JPH0120490B2 - - Google Patents
Info
- Publication number
- JPH0120490B2 JPH0120490B2 JP7555881A JP7555881A JPH0120490B2 JP H0120490 B2 JPH0120490 B2 JP H0120490B2 JP 7555881 A JP7555881 A JP 7555881A JP 7555881 A JP7555881 A JP 7555881A JP H0120490 B2 JPH0120490 B2 JP H0120490B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- magnetic
- protective layer
- ferromagnetic metal
- 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.)
- Expired
Links
- 230000005291 magnetic effect Effects 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 21
- 239000011241 protective layer Substances 0.000 claims description 21
- 230000005294 ferromagnetic effect Effects 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- 238000007740 vapor deposition Methods 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003302 ferromagnetic material Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 15
- 230000008020 evaporation Effects 0.000 description 14
- 229910017052 cobalt Inorganic materials 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000005566 electron beam evaporation Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000007733 ion plating Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
- G11B5/85—Coating a support with a magnetic layer by vapour deposition
Landscapes
- Magnetic Record Carriers (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Thin Magnetic Films (AREA)
Description
本発明は、強磁性金属薄膜層を磁気記録層とす
る磁気記録媒体の製造方法に関する。
従来、磁気記録媒体としては、酸化鉄、酸化ク
ロム等の針状磁性粉或いは、強磁性金属の超微粉
末を樹脂バインダー中に分散しこれを非磁性基材
上に塗布した磁気記録媒体が広く用いられてき
た。
しかし乍ら、近年、情報の高密度記録化の要請
が該磁気記録媒体に対しても強くなされた結果、
種々改良がなされてきたが、上記の従来の塗布型
の磁気記録媒体では、用いている強磁性粉末の粒
子の大きさに記録要素の最小単位としての限界が
あり、それ以上に記録密度を高めることが原理的
に不可能であるため、この高密度記録の要請に答
え難かつた。
このため、最近、記録密度の飛躍的増大を目的
として、樹脂バインダーを使用せず、強磁性金属
薄膜層を磁気記録層とする磁気記録媒体が湿式メ
ツキ法、真空蒸着法、スパツタリング法、イオン
プレーテイング法等の薄膜形成法を用いて精力的
に研究開発され一部は実用に供されている。
しかし乍ら、該強磁性金属薄膜層は通常の保存
状態にあつても酸化され易く磁気性能が経時的に
劣化するという記録保存媒体としては致命的な欠
陥を有している。又、該表面を手指で触れただけ
でも該部分が急速に腐蝕したり、更には、記録再
生時においては、ヘツドとの接触走査により該磁
性層が剥離、摩滅、損傷、脱落等を生じ易いとい
う欠点があつた。
上記欠点を改善するため、これまで該強磁性金
属薄膜の表面上に種々の保護層を設けることが
種々提案されている。例えば、溶液塗布法によつ
て高分子被膜を形成したり、電解メツキ、無電解
メツキ法などの湿式メツキ法によつて金属被膜を
形成したり、クロム酸等の水溶液によるクロム酸
処理によつて反応被膜を形成したり、或いは酸化
雰囲気中で記録媒体を高温加熱処理し強磁性金属
薄膜の表面上に酸化被膜を形成したりする等多く
