JPS6111920A - Magnetic recording body and its manufacture - Google Patents

Abstract

PURPOSE:To form the titled magnetic recording body having a magnetic thin film with excellent adhesive strength by forming a copper thin film on the surface of a plastic supporting body having excellent heat resistance and dimensional stability, and then forming a magnetic alloy thin film thereon. CONSTITUTION:A supporting body is obtained by forming a copper thin film on the surface of a plastic supporting body and forming successively a magnetic alloy thin film thereon. The surface is preferably roughed with an abrasive contg. a surfactant by using a liquid honing device so that pores having 2-6mum depth and <=1mum diameter at the center of the width of the pore may be obtained on the surface. A high-quality magnetic recording body provided with a closely adhered magnetic alloy thin film can be produced on a large scale by conveying the supporting body continuously through respective specified plating baths. The film thickness of the copper thin film and the magnetic alloy thin film can be easily controlled by controlling the time of dipping in the plating bath, and the medium having uniform film thickness and a wide area can be produced on a large scale.

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は均質薄膜の磁性層を設けてなる７ｐツピイディ
スク、磁気テープ等の磁気記録体およびその製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a magnetic recording medium such as a 7p disk or magnetic tape provided with a homogeneous thin magnetic layer, and a method for manufacturing the same.

（従来の技術） ７０ツビイディスク、Ｗｉ磁気テープどの磁気記録体は
、近年のオフィスオートメーションの普及にともない、
急速に発達してきているが、これら磁気記録体の利用範
囲、需要の拡大にともなって性能的に一段と高密度化（
６録密度の向上）が要請されている。他方この種の磁気
記録体はポリエステルなどのプラスチックフィルムの表
面Ｋｒ　−Ｆ９．０３　　などの磁性粉を塩化ビニル樹
脂系接着剤と混合して塗布するか、あるいはスパッタリ
ング装置を用いて直接蒸着するという方法で作られてい
るが、前者の方法には塗布厚さに限界があるために性能
の高−変化に限界があ・）、後者の方法には磁性粉の蒸
着が真空系で行われるため大量生産には不向きであると
いう欠点があった。(Prior art) Magnetic recording media such as 70-tube disks and Wi magnetic tapes have become increasingly popular with the spread of office automation in recent years.
These magnetic recording media have been rapidly developing, but as the range of use and demand for these magnetic recording media expands, performance is becoming even higher density (
6) Improvement in recording density is required. On the other hand, this type of magnetic recording material is produced by coating the surface of a plastic film such as polyester with magnetic powder such as Kr-F9.03 mixed with a vinyl chloride resin adhesive, or by directly depositing it using a sputtering device. However, the former method has a limit to the coating thickness, so there is a limit to the change in performance. The drawback was that it was unsuitable for production.

しかして、磁気記録体における磁性層の磁気特性は、磁
気記録装置における記録再生ヘッドの性能と相まって磁
気記録密度、磁気記録再生速度に大きな影響を与えるも
のであり、この記録密度。Therefore, the magnetic properties of the magnetic layer in a magnetic recording medium, together with the performance of the recording/reproducing head in a magnetic recording device, have a large effect on the magnetic recording density and magnetic recording/reproducing speed.

再生速度と磁気特性である保磁力（Ｈｃ）、残留磁束密
度（Ｂｒ）、および磁性層の膜厚（ｄ）との間には次の
関係があることが指摘されている。It has been pointed out that there is the following relationship between reproduction speed and magnetic properties such as coercive force (Hc), residual magnetic flux density (Br), and thickness (d) of the magnetic layer.

記録密度匡Ｊ這フ；−丁Ｔ 出　　　力　ｃ（Ｊπ７−ア］「；−π：したがって要
請される記録密度および出力に適する磁性層を安定に得
るには磁性層のＨａ　−Ｂｒおよびｄを一定の範囲内に
保つ必要がある。高密度化のためにはｄが１μｍ以下と
益々薄くなＩ）つつあり、従来の塗布方法ではｌ／１１
ｒＬの厚さでしかも一定の範囲内に保ちながら均一に塗
布することができない。また蒸着の場合膜組成を均一に
保つことが難しい。これらについて種々の提案がなされ
ているが解決したものはまだ得られていない。Therefore, in order to stably obtain a magnetic layer suitable for the required recording density and output, Ha - Br and d of the magnetic layer should be It is necessary to maintain it within a certain range.In order to achieve high density, d is becoming thinner and thinner, to 1 μm or less.
It is not possible to apply the coating uniformly to a thickness of rL while keeping it within a certain range. Furthermore, in the case of vapor deposition, it is difficult to maintain a uniform film composition. Various proposals have been made regarding these issues, but no solution has yet been found.

