JPS5956227A - Production of magnetic recording medium - Google Patents

Abstract

PURPOSE:To provide excellent runnability without affecting a magnetic characteristic and to enable mass production by exposing a magnetic recording layer to a glow discharge atmosphere using a gaseous mixture of the gas of a silicon org. compd. and gaseous oxygen and forming a siliceous film on the magnetic recording layer. CONSTITUTION:Plural pinholes each sized about 1mm. diameter are provided to a discharge electrode 2 provided on the magnetic metal side of a magnetic recording medium 1 which is an object to be treated in such a way that org. gas scatters uniformly between the electrodes. A reactor 5 is evacuated to <=10<-3>Torr with a vacuum pump and the valves in a gas introducing port 4 and discharging port 6 are regulated to control the degree of vacuum. When gaseous oxygen is mixed through a gaseous oxygen introducing port 8 with the gaseous monomer introduced from a monomer vessel 7, the oxidation reaction of the gaseous monomer arises and the oxide of the inorg. material is formed with the mixing ratio of the gaseous monomer and the gaseous oxygen according to the conditions of glow discharge, more particularly the conditions of the impressed electric power to deposit uniformly in an ultrafine powder form.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は例えば真空蒸着、イオン！”レーーノ”イング
、スパッタリング及び類似の他の／、法で形成された薄
膜を磁気記録層として有する１１す（気１．１１録媒体
の製造方法に関するものである。[Detailed Description of the Invention] Industrial fields of application The present invention is applicable to, for example, vacuum evaporation, ion! 1.11 Concerns a method of manufacturing a recording medium having as a magnetic recording layer a thin film formed by "Lehno"ing, sputtering and other similar methods.

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１−Ｆｅ２０ｓ粉末、
Ｃｒ０ｚ粉末、純鉄粉末等をバインタ゛−とともに高分
子フィルム上に塗布せしめた、いわゆる塗布型の磁気記
録媒体がある。しかし、従来の塗布型の磁気記録媒体よ
り保磁力、記録密度、その他の電磁変換特性を高めるた
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　、　Ｇｏ　。Its technological development is remarkable. Typical examples of conventional magnetic recording media include 1-Fe20s powder,
There is a so-called coating type magnetic recording medium in which CrOz powder, pure iron powder, etc. are coated on a polymer film together with a binder. However, in order to improve coercive force, recording density, and other electromagnetic conversion characteristics compared to conventional coating-type magnetic recording media, recently, Fe, Go has been developed using oblique incidence deposition method or ion blating method.

Ｎｉ等の強磁性体金属を単独もしくは合金として高分子
フィルム上に蒸着する金属薄膜型磁気記録媒体が検討さ
れ、急速に実用化されつつあり、例えば、ポリエチレン
テレクタレ−１・などの高分子フィルム基体１−にコバ
ルトを主体とする合金の磁性層を形成したビデオ月ｊ磁
気デープが開発されている。しかしながら、ｋ配力法で
形成した磁的；薄膜層は通常化学的に極めて活性なもの
であり、また、表面性が良いために、摩擦係数が高い。Metal thin film magnetic recording media in which ferromagnetic metals such as Ni, alone or as an alloy, are deposited on a polymer film have been studied and are rapidly being put into practical use. A magnetic tape has been developed in which a magnetic layer of a cobalt-based alloy is formed on a substrate 1. However, magnetic thin film layers formed by the k-force method are usually extremely chemically active and have a high coefficient of friction due to their good surface properties.

１ｔＹＨって、シリンダ、磁気ヘッド等との摺接するこ
とにより磁性層が摩耗し、長時間使用に対しては、磁性
層に走行症や傷が生じ、記録、再生がオー〉）ζく不能
となるような実用」二致命的な欠陥が発生する場合があ
る。With 1tYH, the magnetic layer wears out due to sliding contact with cylinders, magnetic heads, etc., and when used for long periods of time, the magnetic layer gets scratches and scratches, making recording and playback impossible. In practical use, two fatal flaws may occur.

そこで、従来、このような蒸着薄膜を用いた磁気記録媒
体の走行性や耐摩耗性を改ｊ”Ｊｌ’するノｊ法として
、磁性体表面に高級脂肪酸、脂１１）ｊ酸エステル。Therefore, conventionally, as a method to improve the running performance and wear resistance of a magnetic recording medium using such a vapor-deposited thin film, higher fatty acids and fat 11) acid esters have been added to the surface of the magnetic material.

