JPS5963031A - Manufacture of magnetic recording medium - Google Patents

Abstract

PURPOSE:To execute repeated running and to improve durability in high temperature and high humidity by forming a magnetic layer whose main component in a ferromagnetic metal on a substrate by a vacuum vapor-depositing method, and thereafter, setting the magnetic layer to a heated state, and exposing it in an ozone atmosphere. CONSTITUTION:A polymer film substrate 7 passes through on a mask 13 from the left and is fed to a winding shaft 10, but a substrate 7' on which a magnetic metal is vapor-deposited is heated on the way by a heating means 16, and on the other hand, an ozone-containing gas is led in from a gas leading-in port 14 provided on a vapor-depositing machine body 1, and the surface part of a vapor- deposited metal or a metallic oxide is oxidized in higher order and uniformly. In order to check an effect of this method, repeated running was executed 100 times as a reliability test by use of a standard deck on the market, variations of electromagnetic converting characteristic and a surface state are observed, and also variations of an electromagnetic converting characteristic and an external appearance are checked as an environment test by allowing it to stand for ten weeks in a high-temperture and high-humidity atmosphere of 60 deg.C and 90%RH, and all the results have been extremely satisfactory.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は真空蒸着法を用いた磁気記録媒体の製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method of manufacturing a magnetic recording medium using a vacuum evaporation method.

従来例の構成とその問題点 近年磁気記録媒体は磁気記録密度の向上に見られるよう
にその技術的発展はめざましいものがある。従来の磁気
記録媒体の代表例としてγ−Ｆ　ｅ　２０３粉末、　Ｃ
ｒＯ２粉末、純鉄粉末等をバインダーとともに高分子フ
ィルムに塗着せしめたいわゆる塗布型の磁気記録媒体が
ある。しかしこの塗布型より、保磁力、その他磁気特性
および記録密度を高めるために最近、斜方入射蒸着法や
、イオンブレーティング法によりＦｅ　、　Ｎｉ　、　
Ｃｏ等の強磁性体金属を単独もしくは合金とし高分子フ
ィルム基板」二に蒸着する蒸着薄膜型磁気記録媒体が検
討され、高い保磁力で高記録密度を有する磁気記録媒体
を得るに至っている。しかし蒸着薄膜型磁気記録媒体の
歴史も浅く、塗布型に比べ量産性及び工業的彦見地から
また十分に検討がなされていない。例えば真空蒸着法に
おいて高分子フィルムに蒸着する磁性金属の付着強度、
磁性金属を蒸着する場合に発生するアウトガスの影響に
よる蒸着膜の不均一性。Conventional Structures and Problems There has been remarkable technological development in magnetic recording media in recent years, as seen in the improvement in magnetic recording density. Typical examples of conventional magnetic recording media include γ-Fe 203 powder, C
There are so-called coated magnetic recording media in which rO2 powder, pure iron powder, etc. are coated on a polymer film together with a binder. However, in order to improve coercive force, other magnetic properties, and recording density, recently, Fe, Ni,
Vapor-deposited thin-film magnetic recording media in which a ferromagnetic metal such as Co, alone or as an alloy, is deposited on a polymer film substrate have been studied, and magnetic recording media with high coercive force and high recording density have been obtained. However, the history of vapor-deposited thin-film magnetic recording media is short, and compared to coating-type magnetic recording media, they have not been sufficiently studied from a mass-productivity and industrial perspective. For example, the adhesion strength of magnetic metal deposited on a polymer film in a vacuum evaporation method,
Non-uniformity of the deposited film due to the effects of outgas generated when depositing magnetic metals.

電磁変換特性等の問題がある。特に磁気テープとして使
用する場合の信頼性、耐久性の向」二が急務とされてい
る。。There are problems with electromagnetic conversion characteristics, etc. In particular, there is an urgent need to improve reliability and durability when used as magnetic tape. .

