JPH01220216A - Magnetic recording medium - Google Patents
Magnetic recording mediumInfo
- Publication number
- JPH01220216A JPH01220216A JP4727188A JP4727188A JPH01220216A JP H01220216 A JPH01220216 A JP H01220216A JP 4727188 A JP4727188 A JP 4727188A JP 4727188 A JP4727188 A JP 4727188A JP H01220216 A JPH01220216 A JP H01220216A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic layer
- magnetic
- thickness direction
- substrate
- nitrogen
- 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 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910001337 iron nitride Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 238000010884 ion-beam technique Methods 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 40
- 150000002500 ions Chemical class 0.000 description 21
- 239000010408 film Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 9
- -1 Fe%Co and Ni Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 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 3
- 230000001133 acceleration Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229910000727 Fe4N Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（発明の分野）
本発明は、金属薄膜磁性層を有する磁気記録媒体に関し
、特に、金属薄膜磁性層の耐蝕性、耐候性及び電磁変換
特性が改良された磁気記録媒体に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a magnetic recording medium having a thin metal magnetic layer, and particularly to a magnetic recording medium in which the corrosion resistance, weather resistance, and electromagnetic conversion characteristics of the thin metal magnetic layer are improved. It is related to.
（従来技術とその問題点）
従来、代表的な磁気記録媒体としては、強磁性粉末をバ
インダ中に分散し、それを非磁性基体上に塗着、乾燥さ
せた、所謂、塗布型媒体（バインダ型媒体とも言う）が
挙げられるが、その媒体は次のような問題を抱えている
。(Prior art and its problems) Conventionally, typical magnetic recording media have been so-called coated media (binder (also referred to as type media), but these media have the following problems.
即ち、バインダを含有するため磁束密度を大きくするこ
とが困難であり、磁性層の薄膜化（例えば、０．７μｍ
）と均一な膜厚を図ることも塗布技術上の限界があるた
め、近年要望が高まっている／、９μｍ以下の記録波長
における高密度記録に適する電磁変換特性を付与せしめ
ることが困難になってきた。That is, since it contains a binder, it is difficult to increase the magnetic flux density, and it is difficult to make the magnetic layer thinner (for example, 0.7 μm).
) Due to the limitations of coating technology in achieving a uniform film thickness, the demand has been increasing in recent years.It has become difficult to provide electromagnetic conversion characteristics suitable for high-density recording at recording wavelengths of 9 μm or less. Ta.
これに対し、金属薄膜磁性層を、真空蒸着法、イオンブ
レーティング法、スパッタリング法等のドライプロセス
で基体上に設ける、所謂、金属薄膜型媒体（非・５イン
ダ型媒体とも言う。）の開発によって、バインダ等の非
磁性成分を排除し、強磁性化合物を主成分とする前記金
属薄膜磁性層が、従来の塗布型媒体では得られない、均
一、薄層かつ高磁束密度を以って、高密度記録な容易に
した。In response to this, the development of so-called metal thin film media (also referred to as non-5-inder media), in which a metal thin film magnetic layer is provided on a substrate using a dry process such as vacuum evaporation, ion blating, or sputtering. By eliminating non-magnetic components such as binders, the metal thin film magnetic layer containing a ferromagnetic compound as a main component has a uniform, thin layer and high magnetic flux density that cannot be obtained with conventional coated media. High-density recording made easy.
しかしながら、前記金属薄膜型媒体の磁性層は、主とし
てＦｅ％Ｃｏ、Ｎｉ等の金属から成り、これらの元素は
化学的安定性に欠け、耐蝕性や耐候性が前記塗布型媒体
に比べ劣っていた。However, the magnetic layer of the metal thin film type medium is mainly composed of metals such as Fe%Co and Ni, and these elements lack chemical stability and are inferior in corrosion resistance and weather resistance compared to the coated type medium. .
