； １０−’ｍ ）のものが好ましく、バインダー：カ
ーボンは重量比にして１００：１０から１００ ：１５
０が好ましい、中間層の厚みは単なる接着剤層の場合０
．１〜２μｍ、非磁性粉体を含む複合層の場合０．５〜
４μｍが好ましい。The binder resin for the carbon-containing intermediate layer can be arbitrarily selected from among various binders used in magnetic layers. The particle size of carbon is preferably 10 to 50 nm (nanometers; 10-'m), and the binder:carbon weight ratio is 100:10 to 100:15.
The thickness of the intermediate layer is preferably 0 if it is just an adhesive layer.
．． 1-2μm, 0.5-2μm for composite layer containing non-magnetic powder
4 μm is preferred.
中間層にはこのほか磁性層に用いている潤滑剤と同じま
たは異なる潤滑剤を添加してもよい。In addition, a lubricant that is the same as or different from the lubricant used in the magnetic layer may be added to the intermediate layer.
前記強磁性粉末と結合樹脂剤の分散方法および非磁性支
持体上への塗布方法などの詳細は特開昭５４−４６０．
１１号公報および同５４−２１８０５号公報に記載され
ている。Details of the method of dispersing the ferromagnetic powder and the binding resin and the method of coating it on a non-magnetic support can be found in JP-A-54-460.
No. 11 and No. 54-21805.
このようにして塗布される磁性層の厚さは、乾燥後の厚
さで一般には約０．５〜１０ＩＩｍの範囲、通常は０．
７〜６．Ｏｚｍの範囲になるよう塗布される。The thickness of the magnetic layer thus applied after drying is generally in the range of about 0.5 to 10 II m, usually 0.5 to 10 II m.
7-6. It is applied to a range of ozm.
非磁性支持体上に塗布された磁性層は磁気記録媒体がテ
ープ状で使用される場合通常、磁性層中の強磁性粉末を
配向させる処理、即ち磁場配向処理を施したあと、乾燥
される。また逆にディスク状媒体で使用される場合は磁
気特性の異方性をとりのぞくために、磁場による無配向
処理が施される。こののち必要により表面平滑化処理が
施される。When a magnetic recording medium is used in the form of a tape, the magnetic layer coated on the non-magnetic support is usually subjected to a treatment for orienting the ferromagnetic powder in the magnetic layer, that is, a magnetic field orientation treatment, and then dried. On the other hand, when used as a disk-shaped medium, non-orientation treatment is performed using a magnetic field in order to eliminate anisotropy in magnetic properties. Thereafter, surface smoothing treatment is performed if necessary.
強磁性金属薄膜の材料としては鉄、コバルト、ニッケル
その他の強磁性金属あるいはＦｅ−Ｃｏ。The material for the ferromagnetic metal thin film is iron, cobalt, nickel, other ferromagnetic metals, or Fe-Co.
Ｆｅ−Ｎｉ、Ｃｏ−Ｎｉ、Ｆｅ−Ｒｈ、、Ｃｏ−ＰＣｏ
−Ｂ、 Ｃｏ−Ｙ、 Ｃｏ−Ｌａ、 Ｃｏ−Ｃｅ。Fe-Ni, Co-Ni, Fe-Rh, Co-PCo
-B, Co-Y, Co-La, Co-Ce.
Ｃｏ−ＰＬ、 Ｃｏ−３ｍ、 Ｃｏ−Ｍｎ、 Ｃｏ−
Ｃｒ、 Ｆｅ−Ｃｏ−Ｎｉ、 Ｃｏ−Ｎｉ −Ｐ、
Ｃｏ −Ｎｉ−Ｂ、Ｃｏ−Ｎｉ−Ａｇ、Ｃｏ−Ｎｔ −
Ｎｄ。Co-PL, Co-3m, Co-Mn, Co-
Cr, Fe-Co-Ni, Co-Ni-P,
Co-Ni-B, Co-Ni-Ag, Co-Nt-
Nd.
Ｃｏ−Ｎｉ−Ｃｅ、Ｃｏ−Ｎｉ−前記ｎ、Ｃｏ−Ｎｉ−
Ｃｕ、 Ｃｏ−Ｎｉ −Ｗ、 Ｃｏ−Ｎｉ−Ｒｅ等の強
磁性合金を電気メツキ、無電解メツキ、気相メツキ、ス
パッタリング、蒸着、イオンブレーティング等の方法に
より形成せしめたもので、その膜厚は磁気記録媒体とし
て使用する場合０．０２〜２μｍの範囲であり、特に０
．０５〜０． ４μｍの範囲が望ましい。Co-Ni-Ce, Co-Ni-n, Co-Ni-
A ferromagnetic alloy such as Cu, Co-Ni-W, Co-Ni-Re, etc. is formed by methods such as electroplating, electroless plating, vapor phase plating, sputtering, vapor deposition, and ion blating, and the film thickness is in the range of 0.02 to 2 μm when used as a magnetic recording medium, especially 0.