発明の目的 本発明は、従来における上述のような点に鑑みなされた
もので、くり返し走行や高温高湿中での１久性にすくれ
、信頼性の高い磁気記録媒体か容易に得られるようにす
ることを目的とする。Purpose of the Invention The present invention has been made in view of the above-mentioned problems in the prior art, and provides a method for easily obtaining a highly reliable magnetic recording medium that is durable for repeated running and high temperature and high humidity. The purpose is to

発明の構成 本発明は、真空蒸着法により強磁性金属を主成分とする
磁性層を基板」−に形成した後、上記磁性層を加熱した
状態にしてオゾン雰囲気に曝し磁気記録媒体を製造する
ものである。Structure of the Invention The present invention involves forming a magnetic layer containing a ferromagnetic metal as a main component on a substrate by a vacuum evaporation method, and then heating the magnetic layer and exposing it to an ozone atmosphere to produce a magnetic recording medium. It is.

実施例の説明 なおここで本発明の詳細な説明に先立ち、理解を容易に
するため従来例の具体的な説明を行う。DESCRIPTION OF EMBODIMENTS Prior to a detailed description of the present invention, a conventional example will be specifically described to facilitate understanding.

第１図は従来の製造方法において用いられた製造装置を
示し、真空蒸着機本体１、フィルム走行系２、磁性金属
蒸発系３、真空排気系４、およびガス導入系５、よりな
っている。高分子フィルム基板７は送り軸にセットされ
、回転キャン９を経て巻取り軸１０で巻取られる。キャ
ン９の下方に、而」熱性セラミックよりなるルツボ１１
内に蒸着材料である磁性金属（Ｃｏ、　Ｎ’ｉ　、　Ｆ
ｅ、　Ｃｒ　）　１５を入れ斜方より電子ヒーム１２で
溶解する。蒸発する金属原子はマスク１３により一部マ
スキングされ、磁性膜形成に必要な成分のみを蒸着する
。図面左方で蒸着した高分子フィルム基板７は右方へ送
られ巻取り輔１０で巻取られる。なお保持力の高い（６
ｏｏ０ｅ以−に）テープを必要とする場合、蒸着時にガ
ス導入系らより酸素ガスを蒸発金属中に導入する。FIG. 1 shows a manufacturing apparatus used in the conventional manufacturing method, which includes a vacuum evaporator body 1, a film running system 2, a magnetic metal evaporation system 3, a vacuum exhaust system 4, and a gas introduction system 5. The polymer film substrate 7 is set on a feed shaft, passes through a rotating can 9, and is wound up on a winding shaft 10. Below the can 9 is a crucible 11 made of thermal ceramic.
Magnetic metals (Co, N'i, F
e, Cr) 15 and melt it with an electronic beam 12 from an oblique direction. The evaporated metal atoms are partially masked by a mask 13, and only the components necessary for forming the magnetic film are deposited. The polymer film substrate 7 deposited on the left side of the drawing is sent to the right and wound up by a winding mechanism 10. In addition, it has a high holding power (6
If a tape is required, oxygen gas is introduced into the evaporated metal from a gas introduction system during vapor deposition.

次に本発明の詳細な説明に入る。A detailed description of the invention will now be entered.

本発明の製造方法において用いられる製造装置の一例を
第２図に示す。FIG. 2 shows an example of a manufacturing apparatus used in the manufacturing method of the present invention.

この装置を用いての蒸着条件、蒸着方法は従来例とほぼ
回しである。只この場合には、蒸着後、高分子フィルム
基板アは図面左方よりマスク１３上を経て巻取り軸１０
に送られ、るが、磁性金属の蒸着された基板′７′は途
中加熱手段１６により加熱し、一方、蒸着機本体１に設
けられたガス導入口１４より含オゾンガスを導入し、蒸
着金属又は金属酸化物の表面部を高次にかつ均一に酸化
する。The vapor deposition conditions and vapor deposition method using this apparatus are almost the same as in the conventional example. In this case, after vapor deposition, the polymer film substrate a passes over the mask 13 from the left side of the drawing, and then passes onto the winding shaft 10.
The substrate '7' on which the magnetic metal is vapor-deposited is heated by the heating means 16 midway through, while an ozone-containing gas is introduced from the gas inlet 14 provided in the vapor deposition machine body 1, and the vapor-deposited metal or The surface portion of the metal oxide is oxidized to a high degree and uniformly.