この欠点を解消するために、種々の提案がなされ、特に
、特開昭ｔｏ−ｚ３ｒｏｔ号公報に開示されたように、
金属薄膜磁性層の表面をイオンブレーティング法により
窒化処理を施す方法や特開昭タ！−３０３０≠号公報に
開示されたように、スパッタリング法により前記磁性層
表面に窒化ケイ素膜を設ける方法、あるいは特開昭１ｓ
−ｔｒ４ｃｏ３号公報に開示されたように、前記磁性層
を窒素ガス等を含む雰囲気中での放電にさらして、その
表面に非磁性保護層を形成する方法が効果的なものであ
る。In order to eliminate this drawback, various proposals have been made;
A method of nitriding the surface of a metal thin film magnetic layer using the ion blating method and JP-A-Shota! A method of forming a silicon nitride film on the surface of the magnetic layer by a sputtering method as disclosed in Publication No. 3030≠, or
As disclosed in the tr4co3 publication, an effective method is to expose the magnetic layer to discharge in an atmosphere containing nitrogen gas or the like to form a nonmagnetic protective layer on the surface thereof.
しかし、これらの方法は前記磁性層の表面に窒化物の層
を設けたことにより、電磁変換特性が低下してしまう欠
点があり、ヨーロッパ特許第１ｒ３２を号、特開昭タタ
ーｒ’ｙｔｏり号、特開昭６Ｏ−２３ｔｔｔｉ号、特開
昭６１−！μ０２３号、等の各公報に開示されている窒
化鉄、鉄と窒化鉄、又は酸化窒化鉄（ＦｅＮｘＯｙ）か
ら成る金属薄膜磁性層をもってしても、変調ノイズが大
きくなると言う電磁変換特性上の欠点が残されていた。However, these methods have the disadvantage that the electromagnetic conversion characteristics deteriorate due to the provision of a nitride layer on the surface of the magnetic layer. , JP-A-6O-23ttti, JP-A-61-! Even with the metal thin film magnetic layer made of iron nitride, iron and iron nitride, or iron oxynitride (FeNxOy) disclosed in publications such as μ023, there is a drawback in electromagnetic conversion characteristics that modulation noise increases. was left behind.
一方、前記磁性層を窒化鉄で構成させかつその窒素含有
比率を表面近傍で最大にするもの←特開昭ｔ ／−６１
１０２０号公報）や逆に基体側近傍で最大にするもの（
％開昭＆／−！ｒ≠０２／号公報）も提案されているが
、これらの媒体も前述した変調ノイズが太き（なってし
まう欠点を有していた。On the other hand, the magnetic layer is composed of iron nitride, and the nitrogen content ratio is maximized near the surface←Unexamined Japanese Patent Application Publication No. 2003-120001/-61
1020 Publication) or conversely, the one that maximizes near the base side (
% Kaisho &/-! r≠02/publication) has also been proposed, but these media also have the drawback that the modulation noise described above becomes thick.
（発明の目的）
本発明は、前述した従来技術の欠点即ち金属薄膜磁性層
の耐蝕性と耐候性を増すと、その電磁変換特性が低下し
てしまうことを解消し、高密度記録が容易な磁気記録媒
体を提供することを目的とするものである。(Objective of the Invention) The present invention solves the above-mentioned drawbacks of the prior art, namely, that increasing the corrosion resistance and weather resistance of a metal thin film magnetic layer causes a decrease in its electromagnetic conversion characteristics, and facilitates high-density recording. The purpose is to provide a magnetic recording medium.
（目的を達成するだめの手段）
本発明のかかる目的は、非磁性基体上に窒化鉄あるいは
酸化窒化鉄を主成分とする金属薄膜磁性層を設けて成る
磁気記録媒体において、前記金属薄膜磁性層の厚さ方向
における窒素原子の鉄原子に対する比率が、該厚さ方向
の中央部近傍で最大となることを特徴とする磁気記録媒
体によって達成される。(Means for Achieving the Object) The object of the present invention is to provide a magnetic recording medium comprising a metal thin film magnetic layer containing iron nitride or iron oxynitride as a main component on a non-magnetic substrate. This is achieved by a magnetic recording medium characterized in that the ratio of nitrogen atoms to iron atoms in the thickness direction is maximum near the center in the thickness direction.