．． 05~0. A range of 4 μm is desirable.
金属薄膜を形成する際たとえば酸素または窒素気流中で
蒸着行う等の方法で、上記各種強磁性金属薄膜中に酸素
または窒素を導入することが電磁変換特性、耐久性をよ
り優れたものにすることができる０、また酸素の他にＮ
、Ｃｒ、Ｇａ、Ａｓ。When forming a metal thin film, introducing oxygen or nitrogen into the various ferromagnetic metal thin films described above by a method such as vapor deposition in an oxygen or nitrogen stream can improve electromagnetic conversion characteristics and durability. 0, and in addition to oxygen, N
, Cr, Ga, As.
Ｓｒ、前記ｒ、Ｎｂ、Ｍｏ、Ｒｈ、Ｐｄ、５ｎＳｂ、Ｔ
ｅ、Ｐｍ、Ｒｅ、Ｏｓ、Ｉｒ、Ａｕ、Ｈｇ、Ｐｂ、Ｂｉ
、Ｍｇ等を含んでいてもよい。Sr, r, Nb, Mo, Rh, Pd, 5nSb, T
e, Pm, Re, Os, Ir, Au, Hg, Pb, Bi
, Mg, etc.
前記強磁性金属薄膜の磁性層の表面形状は特に規定され
ないが、１〜５００ｍｍ（ｎｍ：ナノメートル＝１０−
”メートル）の高さの突起を有して、いる場合特に走行
性・耐久性にすぐれる。The surface shape of the magnetic layer of the ferromagnetic metal thin film is not particularly defined, but is 1 to 500 mm (nm: nanometer = 10-
If it has a protrusion with a height of 1000 meters, it has excellent running performance and durability.
金属薄膜型磁気記録媒体で使用される非磁性支持体の厚
さは４〜５０５ｍが好ましい、また強磁性金属ＷＩＩＩ
ｉの密着向上・磁気特性の改良のために非磁性支持体上
に下地層を設けてもよい。The thickness of the nonmagnetic support used in the metal thin film type magnetic recording medium is preferably 4 to 505 m, and the thickness of the ferromagnetic metal WIII is preferably 4 to 505 m.
An underlayer may be provided on the nonmagnetic support in order to improve the adhesion and magnetic properties of i.
本発明の金属薄膜型の磁気記録媒体で使用される非磁性
支持体としてはポリエチレンテレフタレート、ポリイミ
ド、ボリアミド、ポリ塩化ビニル、三酢酸セルロース、
ポリカーボネート、ポリエチレンナフタレート、ポリフ
ェニレンサルファイドのようなプラスチックベース、又
はＡＩ、Ｔｉ。Examples of the nonmagnetic support used in the metal thin film type magnetic recording medium of the present invention include polyethylene terephthalate, polyimide, polyamide, polyvinyl chloride, cellulose triacetate,
Plastic bases such as polycarbonate, polyethylene naphthalate, polyphenylene sulfide, or AI, Ti.
ステンレス鋼などが挙げられる。Examples include stainless steel.
走行耐久性を向上させるために、金属薄膜を形成する前
に非磁性支持体表面に微小突起を設けておくことが（結
果的に磁性層表面に適度な凹凸を設けることになり）効
果的である。微小突起の存在密度は２ＸｌＯｈ〜２Ｘ１
０”個／■軍でひとつの突起の高さは１〜５０ｎｍ（ｎ
ｍ：ナノメートル＝１０−ｑメートル）のものが好まし
い。In order to improve running durability, it is effective to provide microprotrusions on the surface of the non-magnetic support before forming the metal thin film (resulting in creating appropriate irregularities on the surface of the magnetic layer). be. The density of microprotrusions is 2XlOh~2X1
The height of one protrusion in the army is 1 to 50 nm (n
m: nanometers = 10-q meters) is preferred.
（発明の効果）
炭化水素基を有するオキソ酸またはその塩とフッ素化ポ
リエーテルを磁性層の表面及び内部に保持させることに
より幅広い環境条件下で走行耐久性の優れた磁気記録媒
体を得ることが出来る。(Effect of the invention) A magnetic recording medium with excellent running durability under a wide range of environmental conditions can be obtained by retaining an oxo acid having a hydrocarbon group or its salt and a fluorinated polyether on the surface and inside the magnetic layer. I can do it.
次に以下の実施例をもって本発明を新規な効果を明確に
する。Next, the novel effects of the present invention will be clarified with the following examples.
本発明はこれらに限定されるものではない、なお、実施
例中の「部」との表示は「重量部」を示すものである。The present invention is not limited to these. Note that "parts" in the examples indicate "parts by weight."