の方法が提案されているが、未だに充分な保護層
を得るに到つておらず、又、その形成方法にも
種々の解決しなければならぬ問題点を多くかかえ
ている。即ち、塗布によつて高分子被膜を形成す
る方法では塗布工程が必要であり、又、溶剤回収
或いは、公害防止のための大きな付帯設備を要
し、更に充分な耐腐触性を与えるには数ミクロン
以上の膜厚を要し、これが記録密度の低下を招く
という欠点を有していた。又、クロム酸処理によ
つて被膜を形成する方法では、6価クロムの有毒
性から排水処理等に上記と同様の欠点を有する。
湿式メツキ法による耐蝕性金属被膜を形成する方
法では得られる被膜の耐摩耗性が小さく容易に損
傷を受ける。真空蒸着法によつて上記耐蝕性金属
被膜を形成する方法も試みられているが、耐摩耗
性が充分でないという欠点を有している。更に酸
化雰囲気中で記録媒体を高温加熱処理し、酸化被
膜を形成する方法では、基材をポリエチレンテレ
フタレート等の高分子材料とする記録媒体では、
熱変形を生じるという欠点を有し、又、強磁性金
属薄膜自体も加熱処理により結晶構造等の変化を
受け磁気特性が変化を受ける等の欠点がある。
本発明の目的は、上記の欠点を解消し耐摩耗性
と耐腐蝕性に優れかつ磁気特性の良好な磁気記録
媒体の製造方法を提供することにあり、その要旨
は、非磁性材料からなる基材上に蒸着法により設
けられた強磁性金属からなる磁性薄膜にB,C,
Al,Si,P,Ti,V,Cr,Mn,Fe,Co,Ni,
Cu,Ag,Mo,Au、及びSmの群から選ばれた
元素のイオンに10eVから15KeVの範囲の運動エ
ネルギーを付与して、保護層を形成する材料の中
性蒸発粒子とともに入射せしめることを特徴とす
る磁気記録媒体の製造方法に存する。
本発明に於いて非磁性材料からなる基材上に強
磁性金属薄膜を蒸着により設けるには、真空蒸着
法、スパツタリング法、イオンプレーテイング
法、クラスターイオンビーム法等の従来公知の蒸
着法が採用され得るが、基材との密着強度を大き
く取りかつ磁気特性を良好に保つために、
10-4torrより低圧の高真空下でなされるイオンプ
レーテイング法若しくはクラスターイオンビーム
法が特に好ましい。
本発明に於いて使用される非磁性体材料からな
る基材とは、ポリ塩化ビニル、ポリフツ化ビニ
ル、酢酸セルロース、ポリエチレンテレフタレー
ト、ポリブチレンテレフタレート、ポリエチレ
ン、ポリプロピレン、ポリカーボネート、ポリイ
ミド、ポリエーテルサルフオン、ポリバラバン酸
等の高分子材料、アルミニウム、銅、銅―亜鉛合
金等の非磁性金属材料、焼結休、磁器、陶器、ガ
ラスなどのセラミツク材料などが用いられる。
本発明に於いて、上記非磁性材料からなる基材
の形状は、磁気記録媒体の使用方法によつて適宜
定められればよく、例えば、テープ、フイルム、
デイスク、ドラム等の形状で使用される。
本発明における強磁性金属としては、鉄、ニツ
ケル、コバルトの単体金属や、鉄、ニツケル、コ
バルトの群から選ばれた1種以上の金属を含有す
る合金若しくは混合物が挙げられる。そして、鉄
の合金としては、鉄とコバルト、ニツケル、マン
ガン、クロム、銅、金、チタンなどの合金、コバ
ルトの合金としては、コバルトとリン、クロム、
銅、ニツケル、マンガン、金、チタン、イツトリ
ウム、サマリウム、ビスマスなどとの合金、ニツ
ケルの合金としては、ニツケル、銅、亜鉛、マン
ガンなどとの合金が挙げられ、又上記、鉄、コバ
ルト、ニツケルと他の元素との混合物としては、
該他の元素がリン、クロム、銅、亜鉛、金、チタ
ン、イツトリウム、サマリウム、ビスマスなどの
1種以上である混合物が挙げられる。そして、該
強磁性金属としてはコバルトないしはコバルトを
含有する強磁性材料を用いるのが好適である。
又、形成される強磁性金属薄膜層の厚みは、
200Å〜50000Åの範囲が好ましくより好ましくは
500Å〜5000Åの範囲である。
本発明においては上記強磁性金属からなる磁性
薄膜の上に、保護層が形成されるのであり、該保
護層を形成する材料としては白金、金などの貴金
属、アルミニウム、ニツケル、クロムなどの不動
態化する金属、アルミニウム、ケイ素、クロム、
チタンなどの酸化物や窒化物などが用いられ、該
保護層を形成させるには真空条件下でこれらの保
護層形成材料を蒸発させた中性蒸発粒子を上記磁
性薄膜の上に蒸着させることにより行われる。
そして、本発明においては、上記保護層形成材
料の中性蒸発粒子と共に、B(ホウ素)、C(炭
素)、Si(ケイ素)、P(リン)、Ti(チタン)、V
(バナジウム)、Cr(クロム)、Mn(マンガン)、Fe
(鉄)、Co(コバルト)、Ni(ニツケル)、Cu(銅)、
Ag(銀)、Mo(モリブデン)、Au(金)及びSm(サ
マリウム)からなる群から選ばれた元素のイオン
に10eVから15KeVの範囲の運動エネルギーを付
与した高速イオンを前記磁性薄膜の上に入射せし
めて保護層を形成させるのである。
上記の如くに強磁性金属薄膜の表面上に保護層
を形成させることにより耐摩耗性、耐腐蝕性に優
れるのみならず、磁気基本特性とりわけ坑磁力の
優れた磁気記録媒体が得られる。