本発明は上記諸問題点を解決して所要の特性を有し、付
着強度にすぐれた磁性薄膜を有する磁気記録体を提供す
るもので、これはポリエステル２ポリフエニレンサルフ
アイド等の耐熱性１寸法安定性にすぐれたプラスチック
のフィルム、シートなどの支持体表面に、銅薄膜および
その上に磁性合金薄膜を順次形成した構成からなる磁気
記録体に関する。本発明はまたこの有利な製造方法を開
発したもので、これは上記したプラスチック製支持体表
面に、粗面化処理したのち無電解メッキ法および／また
は電解メッキ法により、銅薄膜および磁性合金薄膜を順
次形成させることを特徴とする方法である。The present invention solves the above-mentioned problems and provides a magnetic recording medium having the required properties and a magnetic thin film with excellent adhesion strength. The present invention relates to a magnetic recording medium having a structure in which a copper thin film and a magnetic alloy thin film are sequentially formed on the surface of a support such as a plastic film or sheet having excellent dimensional stability. The present invention has also developed this advantageous manufacturing method, in which a copper thin film and a magnetic alloy thin film are coated on the surface of the plastic support by electroless plating and/or electrolytic plating after roughening treatment. This method is characterized by sequentially forming .

以下本発明の詳細な説明する。The present invention will be explained in detail below.

本発明に用いられるポリエステル、ポリ７エ二レンサル
フアイドなどのプラスチックフィルム。Plastic films such as polyester and poly-7-ethylene sulfide used in the present invention.

シート等の支持体は、生地のままこの表面に無電解メッ
キ、電解メッキを行うことが困難であるので、予め物理
的、化学的手段で粗面化処理を行うにの粗面化方法とし
ては液体ホーニング装置を使用しプラスチック製支持体
表面に深さ２〜６μｍ。Since it is difficult to perform electroless plating or electrolytic plating on the surface of a support such as a sheet, it is difficult to perform electroless plating or electrolytic plating on the surface of the material as it is. A depth of 2 to 6 μm is applied to the surface of the plastic support using a liquid honing device.

孔中の中心で１μｍ以下の孔となるように界面活性剤入
りの研磨材で粗面化処理を行うことが望ましい。It is desirable to roughen the surface using an abrasive containing a surfactant so that the center of the pores has a diameter of 1 μm or less.

次にとの粗面化処理した面に無電解、メッキ法で密着性
のよい銅を析出させるため鎖、塩化第一すず溶液による
増感処理および塩化パラジウム溶液による活性化処理を
行い、この後無電解銅メッキ液に浸漬して銅薄膜を付着
させるが、膜厚が約０．５μ涌となった時点で電解メッ
キ法に変更し銅メッキを継続して行うことが望ましい。Next, in order to deposit copper with good adhesion by electroless plating on the roughened surface, sensitization treatment with stannous chloride solution and activation treatment with palladium chloride solution are performed. A thin copper film is deposited by immersing it in an electroless copper plating solution, but when the film thickness reaches about 0.5 μm, it is desirable to switch to electrolytic plating and continue copper plating.

銅ンツキ浴は酒石酸塩を錯化剤とした硫酸銅溶液が一般
に用いられるａｇｉ４薄膜の厚さは合計でおおむね７〜
１２μｍとなるようにすればよ（、この厚さがうすすぎ
ると粗面化処理した表面の凹凸がそのま＼銅表面に表わ
れるし、また厚すぎると製品全体の重量が増加して始動
及び回転トルクが増加する。Copper sulfate solution with tartrate as a complexing agent is generally used for the copper nut bath.The total thickness of the agi4 thin film is approximately 7~
The thickness should be 12 μm (If this thickness is too thin, the unevenness of the roughened surface will appear directly on the copper surface, and if it is too thick, the weight of the entire product will increase, making it difficult to start up and Rotational torque increases.

というそれぞれ不利がもたらされる。Each brings disadvantages.

次に上記のようにして銅薄膜を形成したうえに磁性合金
薄膜を形成するために望ましくはコバルト合金系の無電
解メッキ液に浸漬し、コバルト合金薄膜を形成させる。Next, in addition to forming a copper thin film as described above, in order to form a magnetic alloy thin film, it is preferably immersed in a cobalt alloy based electroless plating solution to form a cobalt alloy thin film.