［実施例１］
下記の組成物をボールミルを用いて４８時間混線分散し
たあと、これにポリイソシアネート５部を加え、さらに
１時間混線分散したあと、１μｍの平均孔径を有するフ
ィルタを用いてろ過し、磁性塗料を調整した。得られた
磁性塗料を乾燥後の厚さが４．０μｍになるように、厚
さｌＯｔＩｍのポリエチレンテレフタレート支持体の表
面にリバースロールを用いて塗布した。[Example 1] The following composition was cross-dispersed for 48 hours using a ball mill, 5 parts of polyisocyanate was added thereto, cross-dispersed for another hour, and then filtered using a filter having an average pore size of 1 μm. , Adjusted magnetic paint. The obtained magnetic coating material was applied onto the surface of a polyethylene terephthalate support having a thickness of lOtIm using a reverse roll so that the thickness after drying was 4.0 μm.
磁性塗料［威
強磁性合金粉末（Ｍ戒：Ｆｅ９４％、前記ｎ４％、Ｎ１
２％；抗磁力
ニ１５０００ｅ；比表面
積５４■／ｎ（）
１００部
塩化ビニル／酢酸ビニル／無水マレイン酸共重合体（日
本ゼオン■製 ４ＱＯＸ１１０Ａ。Magnetic paint [strong magnetic alloy powder (M precept: Fe94%, above n4%, N1
2%; Coercive force: 15,000e; Specific surface area: 54/n () 100 parts Vinyl chloride/vinyl acetate/maleic anhydride copolymer (manufactured by Nippon Zeon, 4QOX110A).
重合度４００）
１２部
研磨材（α−アルミナ、平均粒径０．３μｍ）５部
カーボンブラック（平均粒径４０ｎｍ） ２部メチル
エチルケトン ３００部磁性塗料を塗布
した後、磁性塗料が未乾燥にある状態で３０００ガウス
の磁石で磁場配向を行ない、さらに乾燥後、スーパーカ
レンダー処理を行なった後バーコータを用い、炭化水素
基を有するオキソ酸塩として前記（９）弐の化合物５部
とフッ素化ポリエーテルとして前記（４１）式の化合′
＃ｌ（分子量 ２０００．ｎ＝ｍ）５部とをフロン１１
３ １０００部に溶解した溶液を磁性層上にトップコー
トした後日−幅にスリットして、８鴫ビデオテープの試
料を作成した。Degree of polymerization: 400) 12 parts Abrasive material (α-alumina, average particle size 0.3 μm) 5 parts Carbon black (average particle size 40 nm) 2 parts Methyl ethyl ketone 300 parts After applying the magnetic paint, the magnetic paint is still wet Magnetic field alignment was performed using a 3000 Gauss magnet, and after further drying, a super calender treatment was performed using a bar coater, and 5 parts of the compound of (9) 2 above was added as an oxoacid salt having a hydrocarbon group and as a fluorinated polyether. The compound of formula (41)
#l (molecular weight 2000.n=m) 5 parts and Freon 11
A solution of 1,000 parts of the magnetic layer was top coated on the magnetic layer and then slit to a width of 100 ml to prepare a sample of an 8 sliver videotape.
前記の２種の化合物の磁性層表面における塗布量を塗布
した際の前記溶液の減少量から算出する方法で測定した
ところ前記２種の化合物の合計で３０ｍｇ／ポであった
。The amount of the two types of compounds coated on the surface of the magnetic layer was determined by calculating the amount of decrease in the solution upon coating, and the total amount of the two types of compounds was 30 mg/po.
〔実施例−２〕
溶液中に置ける２種の化合物の濃度をかえて、磁性層表
面における塗布量を６０１ｇ／ボとした以外は実施例−
１と同一の条件で８−ビデオテープの試料を作成した。[Example-2] Example-2 except that the concentrations of the two types of compounds placed in the solution were changed and the coating amount on the surface of the magnetic layer was 601 g/bo.
An 8-videotape sample was prepared under the same conditions as in Example 1.
（実施例−３）
炭化水素基を有するオキソ酸塩として前記（１１）式の
化合物とした以外は実施例−１と同一の条件で８閣ビデ
オテープの試料を作成した。(Example 3) A sample of 8-kaku videotape was prepared under the same conditions as in Example 1, except that the compound of formula (11) was used as the oxoacid salt having a hydrocarbon group.
〔実施例−４〕
炭化水素基を有するオキソ酸塩として前記（９）式の化
合物５部をメタノール９９５部に溶解して塗布量が１５
ｍｇ／ｒｒｆとなるように塗布して乾燥した後、更に、
分子量が２０００の前記（４４）式のフッ素化ポリエー
テル５部を９９５部のフロン１１３に溶解した溶液を塗
布量が１５ｍｇ／ｒｒｌとなるように磁性層上に塗布し
た以外は実施例−１と同一の条件で８閣ビデオテープの
試料を作成した。[Example-4] 5 parts of the compound of the formula (9) above as an oxoacid salt having a hydrocarbon group was dissolved in 995 parts of methanol to give a coating amount of 15 parts.
After coating and drying so that it becomes mg/rrf, further,
Example 1 except that a solution prepared by dissolving 5 parts of the fluorinated polyether of formula (44) having a molecular weight of 2000 in 995 parts of Freon 113 was applied onto the magnetic layer at a coating amount of 15 mg/rrl. Eight videotape samples were created under the same conditions.