脂肪酸アミドなどの滑剤を溶媒どＪｌ′：ＶＣ塗布した
り、バノクコ−１・而にイソシア不−１・化合物、ポリ
エステル樹脂、塩化ビニル−酢酸ヒー゛−ル共ｉｌ”１
合体などの結合剤とＣａＣＯ３やカーボン４・どの充て
ん剤を前記滑剤と混合して塗布し、磁ゼト層表面への滑
剤の転写を利用して走行性を向−に−，，”ｒ　、Ｊ−
る方法がある。その他、金属薄膜表面をダ「ｌ−１ｉｋ
電により酸化処理したり、蒸着時に酸素カスを・、す人
することにより表面層を酸化させ、シリングやボスト等
との１ｌｉｉｌ摩耗１／１：を改良する方法がある３、
しかし、これらの方法においても連続繰返し走行でｔ、
１１、？；↑剤が取り除かれたり高湿下での滑剤の吸／
！ｕ！ｌ’ｌ内問題があり、その結果、摩擦係数のｊ、
Ｊｌ、、鳴きＪ）発生。Apply a lubricant such as fatty acid amide to a solvent such as VC, or apply a banocco-1, an isocyanate compound, a polyester resin, or a vinyl chloride-acetic acid mixture.
A binder such as coalescence and a filler such as CaCO3 or carbon 4 are mixed with the lubricant and applied, and the transfer of the lubricant to the surface of the magnetic layer is used to improve running properties. −
There is a way to do it. In addition, the metal thin film surface is
There is a method of oxidizing the surface layer by electrolytic oxidation treatment or removing oxygen scum during vapor deposition to improve the wear rate of 1/1 with shillings, bosses, etc. 3.
However, even in these methods, t,
11,? ；↑The lubricant may be removed or the lubricant may be absorbed under high humidity.
! u! There is a problem within l'l, and as a result, the coefficient of friction j,
Jl,, Squeal J) Occurrence.

あるいは＠Ｉ’１′、層の損傷などが生じ、実１月日り
分解法出来る／ｊ策とはいい難いのが現状で、１する。Alternatively, @I'1', damage to the layer may occur, and the current situation is that it is difficult to say that it is a practical solution.

本発明は磁気特性に影響を及ぼすことなく優れた走行性
を有し、量産可能な金属薄膜型磁気記録媒体の製造方法
を提供することを目的とする。１発明の構成 本発明はシリコン系有機化合物のガスと酸素ガスとの混
合ガスを用いたグロー放電’ｌｈ囲気に磁気記録層をさ
らし、その磁気記録層トに含／リコノ膜を形成するもの
である。An object of the present invention is to provide a method for manufacturing a metal thin film magnetic recording medium that has excellent running properties without affecting magnetic properties and can be mass-produced. 1. Structure of the Invention The present invention involves exposing a magnetic recording layer to a glow discharge atmosphere using a mixed gas of a silicon-based organic compound gas and oxygen gas, and forming a containing/licon film on the magnetic recording layer. be.