以下く、添付した図面を参照して本発明媒体の一実施態
様を詳述する。先ず、本発明媒体の層構成を概説する。Hereinafter, one embodiment of the medium of the present invention will be described in detail with reference to the accompanying drawings. First, the layer structure of the medium of the present invention will be outlined.
第１図において、本発明媒体は、非磁性基体ｌ上に金属
薄膜磁性層２を層設し、更にその表面に摩擦係数を下げ
、媒体の走行安定性と耐久性を付与するための潤滑層３
を設げている。In FIG. 1, the medium of the present invention has a metal thin film magnetic layer 2 layered on a non-magnetic substrate 1, and a lubricating layer on the surface of the magnetic layer 2 for lowering the coefficient of friction and imparting running stability and durability to the medium. 3
has been established.
又、前記基体ｌの裏側には媒体の走行安定性を付与する
だめのバック層μが設けられている。Further, a back layer μ is provided on the back side of the base 1 to provide running stability of the medium.
なお、前記金属薄膜磁性層コは、純鉄（α−Ｆｅ）、窒
化鉄（Ｆｅ２〜３Ｎ、Ｆｅ４Ｎ、Ｆｅ６Ｎ）、酸化鉄（
ＦｅＯｘ）あるいはそれらの混合体、更に必要に応じて
Ｃｏ、Ｃｒ５Ｎｉ、Ｔｉ。The metal thin film magnetic layer is made of pure iron (α-Fe), iron nitride (Fe2-3N, Fe4N, Fe6N), iron oxide (
FeOx) or a mixture thereof, and if necessary, Co, Cr5Ni, and Ti.
Ａｔ等を含有して、真空蒸着法、イオンブレーティング
法、スパッタリング法、等のドライブロセ基体Ｉ上に成
膜されたものである。The film contains At and the like and is formed on a dry broceive substrate I using a vacuum evaporation method, an ion blating method, a sputtering method, or the like.
又、前記非磁性基体ｌは、ポリエチレンテレフタレート
、ポリイミド、ポリアミド、ポリ塩化ビニル、三酢酸セ
ルロース、ポリカーボネート、等のプラスチックフィル
ムから成っている。The nonmagnetic substrate 1 is made of a plastic film such as polyethylene terephthalate, polyimide, polyamide, polyvinyl chloride, cellulose triacetate, polycarbonate, or the like.
前記潤滑層３は、通常、炭素数が１２乃至ｔｒの脂肪酸
、該脂肪酸金属塩、シリコーンオイル、脂肪酸エステル
、等を０．！乃至２０■／ｍ の量で塗着されたもので
ある。The lubricating layer 3 usually contains a fatty acid having 12 to tr carbon atoms, a fatty acid metal salt, a silicone oil, a fatty acid ester, or the like. ! The coating was applied in an amount of 20 to 20 μm/m 2 .
又、前記バック層μは、通常、カーホ゛ンブラック、炭
酸カルシウム、酸化チタン、等の微粉末をバインダー中
に分散させた組成物を塗着して成るものである。The back layer μ is usually formed by coating a composition in which fine powders of carbon black, calcium carbonate, titanium oxide, etc. are dispersed in a binder.
次に、第２図に示した本発明媒体の製造装置を参照して
その製法について述べる。Next, the manufacturing method will be described with reference to the apparatus for manufacturing the medium of the present invention shown in FIG.
先ず、真空槽ｉｏ内の真空度をＩＱ 乃至１Ｏ−７
Ｔｏｒｒになるように真空ポンプ（図示せず）を起動さ
せ、排気口／／から槽内の空気を排出した後、比較的長
尺の非磁性基体！（例えば、ポリエチレンテレフタレー
トフィルム）を、その原反ロール１３から繰り出し、複
数本のガイドローラｌψによって形成される走行路に沿
って巻取ロール／りへ一定速度で連続的に移送させなが
ら、ハース／４内の純鉄１７を該ノ・−ス１６の近傍に
配設したフィラメント／ｒによって発生した電子ビーム
ｌりにより加熱、蒸発させる。First, the degree of vacuum in the vacuum chamber io is from IQ to 1O-7.