〔実施例−５〕
炭化水素基を有するオキソ酸塩として前記（１１）式の
化合物５部をメタノール９９５部に溶解して塗布量が１
５ｕ／ｒｄとなるように塗布して乾燥した後、更に、分
子量が２０００の前記（４４）弐のフッ素化ポリエーテ
ル１０部を９９０部のフロン１１３に溶解した溶液を塗
布量が３０■／ポとなるように磁性層上に塗布した以外
は実施例−１と同一の条件で８ｍビデオテープの試料を
作成した。[Example-5] 5 parts of the compound of formula (11) above as an oxoacid salt having a hydrocarbon group was dissolved in 995 parts of methanol, and the coating amount was 1.
After coating and drying at a coating weight of 5 u/rd, a solution of 10 parts of the fluorinated polyether (44) 2 having a molecular weight of 2000 dissolved in 990 parts of Freon 113 was added to a coating amount of 30 μ/pot. An 8 m videotape sample was prepared under the same conditions as in Example 1, except that the magnetic layer was coated so as to have the following properties.
〔実施例−６〕
炭化水素基を有するオキソ酸塩として前記（２３）式の
化合物のメチルエチルケトン溶液（０，５％）を用い塗
布量が１５ｇ／ｍとなるように塗布して乾燥した後、更
に、分子量が２０００の前記（４４）式のフッ素化ポリ
エーテルのフロン１１３溶液（０，５％）を塗布量が３
０■／ポとなるように磁性層上に塗布した以外は実施例
−１と同一の条件で８馳ビデオテープの試料を作成した
。[Example-6] A methyl ethyl ketone solution (0.5%) of the compound of the formula (23) was used as an oxoacid salt having a hydrocarbon group, and the coating amount was 15 g/m, and after drying, Furthermore, a coating amount of a Freon 113 solution (0.5%) of the fluorinated polyether of formula (44) having a molecular weight of 2000 was 3.
An 8-inch videotape sample was prepared under the same conditions as in Example 1, except that the coating was applied on the magnetic layer at a rate of 0 cm/Po.
〔実施例−７〕
炭化水素基を有するオキソ酸塩として前記（１）式の化
合物のメタノール溶液（０，５％）を塗布量が１５ｍｇ
／ｒｒｆとなるように塗布して乾燥した後、更に、分子
量が２０００の前記（４４）弐のフッ素化ポリエーテル
のフロン１１３溶液（０，５％）を塗布量が３０■／ｄ
となるように磁性層上に塗布した以外は実施例−１と同
一の条件で８ａＩ１１ビデオテープの試料を作成した。[Example-7] A methanol solution (0.5%) of the compound of formula (1) was applied in an amount of 15 mg as an oxoacid salt having a hydrocarbon group.
/rrf, and after drying, further apply a Freon 113 solution (0.5%) of the fluorinated polyether of (44) 2 with a molecular weight of 2000 at a coating amount of 30μ/d.
A sample of 8aI11 videotape was prepared under the same conditions as in Example 1, except that it was coated on the magnetic layer so as to have the following properties.
〔実施例−８〕
炭化水素基を有するオキソ酸塩として、分子両末端がカ
ルボキシル基で変性したファンオイル（モンテフルオス
社製ＦＯＭＢＬＩＮ 前記ＤＩＡＣ）５部をフロン１
１３ ９９５部に溶解して塗布量が１５■／ｒｒｆとな
るように塗布して乾燥した後、更・に、分子量が２００
０の前記（４４）式のフッ素化ポリエーテルｌ０部を９
９０部のフロン１１３に溶解した溶液を塗布量３０■／
ＩＴｒとなるように磁性層上に塗布した以外は実施例−
１と同一の条件で８部ｍビデオテープの試料を作成した
。[Example-8] As an oxoacid salt having a hydrocarbon group, 5 parts of fan oil (FOMBLIN manufactured by Montefluos, DIAC) modified with carboxyl groups at both ends of the molecule was mixed with 1 part of Freon.
After dissolving in 995 parts of 13 and applying it at a coating amount of 15 μ/rrf and drying,
9 parts of the fluorinated polyether of formula (44)
Apply a solution dissolved in 90 parts of Freon 113 in an amount of 30 μ/
Example except that it was coated on the magnetic layer to become ITr.
An 8-part videotape sample was prepared under the same conditions as in Example 1.
〔比較例−１〕
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（９）式の化合物のメタノール溶
液（０，５％）を、表面塗布量が１５■／ｄとなるよう
に塗布した以外は実施例１と同一の条件で８ｍビデオテ
ープの試料を作成した。[Comparative Example-1] Fluorinated polyether was not used, and a methanol solution (0.5%) of the compound of formula (9) above was used as an oxoacid salt having a hydrocarbon group at a surface coating amount of 15 μ/d. An 8 m videotape sample was prepared under the same conditions as in Example 1, except that the coating was applied so that the following results were obtained.