実施例の説明 第１図は本発明の一実施例を示す図であり、１は被処理
物である磁気配録媒体、２，３は相対向して配置された
電極であり、磁気記録媒体１の研１＜Ｌ層側に設けた電
極２は、有機ガス導入１−１４と接続されている。放電
電接２には有機ガスが電極間で均一に飛散するように、
直径１　ｒｔｍ稈度の複数個のピノホールが設けられて
いる。しかし有機ノｊスの飛散口は前記電極２とは別個
に設けても（ｉ’ｌらかまわない。５は反応容器、６は
排気１１である。７はモノマー容器、８は酸素カス導入
１−１．９，９′は娃磁気詔録媒体の表面処理を連続的
にＩＪなうだめのカイトロール、１０．１１は供給ｌｌ
ｌ−ル及び巻取りロールであり、ギヤモータ等の駆動１
．１．４１？Ｔし、１、略している。１２は高周波電源
である１゜次に具体的に処理例を示す。反応容“）’ｉ
’、　５を〆す空ポンプで１０　　’Ｔｏｒｒ以下に排
気し、ガ゛ス３′−人１」４及び、排気１■１６のバル
ブを調整することにより、反応用’Ａｒｉ　５のｔｌ、
＜空席をグロー放電が長時間にわたり安定となるように
コントロールする１、グロー放電条件としてｒｌ、電極
間型１−Ｅ１００〜３００Ｖで周波１１１３．６　Ｍ　
１１　ｚ　、放′市′屯流１００〜２００ｍＡ、真空度
０，３〜１．０Ｔｏｒｒの範囲で、検討した。なお、化
合物の中で、融点や沸点が高くて気化し難く、室温で反
応容器５内が適当なガス圧にならない場合、化合物導入
容器７や、導入系を加クツ５して、前記の」：うな条件
でグロー放電が１−」なわ、Ｉｉる０このＪ：うにして
導入されたモノマーガスＱ、１．プラズマ中に存在する
イオンや電子、これらのｔ１°１１′から派生したラジ
カル、励起分子及び九ｆなどの帖１′１粒子との間で付
加反応、再結合反応など４１、Ｑ　／、な反応が生じ、
被処理記録媒体表面に反応生成物が色情される。しかし
、モノマーガスに酸素カスを混合して導入すると前記プ
ラズマ重合反応とは若干異なり、モノマーガスの酸化反
応が生じ、モノマーガスと酸素ガスの混合比やダロー放
′亀条件、特に印加電力の条件によっては無機系の酸化
物が生成され、極微粒子となって均一に被着する。DESCRIPTION OF THE EMBODIMENTS FIG. 1 is a diagram showing an embodiment of the present invention, in which 1 is a magnetic recording medium as an object to be processed, 2 and 3 are electrodes arranged facing each other, and the magnetic recording medium The electrode 2 provided on the side of the layer 1<L of No. 1 is connected to the organic gas introduction 1-14. Discharge electrode 2 is made so that the organic gas is uniformly scattered between the electrodes.
A plurality of pinotholes with a diameter of 1 rtm culm are provided. However, the organic gas scattering port may be provided separately from the electrode 2. 5 is the reaction container, 6 is the exhaust 11, 7 is the monomer container, and 8 is the oxygen gas introduction 1. -1.9,9' is a kit roll that continuously performs surface treatment of magnetic recording media, and 10.11 is supplied by IJ.
L-roll and take-up roll, drive gear motor etc. 1
．． 1.41? T and 1 are omitted. Reference numeral 12 denotes a high frequency power supply.Next, a specific processing example will be shown. Reaction volume ")'i
Evacuate to below 10 Torr with an empty pump, and adjust the gas 3' - 1' 4 and the exhaust 1'16 valves to reduce the tl of Ari 5 for reaction.
<Control the vacant seat so that the glow discharge is stable for a long time 1, Glow discharge conditions are RL, interelectrode type 1-E 100 to 300V, frequency 1113.6M
11z, an output current of 100 to 200 mA, and a degree of vacuum in the range of 0.3 to 1.0 Torr. In addition, if a compound has a high melting point or boiling point and is difficult to vaporize, and the inside of the reaction container 5 does not have an appropriate gas pressure at room temperature, the compound introduction container 7 or the introduction system may be adjusted 5 to prepare the compound as described above. : Under such conditions, the glow discharge is 1-", Ii ru 0 this J: Monomer gas Q introduced in this way, 1. 41, Q /, reactions such as addition reactions and recombination reactions between ions and electrons existing in the plasma, radicals derived from these t1°11', excited molecules, and 1'1 particles such as 9f. occurs,
The reaction product is deposited on the surface of the recording medium to be processed. However, when a mixture of oxygen scum is introduced into the monomer gas, an oxidation reaction of the monomer gas occurs, which is slightly different from the plasma polymerization reaction described above. In some cases, inorganic oxides are produced and are deposited uniformly in the form of extremely fine particles.