After starting the vacuum pump (not shown) so that the pressure becomes Torr and exhausting the air in the tank from the exhaust port, a relatively long non-magnetic substrate is removed! (For example, polyethylene terephthalate film) is unwound from the raw roll 13 and continuously transferred at a constant speed to the take-up roll/roll along the running path formed by the plurality of guide rollers lψ. The pure iron 17 in 4 is heated and evaporated by the electron beam generated by the filament /r placed near the nose 16.
蒸発した前記純鉄１７は蒸気流コθとなってその一部は
マスク２１により上昇、拡散運動が遮断されるが他の大
部分は前記マスク２１の開口部１２を通過して前記走行
路の一部を構成する支持板２コの傾斜面上に沿って移動
する前記基体ｌの表面に近接して行（。The evaporated pure iron 17 becomes a vapor flow θ, and a part of it rises by the mask 21 and its diffusion movement is blocked, but most of the other part passes through the opening 12 of the mask 21 and flows along the traveling path. A row (.
前記基体ｌの表面に近接した前記蒸気流２０の鉄原子は
、イオン銃−２３から引き出された窒素ガスのイオン・
中性高速粒子、励起分子、原子等が混在するイオンビー
ム２夕に照射されて、それらと反応して窒化鉄を主体と
する金属薄膜磁性層コが前記基体ｌの表面に形成される
。The iron atoms in the vapor stream 20 that are close to the surface of the base 1 are ionized by nitrogen gas ions extracted from the ion gun 23.
It is irradiated with an ion beam containing a mixture of neutral high-velocity particles, excited molecules, atoms, etc., and reacts with them to form a metal thin film magnetic layer mainly composed of iron nitride on the surface of the substrate 1.
なお、前記イオン銃２３は後部の導入口２≠から窒素ガ
スを導入し、その内部でプラズマを発生させ、前記イオ
ンビーム２夕を外部に引き出すもので、カウフマン型あ
るいはフリーマン型イオン銃が広く用いられている。The ion gun 23 introduces nitrogen gas from the rear introduction port 2≠, generates plasma inside it, and extracts the ion beam 2 to the outside. Kaufman type or Freeman type ion guns are widely used. It is being
又、前記イオンビーム２よの中心流は、前記マスク２１
の開口部１２の中心線２６を通って前記支持板ココ上の
基体／に略垂直に向けられているので、前記基体ｌ上の
成膜領域の中央部が最大のイオン電流密度が与えられ、
第３図に示したように、前記磁性層コ全体の厚さ方向に
おける窒素原子の鉄原子に対する比率は、その中央部近
傍ｄ３〜ｄ５で最大値ｅ３を示し、最小値ｅ１又はｅ２
は前記磁性層コの表面近傍ｄ１又は前記基体ｌの近傍ｄ
７に存在する山型の分布パターンを呈することになる。Further, the central flow of the ion beam 2 is directed to the mask 21.
is oriented substantially perpendicularly to the substrate on the support plate through the center line 26 of the opening 12, so that the maximum ion current density is applied to the center of the film forming area on the substrate.
As shown in FIG. 3, the ratio of nitrogen atoms to iron atoms in the thickness direction of the entire magnetic layer has a maximum value e3 in the vicinity of the central portion d3 to d5, and a minimum value e1 or e2.
is the vicinity d1 of the surface of the magnetic layer 1 or the vicinity d of the base 1
This results in the mountain-shaped distribution pattern that exists in No. 7.
なお、第３図の窒素原子含有ノターンは、オージェ電子
分光法により磁性層の厚さ方向に電子線でエツチングし
ながら元素分布を測定したとぎに得られるものである。The nitrogen atom-containing noturns shown in FIG. 3 are obtained by measuring the elemental distribution while etching the magnetic layer with an electron beam in the thickness direction using Auger electron spectroscopy.