〔比較例−２〕
フッ素化ポルエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（９）式の化合物のメタノール溶
液（１％）を、表面塗布量が３０ｗｔ／ｒｄとなるよう
に塗布した以外は実施例−１と同一の条件で８ｍビデオ
テープの試料を作成した。[Comparative Example-2] Fluorinated polyether was not used, and a methanol solution (1%) of the compound of formula (9) above was used as an oxoacid salt having a hydrocarbon group so that the surface coating amount was 30 wt/rd. An 8 m videotape sample was prepared under the same conditions as in Example 1 except for coating.
〔比較例−３〕
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（１）式の化合物のメチルエチル
ケトン溶液（０，５％）を、表面塗布量が１５ｍｇ／ｒ
ｄとなるように塗布した以外は実施例−１と同一の条件
で８Ｂビデオテープの試料を作成した。[Comparative Example-3] Fluorinated polyether was not used, and a methyl ethyl ketone solution (0.5%) of the compound of formula (1) was used as an oxoacid salt having a hydrocarbon group at a surface coating amount of 15 mg/r.
A sample of 8B videotape was prepared under the same conditions as in Example 1, except that the coating was applied so as to obtain d.
〔比較例−４〕
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（１）式の化合物５部とブチルス
テアレート５部とをメチルエチルケトン１２００部に溶
解した溶液を、表面塗布量が２種の潤滑剤の合計で２２
．５■／ボとなるように塗布した以外は実施例−１と同
一の条件で８閣ビデオテープの試料を作成した。[Comparative Example-4] No fluorinated polyether was used, and a solution of 5 parts of the compound of formula (1) and 5 parts of butyl stearate dissolved in 1200 parts of methyl ethyl ketone was used as an oxo acid salt having a hydrocarbon group. The total surface coating amount of the two types of lubricants is 22
．． Samples of 8-kaku videotape were prepared under the same conditions as in Example 1, except that the coating was applied at a rate of 5 cm/cm.
〔比較例−５〕
炭化水素基を有するオキソ酸塩及びフッ素化ポリエーテ
ルをともに使用しなかった以外は実施例−１と同一の条
件で８醜ビデオテープの試料を作成した。[Comparative Example-5] A sample of 8-ugly videotape was prepared under the same conditions as in Example-1 except that neither the oxo acid salt having a hydrocarbon group nor the fluorinated polyether was used.
〔実施例−９〕
非磁性支持体である１３μｍ厚のポリエチレンテレフタ
レートフィルム上にゴバルトーニッケルよりなる強磁性
金属薄膜（膜厚１５０ ｎｍ）を斜め蒸着し、金属薄膜
型磁気記録媒体を作成した。[Example 9] A ferromagnetic metal thin film (thickness: 150 nm) made of gobalt nickel was obliquely deposited on a 13 μm thick polyethylene terephthalate film serving as a nonmagnetic support to create a metal thin film type magnetic recording medium.
蒸発源としては電子ビーム蒸発源を使用し、これにコバ
ルト−ニッケル合金（Ｃｏ ： ８０ ｗ ｔ％、Ｎ１
ｊ−２０％）を＋＋−ジＬ真空度５ＸｌＯ−’Ｔｏｒｒ
中にて酸素気流中で入射角が５０度となるよう斜め蒸着
を行った。An electron beam evaporation source was used as the evaporation source, and a cobalt-nickel alloy (Co: 80 wt%, N1
j-20%) ++-diL vacuum degree 5XlO-'Torr
Oblique vapor deposition was performed in an oxygen stream at an incident angle of 50 degrees.
前記の金属薄膜型磁気記録媒体の強磁性金属薄膜上に、
バーコータを用い、炭化水素基を有するオキソ酸塩とし
て前記（９）式の化合物５部とフッ素化ポリエーテルと
して前記（４１）式の化合物（分子１ ２０００．ｎ＝
ｍ）５部とをフロン１１３ １０００部に溶解した溶液
を磁性層上にトップコートした８Ｗ４１！にスリットし
て、８ｍビデオテープの試料を作成した。On the ferromagnetic metal thin film of the metal thin film type magnetic recording medium,
Using a bar coater, 5 parts of the compound of formula (9) above as an oxoacid salt having a hydrocarbon group and the compound of formula (41) (molecule 1 2000.n=
m) 5 parts dissolved in 1000 parts of Freon 113 was top-coated on the magnetic layer to form 8W41! An 8 m videotape sample was prepared by slitting the sample into 8 m.
（実施例−１０〕
溶液中に置ける２種の化合物の濃度を変えて、磁性層表
面における塗布量を４０■／ボとした以外は実施例−９
と同一の条件で８ｍビデオテープの試料を作成した。(Example-10) Example-9 except that the concentrations of the two types of compounds placed in the solution were changed and the coating amount on the magnetic layer surface was set to 40 μ/bo.
An 8m videotape sample was prepared under the same conditions.