本発明による場合と従来例の蒸着条件は前述のようにほ
ぼ同一で、蒸着スピード５０ｍ／分、入射角３００〜６
００で行い、磁性膜の厚さは１０００人。The deposition conditions of the present invention and the conventional example are almost the same as described above, with a deposition speed of 50 m/min and an incident angle of 300 to 600 m/min.
00, and the thickness of the magnetic film was 1000.

高分子フィルム基板の厚さは１０μである。磁性膜の保
磁力は８６００ｅであった。また蒸着時の真空度は２ｘ
ｉｏ　　ｔｏｒｒであ−）だ。オゾンガスの供給は、ボ
ンベガスより純酸素をガラス管に導入し、無声放電させ
、２〜３　ｖｏｌ　％オゾン化させたものを導入口より
入れた１、又、オゾン導入時、基板７′の温度を約１０
０℃に加熱して検討し７た。The thickness of the polymer film substrate is 10μ. The coercive force of the magnetic film was 8600e. Also, the degree of vacuum during deposition is 2x
io torr). Ozone gas was supplied by introducing pure oxygen from a cylinder gas into a glass tube, causing a silent discharge, and adding 2 to 3 vol% ozonized oxygen from the inlet. about 10
A study was conducted by heating to 0°C.

次に本発明の効果を調べるために、信頼性試験として市
販の標準デツキを用いてｉｏｏ回のくり返し走行を行い
、電磁変換特性と表面状態の変化を観察した。丑だ環境
試験として、６０℃・９゜％ＲＨの高温高湿雰囲気中１
０週間放置による電磁変換特性、および外観の変化を調
べた。その結果を下の表に示す。Next, in order to examine the effects of the present invention, as a reliability test, a commercially available standard deck was used to repeatedly run ioo times, and changes in electromagnetic conversion characteristics and surface conditions were observed. As a Ushida environment test, 1 in a high temperature and high humidity atmosphere of 60℃ and 9%RH
Changes in electromagnetic characteristics and appearance after being left for 0 weeks were investigated. The results are shown in the table below.

以　　　下　　　余　　　　白 なお従来例ではデツキのくり返し走行で酸素を導入しな
い場合テープ表面に傷がつき易く、６ｅ℃・９０　ＲＨ
の環境雰囲気下でも表面が変色し錆が発生していた。−
力木発明の如く、基板を加熱しなか、らオゾンガスで蒸
着直後の膜を処理した場合、はとんど走行時の傷および
錆は見られなかった。Below Margin In the conventional example, the tape surface is easily scratched if oxygen is not introduced due to repeated running of the deck, and the tape surface is easily scratched at 6e℃/90RH.
The surface was discolored and rusted even in the environmental atmosphere. −
When the film immediately after vapor deposition was treated with ozone gas while the substrate was being heated, as in Rikiki's invention, no scratches or rust were observed during running.

本発明の作用効果を解析するためにＥＳＣＡ及び反射電
子線回折法により各々の磁性膜表面及び内部の酸化状態
について調べたところ、従来例で例えばＣＯ金金属使用
し酸素ガスを導入しない場合、磁性膜はほとんとコバル
ト金属から構成されたものであるか、酸素ガスを導入し
た場合磁性脱勢 の内部Ｃｏ　　２価の酸化物すなわちＣ００及び金属コ
・・ルトの混合体からなり、表面部でばＣ００とＣＯ３
Ｏ４の高次な酸化物か一部形成されていた。一方、本発
明の実施例で蒸着時に酸素ガスを導入しない場合、内部
はほとんとコバルト金属からなるが、表面部１はＣＯ３
０４，ＣＯ２Ｏ３の複合体の酸化物から構成され、酸素
カスを導入した場合、内部はＣｏｏ及び金属コバルトの
混合体からなり、Ｃｏ３Ｏ４とＣＯ２０３の複合体か形
成されていた。又、オゾン導入時、基体の温度を４０℃
〜ＩＥ５０℃に加熱した場合、常温の捷まの場合に比べ
より酸化が促進されていた。このように本発明は同じ真
空装置内で蒸着直後の磁性膜を加熱しなからオゾンガス
を導入することにより、磁性膜の表面部により安定な金
属酸化物の保護層か生成しており、テツギでのくり返し
走行および６０℃・９０％ＲＨ中での環境試験に耐えつ
るものである。′−１だｃｏ金属以外にＦｅ。In order to analyze the effects of the present invention, we investigated the oxidation state on the surface and inside of each magnetic film using ESCA and reflection electron diffraction methods. The film is composed mostly of cobalt metal, or it is composed of a mixture of internal Co divalent oxide, that is, C00, and metal cobalt, which is magnetically de-energized when oxygen gas is introduced, and the surface part C00 and CO3
Some high-order oxides of O4 were formed. On the other hand, when oxygen gas is not introduced during vapor deposition in the embodiment of the present invention, the interior is mostly made of cobalt metal, but the surface portion 1 is CO3
04, is composed of a complex oxide of CO2O3, and when oxygen gas is introduced, the interior is composed of a mixture of Coo and metal cobalt, and a complex of Co3O4 and CO203 is formed. Also, when introducing ozone, the temperature of the substrate was set to 40℃.
When heated to ~IE50°C, oxidation was more accelerated than when kneaded at room temperature. In this way, the present invention generates a more stable protective layer of metal oxide on the surface of the magnetic film by introducing ozone gas without heating the magnetic film immediately after evaporation in the same vacuum device. It can withstand repeated running and environmental tests at 60°C and 90% RH. '-1 is Fe in addition to metals.