なお、第３図の横軸の各点は前記点ｄ１からｄ７までの
間を６等分したときの各区分点を示している。Note that each point on the horizontal axis in FIG. 3 indicates a dividing point when the area from the points d1 to d7 is divided into six equal parts.
前述したような方法で窒化鉄の磁性膜を種々の条件で形
成し、各特性について評価を行った結果、次のような結
論が得られた。As a result of forming iron nitride magnetic films under various conditions using the method described above and evaluating each characteristic, the following conclusions were obtained.
−ｌ、 前記磁性層コの全体に含まれる窒素は元素百分
率で２原子％乃至３０原子％、望ましくは４Ｌ原子％乃
至２０原子％、特に！原子う乃至ｌ！原子％が望ましい
。-1, Nitrogen contained in the entire magnetic layer is in an elemental percentage of 2 atomic % to 30 atomic %, preferably 4L atomic % to 20 atomic %, especially! Atomic u-no-l! Atomic % is preferable.
窒素の含有量が前述した数値よりも少ないと耐蝕性と耐
候性が低下する一方、多いと飽和磁束密度（Ｂｍ）、抗
磁力（Ｈｅ）が低下してしまう。If the nitrogen content is less than the above-mentioned value, the corrosion resistance and weather resistance will decrease, while if it is higher than the above value, the saturation magnetic flux density (Bm) and coercive force (He) will decrease.
−λ、 第３図における最大値ｅ３と最小値ｅ１又はｅ
２との差は鉄原子に対する窒素原子の比率で、２原子％
以上、望ましくはｌ原子％以上である。-λ, maximum value e3 and minimum value e1 or e in Fig. 3
The difference from 2 is the ratio of nitrogen atoms to iron atoms, which is 2 atomic%.
The content is desirably 1 atomic % or more.
その差が小さいと変調ノイズが小さ（ならない。If the difference is small, the modulation noise will be small (or not).
−３，前記最小値ｅ１又はｅ２はコ原子％以上が好まし
く、望ましくは４ｃ原子％以上である。-3, the minimum value e1 or e2 is preferably coatom % or more, and desirably 4c atom% or more.
この最小値ｅ１又はｅ２が小さいと、耐蝕性と耐候性が
劣化する。If this minimum value e1 or e2 is small, corrosion resistance and weather resistance will deteriorate.
一層、 第２図において、酸素導入口２７より前記開口
部１２に向けて酸素ガスを導入し、前記磁性層コ中に構
成原子として酸素を含有させると、抗磁力（Ｈｃ）が大
きくなり、耐久性も増すが、含有量を増すと飽和磁束密
度（Ｂｍ）が低下してしまうので、酸素の含有比率は元
素百分率で２原子％乃至３θ原子％、望ましくは！原子
％乃至コＯ原子％である。Further, in FIG. 2, when oxygen gas is introduced from the oxygen inlet 27 toward the opening 12 and oxygen is contained as a constituent atom in the magnetic layer, the coercive force (Hc) increases and the durability increases. However, increasing the content lowers the saturation magnetic flux density (Bm), so the content ratio of oxygen should be between 2 atomic % and 3θ atomic % in terms of element percentage! atomic % to CoO atomic %.
（発明の効果）
本発明の窒素のイオンビームを成膜領域の中心でそのイ
オン電流密度が最大になる様に分布させたので、磁性膜
中の窒素原子の分布がその厚さ方向での最大値が中央部
近傍に存在し、その結果、磁性層の耐蝕性、耐候性及び
電磁変換特性が揃って良化される。(Effects of the Invention) Since the nitrogen ion beam of the present invention is distributed so that its ion current density is maximized at the center of the film forming region, the distribution of nitrogen atoms in the magnetic film is maximized in the thickness direction. As a result, the corrosion resistance, weather resistance, and electromagnetic conversion characteristics of the magnetic layer are all improved.