〔実施例−１１〕
炭化水素基を有するオキソ酸塩として前記（１１）式の
化合物とした以外は実施例−９と同一の条件で８ＩＩＩ
ｌビデオテープの試料を作成した。[Example-11] 8III was prepared under the same conditions as Example-9 except that the compound of formula (11) was used as the oxoacid salt having a hydrocarbon group.
A videotape sample was prepared.
〔実施例−１２〕
炭化水素基を有するオキソ酸塩として前記（９）式の化
合物を５部メタノール９９５部に溶解して塗布量が１２
ｍｇ／ｉｆとなるように塗布して乾燥した後、更に、分
子量が２０００の前記（４４）式のフッ素化ポリエーテ
ル５部を９９５部のフロン１１３に溶解した溶液を塗布
量が１５ｍ／ｎｆとなるように磁性層上に塗布した以外
は実施例−９と同一の条件で８閣ビデオテープの試料を
作成した。[Example-12] As an oxoacid salt having a hydrocarbon group, 5 parts of the compound of formula (9) above was dissolved in 995 parts of methanol to give a coating amount of 12 parts.
After coating and drying, a solution of 5 parts of the fluorinated polyether of the formula (44) with a molecular weight of 2000 dissolved in 995 parts of Freon 113 was added to a coating amount of 15 m/nf. A sample of 8-kaku videotape was prepared under the same conditions as in Example 9, except that the magnetic layer was coated so as to be as follows.
〔実施例−１３〕
炭化水素基を有するオキソ酸塩として前記（１１〉式の
化合物５部をメタノール９９５部に溶解して塗布量が１
０■／ｒｒｆとなるように塗布して乾燥した後、更に、
分子量が２０００の前記（４４）式のフッ素化ポリエー
テル１０部を９９０部のフロン１１３に溶解した溶液を
塗布量が１５ｍｇ／ポとなるように磁性層上に塗布した
以外は実施例−９と同一の条件で８鵬ビデオテープの試
料を作成した。[Example-13] As an oxoacid salt having a hydrocarbon group, 5 parts of the compound of formula (11) above was dissolved in 995 parts of methanol, and the coating amount was 1
After coating and drying so that it becomes 0■/rrf,
Example 9 except that a solution prepared by dissolving 10 parts of the fluorinated polyether of formula (44) having a molecular weight of 2000 in 990 parts of Freon 113 was applied onto the magnetic layer at a coating amount of 15 mg/polymer. Eight-peng videotape samples were prepared under the same conditions.
〔実施例−１４〕
炭化水素基を有するオキソ酸塩として前記（２３）式の
化合物の０．５重量％のメチルエチルケトン溶液部に溶
解して塗布量が１０■／ｎ（となるように塗布して乾燥
した後、更に、分子量が２０００の前記（４４）式のフ
ン素化ポリエーテルのフロン１１３溶液（０，５重量％
）を塗布量が２０部ｇ／ボとなるように磁性層上に塗布
した以外は実施例−９と同一の条件で８耽ビデオテープ
の試料を作成した。[Example-14] As an oxoacid salt having a hydrocarbon group, the compound of formula (23) was dissolved in a 0.5% by weight solution of methyl ethyl ketone and applied at a coating amount of 10 μ/n. After drying, a Freon 113 solution (0.5 wt%
) was coated on the magnetic layer at a coating amount of 20 parts g/bo, but an 8-videotape sample was prepared under the same conditions as in Example 9.
〔実施例−１５〕
炭化水素基を有するオキソ酸塩として前記（１）弐の化
合物の０．５重量％メタノール溶液を塗布量が１０■／
ポとなるように塗布して乾燥した後、更に、分子量が２
０００の前記（４４）式のフン素化ポリエーテルのフロ
ン１１３溶液（０，５１置％）を塗布量が２０ｍｇ／ポ
となるように磁性層上に塗布した以外は実施例−９と同
一の条件で８閣ビデオテープの試料を作成した。[Example-15] A 0.5 wt% methanol solution of the compound of (1) 2 was applied as an oxoacid salt having a hydrocarbon group at a coating amount of 10 μ/
After applying and drying, the molecular weight is 2.
Same as Example-9 except that a Freon 113 solution (0.51%) of fluorinated polyether of formula (44) of 000 was applied on the magnetic layer at a coating amount of 20 mg/polymer. Samples of eight video tapes were created under certain conditions.
〔実施例−１６）
炭化水素基を有するオキソ酸塩として、分子両末端がカ
ルボキシル基で変性したフッフォイル（モンテフルオス
社製ＦＯＭＢＬＩＮ 前記ＤＩＡＣ）５部をフロン１
１３ ９９５部に溶解して塗布量が１０ｍｇ／ｎｆとな
るように塗布して乾燥した後、更に、分子量が２０００
の前記（４４）式のフッ素化ポリエーテル１０部を９９
０部のフロン１１３に溶解した溶液を塗布量が２０■／
ｒｒｒとなるように磁性層上に塗布した以外は実施例−
９と同一の条件で８閣ビデオテープの試料を作成した。[Example-16] As an oxoacid salt having a hydrocarbon group, 5 parts of fluoroyl (FOMBLIN manufactured by Montefluos, said DIAC) modified with carboxyl groups at both ends of the molecule was mixed with 1 part of Freon.