コバルト合金系のメッキ浴としては硫酸コバルト、硫酸
ニッケルおよび次亜リン酸ナトリウムを主成分とするも
のを用いることが好ましい。このようにして形成される
コバルト合金薄膜の厚さはおおむね０．１〜２μｍであ
ることが望ましく、この理由は媒体の高密度化１表面の
平滑化および磁性粒子の高配向化が可能なことである。As the cobalt alloy plating bath, it is preferable to use one containing cobalt sulfate, nickel sulfate, and sodium hypophosphite as main components. The thickness of the cobalt alloy thin film formed in this way is preferably approximately 0.1 to 2 μm, and the reason for this is that it is possible to increase the density of the medium, smooth the surface, and highly orient the magnetic particles. It is.

・本発明の方法によれば、粗面化処理されたプラスチッ
ク製フィルムあるいはシート等を上記したそれぞれの所
定のメッキ浴中を連続して搬送して行くことにより、き
わめて密着性のよい磁性合金薄膜を備えた磁気記録体が
大量生産的にかつ高品質のものとして得られる。銅薄膜
および磁性合金薄膜の膜厚管理はメッキ浴中に浸漬して
いる時間を制御することにより容易に行うことができ、
膜厚が均一でしかも広面積のものが大量生産的に得られ
る。・According to the method of the present invention, a magnetic alloy thin film with extremely good adhesion is formed by continuously transporting a roughened plastic film or sheet through each of the above-mentioned predetermined plating baths. Magnetic recording bodies equipped with this can be mass-produced and of high quality. The thickness of copper thin films and magnetic alloy thin films can be easily controlled by controlling the time they are immersed in the plating bath.
A film with a uniform thickness and a wide area can be obtained in mass production.

つぎに具体的実施例をあげる。Next, specific examples will be given.

実施例１ 厚さ７５μｍのポリエステルフィルムを水で洗浄、トリ
クレ、ン等で脱脂の後、液体ホーニング処理法により粗
面化処理を行った。すなわち研磨材としてエメリーナ３
２０およびアランダムナ４００の混合物を界面活性剤３
チｉむ水に混合して得た研磨液を、圧力３Ｋｐ／ａｌ搬
送速度毎分０．５ｍでポリエステルフィルムに当てるこ
とにより粗面化処理し、二″ツチング孔巾中心で１ｐｍ
以下。Example 1 A polyester film having a thickness of 75 μm was washed with water, degreased with Tri-Clean, etc., and then subjected to surface roughening treatment using a liquid honing treatment method. In other words, Emelina 3 as an abrasive
20 and Alundumna 400 as surfactant 3
The polishing liquid obtained by mixing with water was roughened by applying it to the polyester film at a pressure of 3 Kp/al and a conveying speed of 0.5 m/min, and the surface was roughened to 1 pm at the center of the 2" hole width.
below.

深さ３〜３．５μｍの鋭角状の孔を多数形成した。粗面
化処理後水洗して次工程である塩化第一すず溶液および
塩化バヲジウム溶液に浸漬することにより増感処理、活
性化処理を行った。A large number of acute-angled holes with a depth of 3 to 3.5 μm were formed. After the surface roughening treatment, it was washed with water, and the next step, sensitization treatment and activation treatment, was performed by immersing it in a stannous chloride solution and a baodium chloride solution.

次にこのポリエステルフィルムを硫酸銅溶液に入れて無
電解銅メッキを行わせ、無電解銅メッキの膜厚が約０．
５μｍになった時点で次工程に移して電解銅メッキを継
続して行わせ、厚さ約８μｍの電解銅メッキを形成した
。電解銅メッキは硫酸銅メッキ液を用いて陰極電流密度
Ｌ５Ａ／ｄ−直流６■で実施した。Next, this polyester film was placed in a copper sulfate solution and subjected to electroless copper plating, so that the film thickness of the electroless copper plating was approximately 0.
When the thickness reached 5 μm, the next step was carried out and electrolytic copper plating was continued to form electrolytic copper plating with a thickness of about 8 μm. Electrolytic copper plating was carried out using a copper sulfate plating solution at a cathode current density of L5A/d-DC6.

次に硫酸コバルト−硫酸ニッケルおよび次亜リン酸ナト
リウムを含む溶液からなるコバルト合金メッキ浴に、上
記銅メッキを施こしたポリエステルフィルムを浸漬し、
銅薄上Ｋ　Ｃｏ−Ｎｔ　−ｐか、らなるコバルト合金薄
膜（磁性合金薄ｊｌ［）を膜厚的０．５μｍとなるよう
に形成した。Next, the copper-plated polyester film is immersed in a cobalt alloy plating bath consisting of a solution containing cobalt sulfate-nickel sulfate and sodium hypophosphite,
A cobalt alloy thin film (magnetic alloy thin jl[) consisting of K Co--Nt-p was formed on a copper thin film to have a film thickness of 0.5 μm.