以上、記述した本発明媒体の新規な効果を実施例と比較
例によって一層明確に示す。The novel effects of the medium of the present invention described above will be more clearly demonstrated through Examples and Comparative Examples.
（実施例−ｌ） 第２図に示した装置を用い、真空度を一旦！。(Example-l) Use the device shown in Figure 2 to establish the degree of vacuum! .
Ｏｘｌ’ Ｔｏｒｒにした後、窒素ガスを導入して
真空度Ｙ／、ｒｘｔｏ Ｔｏｒｒして、純度タタ、
り％の鉄を電子ビームにより加熱、蒸発させた。After setting the temperature to Oxl' Torr, introduce nitrogen gas and increase the vacuum degree to Y/, rxto Torr, and reduce the purity to
% of iron was heated and evaporated by an electron beam.
蒸発速度は蒸着膜が６０Ａ／秒となる。！、つに電子ビ
ームのパワーを調節した。The evaporation rate of the deposited film is 60 A/sec. ! First, the power of the electron beam was adjusted.
同時に巾ｔ００ｍｍ厚さ１３μｍのポリエチレンテレフ
タレートフィルムをμθｃＩＣに保ってコｏｏｏ人の膜
厚となるようにその移送速度を定め、前記鉄の蒸発流の
入射角を６タ０に設定した。At the same time, a polyethylene terephthalate film having a width of t00 mm and a thickness of 13 μm was maintained at μθcIC, the transport speed was determined so as to have a film thickness of 100 mm, and the incident angle of the evaporated iron flow was set at 600 mm.
又、矩形状のｓ ｏｍｍｘ ／ ｏｏｍｍの口径を有す
るカウフマン型イオン銃を第μ図の曲線■に示したイオ
ン電流密度分布となるようにイオン銃の加速電圧をｒｏ
ｏＶとし、放電室のグロー条件を設定して、前記蒸発流
の鉄原子にイオンビームを照射し、金属薄膜磁性層を形
成した。なお、マスクの開口部は巾デｏｍｍ、長さｔｏ
ｍｍとした。In addition, the accelerating voltage of the ion gun was set to ro so that the ion current density distribution of a rectangular Kaufmann type ion gun with a diameter of sommx/oomm would be as shown by the curve
oV and glow conditions in the discharge chamber were set to irradiate the iron atoms in the evaporated flow with an ion beam to form a metal thin film magnetic layer. The opening of the mask has a width of 0 mm and a length of
mm.
（実施例−コ）
実施例−７と同じ装置を用い、真空度を一旦、／、０ｘ
１０−５Ｔｏｒｔにした後、酸素ガスを導入して真空度
’１３．ＯＸ／ ０−５Ｔｏｒｒとし、更に、窒素ガス
を導入して真空度を／、ｊ×１０−’Ｔｏｒｒとした。(Example-7) Using the same equipment as in Example-7, the degree of vacuum was once changed to /, 0x.
After setting the pressure to 10-5 Tort, oxygen gas was introduced and the vacuum level was set to '13. OX/ was set to 0-5 Torr, and nitrogen gas was further introduced to set the degree of vacuum to /,j×10-'Torr.
イオン電流密度分布は第μ図の曲線■となるように、イ
オン銃の加速電圧なｒｏｏＶとし、放電室のグロー条件
を設定した以外は実施例−ｌと同じ条件で磁性膜を形成
した。A magnetic film was formed under the same conditions as in Example 1, except that the acceleration voltage of the ion gun was set to rooV and the glow conditions of the discharge chamber were set so that the ion current density distribution was as shown by curve 2 in Figure μ.
（比較例−ｌ）
イオン電流密度が第μ図の曲線■となるように、イオン
銃の加速電圧を２ｊＯ■として放電室のグロー条件を設
定した以外は、実施例−ｌと同じ条件で磁性層を形成し
た。(Comparative Example-l) The magnetic field was heated under the same conditions as in Example-l, except that the acceleration voltage of the ion gun was set to 2jO■ and the glow conditions of the discharge chamber were set so that the ion current density became the curve ■ in Figure μ. formed a layer.