After dissolving in 995 parts of 13 and applying it to a coating amount of 10 mg/nf and drying,
10 parts of the fluorinated polyether of formula (44) was added to 99
A coating amount of a solution dissolved in 0 parts of Freon 113 is 20 /
Example except that it was coated on the magnetic layer so that rrr
Samples of 8 cabinet video tapes were created under the same conditions as in 9.
〔比較例−６〕
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（９）式の化合物の０．５重量％
メタノール溶液を、表面塗布量が１０■／ポとなるよう
に塗布した以外は実施例−ｌと同一の条件で８鴎ビデオ
テープの試料を作成した。[Comparative Example-6] No fluorinated polyether was used, and 0.5% by weight of the compound of formula (9) above as an oxoacid salt having a hydrocarbon group
A sample of 8 gull videotape was prepared under the same conditions as in Example 1 except that the methanol solution was applied to the surface at a coating amount of 10 cm/pot.
〔比較例−７〕
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（９）式の化合物の１重量％のメ
タノール溶液を、表面塗布量が２０■／ｎ（となるよう
に塗布した以外は実施例−１と同一の条件で８閤ビデオ
テープの試料を作成した。[Comparative Example-7] Fluorinated polyether was not used, and a 1% by weight methanol solution of the compound of formula (9) above was used as an oxoacid salt having a hydrocarbon group, and the surface coating amount was 20 μ/n (and An 8-pan videotape sample was prepared under the same conditions as in Example 1, except that the coating was applied so that the coating was applied in such a manner that the coating was applied in such a manner that the coating was carried out under the same conditions as in Example-1.
〔比較例−８］
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（１）式の化合物の１０．５重量
％のメチルエチルケトン溶液を、表面塗布量が１０■／
ＩＴ？となるように塗布した以外は実施例−１と同一の
条件で８閣ビデオテープの試料を作成した。[Comparative Example-8] Fluorinated polyether was not used, and a 10.5% by weight methyl ethyl ketone solution of the compound of the formula (1) was used as an oxoacid salt having a hydrocarbon group at a surface coating amount of 10 cm/
IT? Samples of 8-kaku videotape were prepared under the same conditions as in Example 1, except that the coating was applied so that the following was applied.
〔比較例−９］
フッ素化ポリエーテルは使用せず、炭化水素基を有する
オキソ酸塩として前記（］）弐の化合物５部とブチルス
テアレート５部とをメチルエチルケトン１２００部に溶
解した溶液を、表面塗布量が前記２種の化合物の合計で
１５■／ボとなるように塗布した以外は実施例−１と同
一の条件で８閤ビデオテープの試料を作成した。[Comparative Example-9] No fluorinated polyether was used, but a solution of 5 parts of the compound (2) and 5 parts of butyl stearate dissolved in 1200 parts of methyl ethyl ketone was used as an oxoacid salt having a hydrocarbon group. An 8-pan videotape sample was prepared under the same conditions as in Example 1, except that the surface coating amount was 15 cm/bot in total of the above two types of compounds.
〔比較例−１０〕
炭化水素基を有するオキソ酸塩及びフッ素化ポリエーテ
ルをともに使用しなかった以外は実施例−１と同一の条
件で８閣ビデオテープの試料を作威した。[Comparative Example-10] A sample of 8-kaku videotape was produced under the same conditions as in Example-1 except that neither the oxoacid salt having a hydrocarbon group nor the fluorinated polyether was used.
以上のようにして得られた８ｍビデオテープの試料の繰
り返し走行後の出力及び摩擦係数について低下の条件で
測定した。得られた結果が第１表である。The output and friction coefficient after repeated running of the 8 m videotape sample obtained as described above were measured under conditions of decrease. The results obtained are shown in Table 1.
出力の測定：８ｓｉビデオ用ＶＴＲ（富士写真フィルム
■： ＦＵＪ ｌＸ−８）を用いてＩＭＨｚの信号を記
録し、２３℃７０％の環境条件下で１２０分長を３００
回走行後の再生出力を測定した。Output measurement: Record an IMHz signal using an 8si video VTR (Fuji Photo Film ■: FUJ lX-8), and record a 120-minute length at 300 minutes under the environmental condition of 23°C and 70%.
The reproduction output was measured after running twice.
基準テープに記録したＩＭＨｚの再生出力をＯｄＢとし
たときのビデオテープの各試料の相対的な再生出力を測
定した。The relative reproduction output of each videotape sample was measured when the reproduction output of IMHz recorded on the reference tape was set as OdB.