モノマーどしてシラノカソブリノグ削、例エバビニルト
リクロシラ／ｌビニルトリエトギン７ラン、などを用い
て、モノマーガスと酸素ガスの割合全１：０．１〜１０
の割合で桃々形成し／Ｃ・もの（／コついて、光学顕微
鏡、走査型電子顕微鏡で表面を観察しだところ、１００
人〜１０７１の粒子−状の（＝１着物が認められた。た
だし、磁気記録媒体を走行させずに固定させた場合、粒
子状堆積物が全面的に広がり、白色状の皮膜が形成され
た。このような堆積物を赤外分尤分析及び光電子分）を
分析（ＥＳＣＡ）で厘ｒ析した結果、主に／リコノの酸
化物である５１０２であり、ガス導入条件、グロー条件
を変えることｐｃより、５１０２の仙に／リコ／系の有
機化合物が」（存していることが確１．ｉ！−さ、＃ま
た３゜このようにして得られた磁気記録媒体の）ｊ１行
Ｐｌを調へるため静摩擦係数を測定し／、−１１１こ／
）、末処Ｊ］１１では○、！５〜０゜６．処理し／こ場
合、０．２−０．ζ３と向−１−Ｌ、ていることがわか
った。′ｉ／１−１１ｉｉ４　Ｉ’ｄ’耗＋’ｌに゛つ
いて、磁気ヘッドによる引−）かき１１１（験υどｃ　
１ｓ”Ｙ価したところ、未処坤の場合、荷重３０〜６０
ｇで引−・かきノド行痕が生じるのに対し、６０〜７０
ｇでもほとんど損傷しないことがわか−）だ１、発明の
効１４走 不発明は、以１・に説明し／辷如く、グｊｌ−放電によ
り、１１反微粒子の酸化ケイ素お、ｆ　（：）イ酉幾ン
リコン化合物等を磁気記録層−ヒ均−ｐｃり旨′ｌさ１
ｔて保護膜とするものであり、走行性、１６ｔｔ　斤：
　Ｊ　ｌ−；　ｌ’ｌの向Ｉ−を図るだけでなく、金属
簿膜表面に比−１１１−学的に安定である／こめ耐食Ｉ
１１゛にも優れたもの−Ｃある。１／ζ、放電処理にお
ける被着基板のｌＬ行ｊ・（ζＩＣ−を調部することに
より、保護膜の厚さ姓よ１００八イ、′、！度、あるい
ｄ、それ以トでも充分可能であり、電磁変換特性にも全
く間１迫がなく、その実１４４１’Ｌ　ｉｌ、Ｉ會めて
入なるものである。Using a monomer such as cyanocasobrinog, e.g., evavinyltricrosila/l vinyltriethogine 7ran, the ratio of monomer gas to oxygen gas is 1:0.1 to 10.
When I observed the surface using an optical microscope and a scanning electron microscope, I found that 100
Human ~ 1071 particles (= 1 kimono) were observed. However, when the magnetic recording medium was fixed without running, the particulate deposits spread over the entire surface and a white film was formed. As a result of analyzing such deposits by infrared spectrum analysis and photoelectron analysis (ESCA), it was found that it was mainly 5102, which is an oxide of /licon, and that it was necessary to change the gas introduction conditions and glow conditions. From pc, it is certain that an organic compound of the /lico/ system is present at the base of 5102. In order to find out, the coefficient of static friction was measured /, -111 /
), End J] In 11, ○,! 5~0°6. In this case, 0.2-0. It was found that ζ3 and direction -1-L. 'i/1-11ii4 Regarding I'd'wear+'l, the magnetic head pull-)
When tested for 1s'', the load was 30 to 60 if it was untreated.
At 60 to 70 g, scratches and scratches occur.
It was found that there was almost no damage even when the 11-fine particles of silicon oxide were removed by the electric discharge, as explained in 1. 1. Addition of a compound such as a silicon compound to the magnetic recording layer.
It is used as a protective film, and has a running property of 16tt.
J l-; Not only does it aim for the direction of l'l, but it also provides comparatively stable corrosion resistance on the surface of the metal film.
11゛ also has an excellent one-C. 1/ζ, the thickness of the protective film can be determined to be 100 degrees, ', ! degrees, or d or more by measuring the 1L row j (ζ IC-) of the adherend substrate during discharge treatment. It is possible, and the electromagnetic conversion characteristics are completely impractical, and the reality is that it is a combination of the two.

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

図は本発明の一実施例を示す図である０、１・・・・・
・磁気記録媒体、２，３・・・・・・放電７（Ｌ極、４
・・・・・・ガス導入１−１．５・・・・・・反応容器
、６・・・・・・排気＋１−１、了・・・・・・モノマ
ー容器、８・・・・・・酸素ガス導入（−１，９゜９′
・・・・・・カイトロール、１０・・・・・・供給ロー
ル、１１・・・・・・巻取りロール、１２・・・・・・
高周波型４ｆ　、、、、。The figure shows one embodiment of the present invention. 0, 1...
・Magnetic recording medium, 2, 3...Discharge 7 (L pole, 4
...Gas introduction 1-1.5...Reaction vessel, 6...Exhaust +1-1, completed...Monomer container, 8...・Oxygen gas introduction (-1,9°9'
... Kite roll, 10 ... Supply roll, 11 ... Winding roll, 12 ...
High frequency type 4f.

Claims (2)

【特許請求の範囲】[Claims] （１）シリコノ系有機化合物のガスと酸素ガスとの混合
ガスを用いたグロー放電雰囲気中に磁気記録層をさらし
、ｌ記磁気記録層上に含シリコ／膜を形成することを特
徴とする磁気記録媒体の製造方法。(1) A magnetic recording layer characterized by exposing the magnetic recording layer to a glow discharge atmosphere using a mixed gas of silicone organic compound gas and oxygen gas to form a silicon-containing film on the magnetic recording layer. A method for manufacturing a recording medium. （２）磁気記録層がコバルト系合金の薄膜からなること
を特徴とする特許請求の範囲第１．１Ｊ′ｌ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 1.1J'l, wherein the magnetic recording layer is made of a thin film of a cobalt-based alloy.