（比較例−２）
イオン電流密度分布が第μ図の曲線■となるように、イ
オン銃の加速電圧を、２ｊＯＶとし、放電室のグロー条
件を設定した以外は実施例−１と同じ条件で磁性層を形
成した。(Comparative Example-2) The same conditions as Example-1 were used, except that the acceleration voltage of the ion gun was set to 2jOV and the glow conditions of the discharge chamber were set so that the ion current density distribution became the curve ■ in Figure μ. A magnetic layer was formed.
実施例−ｌ、−２、比較例−７、−２によって得られた
試料中の鉄、窒素、酸素の各原子について膜厚方向の分
布を測定した結果は第５図乃至第ｒ図の通りであった。The results of measuring the distribution of iron, nitrogen, and oxygen atoms in the film thickness direction in the samples obtained in Examples-l and -2 and Comparative Examples-7 and -2 are as shown in Figures 5 to R. Met.
（比較例−３）
実施例−１において、イオン銃の位置を基体搬送方向に
沿って下方に平行移動した。その他の条件は実施例−１
と同一の条件で成膜を行った。(Comparative Example-3) In Example-1, the position of the ion gun was translated downward along the substrate transport direction. Other conditions are Example-1
Film formation was performed under the same conditions as .
（比較例−４ｃ）
実施例−７において、イオン銃位置を基体搬送方向に沿
って上方に平行移動した。その他の条件は、実施例−ｌ
と同一の条件で成膜した。(Comparative Example-4c) In Example-7, the ion gun position was translated upward along the substrate transport direction. Other conditions are Example-1
The film was formed under the same conditions as .
比較例−３、−μによって得られた試料中の鉄、窒素、
酸素の各原子についての膜厚方向の分布を測定した結果
は、第２図乃至第１Ｏ図の通りであった。Comparative Example-3, iron, nitrogen in the sample obtained by -μ,
The results of measuring the distribution of each oxygen atom in the film thickness direction are shown in FIGS. 2 to 1O.
次に、以上のようにして得られた蒸着原反にパック層を
塗設し、さらに磁性層の表面には、ミリスチン酸を１０
ｍ９７ｍ となるようＭＥＫの溶液にして塗布した。Next, a pack layer was applied to the vapor-deposited original fabric obtained in the above manner, and the surface of the magnetic layer was further coated with 10% of myristic acid.
It was coated as a solution of MEK so that the thickness was 97 m.
次いでｒミリ巾に裁断し、ｒミリビデオ用カセットに組
込み電磁変換特性を測定した。Next, it was cut into r mm width and incorporated into an r mm video cassette, and the electromagnetic conversion characteristics were measured.
測定は、富士写真フィルム製ＦＵＪＩＸ−Ｊ’Ｍ４−Ａ
Ｆを改造し、さらにヒューレットノ署ツカード社製スイ
クトロアナライザー３．ｆｌｒｊＡを用いてＣＮ比を求
めた。なお、キャリヤー周波数は６ＭＨｚノイズ周波数
は２ Ｍ Ｈｚである。その結果を第７表に示す。Measurement was done using Fuji Photo Film FUJIX-J'M4-A.
Modified the F, and added a Suictro Analyzer 3. manufactured by Hewlett-Packard Corporation. The CN ratio was determined using flrjA. Note that the carrier frequency is 6 MHz and the noise frequency is 2 MHz. The results are shown in Table 7.
実施例のサンプルは比較例のサンプルに比較し【、出力
が大きく、かつノイズも低くなっており、ＣＮ比を大き
くでき、高特性であることが分る。It can be seen that the sample of the example has a larger output and lower noise than the sample of the comparative example, can increase the CN ratio, and has high characteristics.