摩擦係数の測定：８■ビデオテープの試料とステンレス
ポールとを５０ｇの張力（Ｔ Ｉ ＞で接触（巻きつけ
角１８０＠）させて、８ｍビデオテープの試料を３．３
ｃｍ／ｓの速度で走行させるのに必要な（Ｔ２）を測定
した。この測定値をもとに、下記計算式により、摩擦係
数μを算出したｕ＝１／ｚ −１ｎ （Ｔ２／Ｔｌ）
尚、摩擦係数のテストは、ａ、２０℃、８０％ＲＨ，ｂ
、４０°Ｃ１９０％ＲＨの２条件で行なった。Measurement of friction coefficient: 8 ■ Bring the videotape sample into contact with the stainless steel pole at a tension of 50g (T I > (wrapping angle 180@), and the 8m videotape sample was 3.3
The (T2) required to run at a speed of cm/s was measured. Based on this measurement value, the friction coefficient μ was calculated using the following formula: u = 1/z -1n (T2/Tl) The friction coefficient test was performed at
The test was carried out under two conditions: , 40° C., 190% RH.
また−１０”Ｃ１１０％の条件で１２０分長を２００パ
ス繰り返し走行したあとの２３°Ｃ７０％におけるｌ！
！擦係数を測定した。In addition, l at 23°C and 70% after repeatedly running 200 passes for 120 minutes under the condition of -10"C and 110%!
! The friction coefficient was measured.
第１表より明白な如く、本発明の、炭化水素系オキソ酸
とパーフルオロポリエーテルの組合せを用いた実施例１
〜１６はいずれもａ、ｂ両条件でも摩擦係数が低く、低
温での繰り返し走行によっても摩擦係数が上昇せず性能
が安定であることが分かった。As is clear from Table 1, Example 1 using a combination of hydrocarbon oxoacid and perfluoropolyether of the present invention
It was found that all of No. 1 to No. 16 had low friction coefficients under both conditions a and b, and the performance was stable with no increase in friction coefficient even after repeated running at low temperatures.
一方、本発明の化合物を使用せず、炭化水素系オキソ酸
やパーフルオロポリエーテルのみを用いた場合や、他の
タイプの組合せで、高温、高温（ｂ条件）下での摩擦係
数が大きく、低湿で繰り返し走行することで摩擦係数が
著しく上昇し、問題が大きいことがわかった。On the other hand, when the compound of the present invention is not used and only a hydrocarbon-based oxoacid or perfluoropolyether is used, or when other types of combinations are used, the coefficient of friction at high temperatures (b condition) is large. It was found that repeated driving in low humidity caused a significant increase in the coefficient of friction, posing a serious problem.
Claims (3)
おいて、炭化水素基を有するオキソ酸またはその塩とフ
ッ素化ポリエーテルとが該磁性層表面もしくは内部に保
持されていることを特徴とする磁気記録媒体(1) A magnetic recording medium having a magnetic layer on a non-magnetic support, characterized in that an oxo acid having a hydrocarbon group or a salt thereof and a fluorinated polyether are held on the surface or inside the magnetic layer. magnetic recording media
化水素置換硫酸エステルもしくは炭化水素系スルホン酸
またはこれらの塩である請求項１記載の磁気記録媒体(2) The magnetic recording medium according to claim 1, wherein the oxoacid having a hydrocarbon group or its salt is a hydrocarbon-substituted sulfuric acid ester, a hydrocarbon-based sulfonic acid, or a salt thereof.
気記録媒体(3) The magnetic recording medium according to claim 1, wherein the magnetic layer is a ferromagnetic metal thin film.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18213389A JP2941849B2 (en) | 1989-07-14 | 1989-07-14 | Magnetic recording media |
| DE19904022202 DE4022202C5 (en) | 1989-07-14 | 1990-07-12 | Magnetic recording medium |
| US07/858,432 US5268227A (en) | 1989-07-14 | 1992-03-24 | Magnetic recording medium comprising a ferromagnetic metallic then film having a top coat of (a) a hydrocarbonsulfuric or hydrocarbonsulfonic acid or salt and (b) a fluorinated polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18213389A JP2941849B2 (en) | 1989-07-14 | 1989-07-14 | Magnetic recording media |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0346121A true JPH0346121A (en) | 1991-02-27 |
| JP2941849B2 JP2941849B2 (en) | 1999-08-30 |
Family
ID=16112913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18213389A Expired - Fee Related JP2941849B2 (en) | 1989-07-14 | 1989-07-14 | Magnetic recording media |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2941849B2 (en) |
| DE (1) | DE4022202C5 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192028A (en) * | 1986-02-18 | 1987-08-22 | Hitachi Maxell Ltd | Magnetic recording medium |
-
1989
- 1989-07-14 JP JP18213389A patent/JP2941849B2/en not_active Expired - Fee Related
-
1990
- 1990-07-12 DE DE19904022202 patent/DE4022202C5/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4022202C2 (en) | 1999-11-11 |
| JP2941849B2 (en) | 1999-08-30 |
| DE4022202C5 (en) | 2005-06-23 |
| DE4022202A1 (en) | 1991-01-24 |
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