以上のようにしてポリエステルフィルムの表面に銅薄膜
および磁性合金Ｎｉ膜（：２バルト合金薄Ｍ）をそれぞ
れの厚さで形成してなる磁気記録体を得た。これについ
て下記のよう和してメッキ膜の付着強度を測定したとこ
６．結果はＬ７Ｖ４１０ｎであった。As described above, a magnetic recording body was obtained in which a copper thin film and a magnetic alloy Ni film (2 balt alloy thin M) were formed on the surface of a polyester film with respective thicknesses. Regarding this, the adhesion strength of the plating film was measured by adding the following sum.6. The result was L7V410n.

〔メッキ膜についての付着強度の測定〕磁気記録体を幅
１０ｍのテープ状に切って引はがし試験を行った。引は
がし試験の条件は引はがし速さ５０朋／分で行い、引き
はがしの過程で得られた荷重の平均値を付着強度とした
。[Measurement of adhesion strength of plated film] The magnetic recording material was cut into a tape shape with a width of 10 m and a peel test was conducted. The peeling test was conducted at a peeling speed of 50 mm/min, and the average value of the loads obtained during the peeling process was taken as the adhesive strength.

Ｏｏ　−Ｎｉ　−Ｐ　　からなるコバルト合金薄膜の磁
気特性を測定したところ、記録媒体層の保磁力は３２０
エルステツドであった。When we measured the magnetic properties of a cobalt alloy thin film consisting of Oo-Ni-P, we found that the coercive force of the recording medium layer was 320
It was Ersted.

実施例２ 実施例上において、液体ホーニング装置による物理的粗
面化処理に代えて、２０チ水酸化ナトリウム水溶液（温
度６０℃）中で３分間浸漬処理する化学的粗面化処理を
行った以外は同様にして銅薄膜およびコバルト合金薄膜
を形成させることにより磁気記録体を得た。Example 2 In Example 2, except that instead of the physical roughening treatment using a liquid honing device, a chemical roughening treatment was performed by immersion treatment in a 20% sodium hydroxide aqueous solution (temperature 60 ° C.) for 3 minutes. obtained a magnetic recording medium by forming a copper thin film and a cobalt alloy thin film in the same manner.

このものについて前例と同様にメッキ膜の付着強度を測
定したところ、結果は１．２　Ｋ４／　ａｎであった。When the adhesion strength of the plating film was measured on this product in the same manner as in the previous example, the result was 1.2 K4/an.

比較例 実施例上において、ポリエステルフィルムについての液
体ホーニング処理法による表面粗面化処理を全く省略し
たほかは同様にして増感処理、活性化処理を行い、銅薄
膜およびコバルト合金薄膜を形成させた。Comparative Example: A thin copper film and a thin cobalt alloy film were formed by carrying out sensitization treatment and activation treatment in the same manner as in Example, except that the surface roughening treatment using the liquid honing method for the polyester film was completely omitted. .

このものについて同ｓＫメッキ膜の付着強度を測定した
ところ、結果はＯ，ｌ　ｈ　／　ｏｎ以下であった。When the adhesion strength of the same sK plating film was measured on this product, the result was less than O,l h /on.

この値から実施例１および実施例２での付着強度がきわ
めてすぐれたものであることがわかる。From this value, it can be seen that the adhesion strengths in Examples 1 and 2 were extremely excellent.

Claims (1)

【特許請求の範囲】 １、プラスチック製支持体表面に、銅薄膜およびその上
に磁性合金薄膜を順次形成してなる磁気記録体 ２、プラスチック製支持体表面に、粗面化処理したのち
無電解メッキ法および／または電解メッキ法により、銅
薄膜および磁性合金薄膜を順次形成させることを特徴と
する磁気記録体の製造方法 ３、プラスチック製支持体表面に、液体ホーニング法に
より界面活性剤入りの研磨材を用いて粗面化処理するこ
とにより、深さ２〜６μｍ、孔巾中心で１μｍ以下の孔
を多数形成することを特徴とする特許請求の範囲第１項
記載の磁気記録体の製造方法[Claims] 1. A magnetic recording body formed by sequentially forming a thin copper film and a thin magnetic alloy film on the surface of a plastic support. Method 3 for producing a magnetic recording medium characterized by sequentially forming a copper thin film and a magnetic alloy thin film by a plating method and/or an electrolytic plating method, polishing a plastic support surface with a surfactant by a liquid honing method A method for manufacturing a magnetic recording body according to claim 1, characterized in that a large number of holes with a depth of 2 to 6 μm and a center width of 1 μm or less are formed by roughening the magnetic recording material using a material.