第１表Table 1
第１図・・・・・・本発明の磁気記録媒体の層構成の一
例。
第２図・・・・・・本発明の磁気記録媒体の製造装置の
一例。
第３図・・・・・・本発明の磁気記録媒体の金属薄膜磁
性層の厚さ方向における窒素原子の
分布。
第μ図・・・・・・第２図の製造装置の成膜部分におけ
るイオン電流密度の分布。
第を図乃至第１Ｑ図・・・・・・本発明の実施例、比較
例における金属薄膜磁性層の厚さ方
向における窒素原子、鉄原子、酸素
原子の分布。
ｌ：非磁性基体 ２＝金属薄膜磁性層１２：マス
クの開口部 １７：純鉄
２０：蒸気流 ２２二支持板
２３：イオン銃 ２ｊ＝イオンビ一ム第！図乃至
第１Ｑ図の図中におげろ曲線Ｎ。
Ｆｅ及びＯは夫々窒素原子、鉄原子及び酸素原子の膜厚
方向における含有率を示す。
特許出願人 富士写真フィルム株式会社第１図
第２図
第５図
第６図
第７図
「ρ
第８図FIG. 1: An example of the layer structure of the magnetic recording medium of the present invention. FIG. 2: An example of a magnetic recording medium manufacturing apparatus according to the present invention. FIG. 3: Distribution of nitrogen atoms in the thickness direction of the metal thin film magnetic layer of the magnetic recording medium of the present invention. Figure μ: Distribution of ion current density in the film forming part of the manufacturing apparatus shown in Figure 2. Figures 1 to 1Q: Distribution of nitrogen atoms, iron atoms, and oxygen atoms in the thickness direction of the metal thin film magnetic layer in Examples and Comparative Examples of the present invention. 1: Non-magnetic substrate 2 = Metal thin film magnetic layer 12: Mask opening 17: Pure iron 20: Vapor flow 22 Support plate 23: Ion gun 2j = Ion beam 1st! There is a curve N in the figures from Figures to Figures 1Q. Fe and O indicate the content of nitrogen atoms, iron atoms, and oxygen atoms in the film thickness direction, respectively. Patent applicant: Fuji Photo Film Co., Ltd. Figure 1 Figure 2 Figure 5 Figure 6 Figure 7 "ρ Figure 8
Claims (1)
る金属薄膜磁性層を設けて成る磁気記録媒体において、
前記金属薄膜磁性層の厚さ方向における窒素原子の鉄原
子に対する比率が、該厚さ方向の中央部近傍で最大とな
ることを特徴とする磁気記録媒体。In a magnetic recording medium comprising a metal thin film magnetic layer mainly composed of iron nitride or iron oxynitride on a non-magnetic substrate,
A magnetic recording medium characterized in that the ratio of nitrogen atoms to iron atoms in the thickness direction of the metal thin film magnetic layer is maximum near the center in the thickness direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4727188A JPH01220216A (en) | 1988-02-29 | 1988-02-29 | Magnetic recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4727188A JPH01220216A (en) | 1988-02-29 | 1988-02-29 | Magnetic recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01220216A true JPH01220216A (en) | 1989-09-01 |
Family
ID=12770629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4727188A Pending JPH01220216A (en) | 1988-02-29 | 1988-02-29 | Magnetic recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01220216A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5426006A (en) * | 1993-04-16 | 1995-06-20 | Sandia Corporation | Structural micro-porous carbon anode for rechargeable lithium-ion batteries |
| US5510212A (en) * | 1993-01-13 | 1996-04-23 | Delnick; Frank M. | Structural micro-porous carbon anode for rechargeable lithium ion batteries |
-
1988
- 1988-02-29 JP JP4727188A patent/JPH01220216A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510212A (en) * | 1993-01-13 | 1996-04-23 | Delnick; Frank M. | Structural micro-porous carbon anode for rechargeable lithium ion batteries |
| US5426006A (en) * | 1993-04-16 | 1995-06-20 | Sandia Corporation | Structural micro-porous carbon anode for rechargeable lithium-ion batteries |
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