Ｃｒ、Ｎｉ金属を用いた場合にもＣＯ金属での蒸着同様
にオゾン処理により高次な酸化状態に表面か改質されて
いた。Even when Cr and Ni metals were used, the surface was modified to a higher oxidation state by ozone treatment, as in the case of vapor deposition with CO metals.

なお本発明を実施するにあたり、磁性金属は一種又は二
種以上の合金を蒸着してもその効果は同様である。寸だ
オゾンガスの発生および導入方法を変えた場合、あるい
はオゾンガスに他の種類のガスを混合した場合にも同様
な効果が得られる。In carrying out the present invention, the same effect can be achieved even if one or more alloys of magnetic metals are deposited. A similar effect can be obtained by drastically changing the method of generating and introducing ozone gas, or by mixing other types of gas with ozone gas.

さらに蒸着条件としての真空度、蒸着速度、蒸着レ−１
・、磁性膜の膜厚なとは自由に選択される。Furthermore, the vacuum degree, evaporation rate, and evaporation rate 1 as evaporation conditions
・The thickness of the magnetic film can be freely selected.

発明の効果 本発明に」：ろと、くり返し走行および高温高湿中での
耐久性にすぐれるなと信頼性の高い磁気記録媒体を容易
に得ることができる。Effects of the Invention According to the present invention, a highly reliable magnetic recording medium can be easily obtained that has excellent durability against repeated running and at high temperature and high humidity.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は従来の方法において用いられた製造装置を示す
図、第２図は本発明の方法において用いられる製造装置
の一例を示す図である。 機 １　・・真空装ｆｉ”Ｊ−ＦＰ本体、３・・・・・蒸発
源、７・・・・、・高分子フィルノ・基板、９　・・・
回転キャン、１６・・・・・・加熱手段。 第１図 ０ 第２図FIG. 1 is a diagram showing a manufacturing device used in the conventional method, and FIG. 2 is a diagram showing an example of the manufacturing device used in the method of the present invention. Machine 1... Vacuum equipment fi"J-FP main body, 3... Evaporation source, 7..., Polymer filno substrate, 9...
Rotating can, 16... Heating means. Figure 10 Figure 2

Claims (2)

【特許請求の範囲】[Claims] （１）真空蒸着法により強磁性金属を主成分とする磁性
層を基板上に形成した後、上記磁性層を加熱した状態に
してオゾン雰囲気に曝すことを特徴とする磁気記録媒体
の製造方法。(1) A method for manufacturing a magnetic recording medium, which comprises forming a magnetic layer containing a ferromagnetic metal as a main component on a substrate by vacuum evaporation, and then heating the magnetic layer and exposing it to an ozone atmosphere. （２）磁性層を基板上に形成する際酸素を真空系内に導
入することを特徴とする特許請求の範囲第１項記載の磁
気記録媒体の製造方法。(2) The method for manufacturing a magnetic recording medium according to claim 1, characterized in that oxygen is introduced into a vacuum system when forming the magnetic layer on the substrate.