保護層形成時に上記特定元素の高速イオンの照
射が強磁性金属薄膜及び保護層の微細構造にどう
作用するか現在のところ明確ではないが、イオン
注入効果、蒸着中の連続したイオン衝撃が蒸着膜
の核形成や膜成長に及ぼす影響、被蒸着物表面上
でのマイグレーシヨン効果等により、磁気記録媒
体として好適な微細構造をもたらしたものと考え
られる。
次に図面を用いて本発明を更に詳細に説明す
る。
第1図は、本発明に基づく磁気記録媒体の製造
方法の1例を示す態様図である。
真空室1内は、排気口2に連結されている非気
系装置(油回転ポンプ、油拡散ポンプ等で構成さ
れているが図示されていない)によつて10-7torr
までの高真空に排気することができる様になされ
ている。真空室1内には、保護層を蒸着形成する
主たる材料が供給された電子ビーム蒸発源3、蒸
気遮蔽板4、特定元素の加速イオンを照射するイ
オン源5、イオンを加速するために負の直流高電
圧を印加された加速電極6及びその電源7、強磁
性金属薄膜が蒸着形成されたフイルム8、該フイ
ルムの供給ロール9、巻き取りロール10、及び
ガイドロール11,12が配置されている。但
し、電子ビーム蒸発源3、イオン源5の動作用電
源回路及びフイルム8の走行に要するロール駆動
系は図示していない。電子ビーム蒸発源3は180
偏向Eガン13、ルツボ14、保護層を形成する
ための材料15とから構成されている。
又、第2図はイオン源5の構成を示す断面図で
あり、方向性を揃えた原子状粒子を発生させるた
めの蒸発源部15、及び蒸発粒子をイオン化させ
るためのイオン化部16とからなつている。蒸発
源部15は通電により加熱するヒータールツボ1
7、水冷ジヤケツト18を有する電極19及びル
ツボ17内に供給された蒸発材料20とからなつ
ている。該蒸発源部15の動作は真空室1外に設
置された低電圧交流電源21を印加することによ
りなされる。イオン化部16は、熱電子放出用の
フイラメント22と放出された電子を電界加速す
る網状電極23及び電界制御のためのガード24
とで構成されている。このイオン化部16の動作
は、低電圧交流電源25によりフイラメント22
を加熱し熱電子を放出させ、直流高圧電源26に
よりフイラメント22に負の電位を与えかつ網状
電極23を接地することによつて形成される電界
で該電子を加速せしめて蒸発源部15で発生した
蒸気粒子に衝突させこれをイオン化させることに
よつてなされる。
次に本発明にもとづいて磁気記録媒体を製造す
る方法の一例について説明するに、まず、10-5ト
ールよりも高真空度の条件下でコバルトを蒸発さ
せ、該蒸発粒子に加速電子を衝撃させてこれをイ
オン化し、該イオン化粒子を電界加速させて基材
面に入射させるという高真空イオンプレーテイン
グ法の手法により厚さ15μのポリエチレンテレフ
タレートフイルム上に1500Åのコバルト薄膜層を
設けた蒸着テープを用意し、これをフイルム8と
して第1図における供給ロール9に巻き取り、同
図の如くセツトする。
次いで保護層を形成するための材料をルツボ1
4に供給し、又イオン源5の第2図に示されるヒ
ータールツボ17に本発明において特定される群
から選ばれた元素からなる蒸発材料を供給し、そ
れぞれ第1図に示される様に配置する。次いで排
気口2から排気系装置によつて真空室1内を8×
10-4トールから10-8トールの範囲の高真空に排気
する。
真空度が安定したところでフイルム8をガイド
ロール11から12の方向へ走行させながら、イ
オン源5、蒸発源3及び加速電極6を動作させ、
フイルム8の強磁性金属磁性薄膜上に、蒸発源3
から発生する中性蒸発粒子と共に、イオン源5か
ら発生し、加速電極6によつて10eVから15KeV
の範囲の運動エネルギーを有するように加速され
た特定元素のイオンを入射させ保護層を形成させ
るのである。
なお、図示される実施例においては、イオン源
5はフイルム8の面に対して略正面に、又蒸発源
3はフイルム8の面に対して斜め方向にそれぞれ
位置する様に配置されているが、本発明において
はこれに制限されることはなく、フイルム8の面
に対するイオン源5及び蒸発源3の配置角度は自
由に選択し得る。
かくして本発明にもとづいて得られる磁気記録
媒体は、単に保護層を蒸着形成したものと比較し
て、保護層機能の中で特に耐摩耗が改善され、か
つ、磁気基本特性の中で特に抗磁力の向上した磁
気記録媒体となるのである。
以下本発明の実施例及び比較例について説明す
る。
実施例
厚さ15μのポリエチレンテレフタレートテープ
を、一定速度で走行させながら、該テープ表面
に、5×10-6トールの高真空中で、加速電子衝突
によつてイオン化されたコバルト蒸発粒子を電界
加速させて入射させることにより、1500Åの厚さ
のコバルト蒸着層を設けた蒸着テープを用意し
た。
第1図に示される装置を用いて、該蒸着テープ
上に約500Åの厚さの保護層を形成させた。その
際に用いた中性蒸発粒子及びイオンの種類は第1
表の通りであり、又、イオン蒸着時における条件
はイオン運動エネルギー:1KeV、イオン電流:
150μAとした。
かくして得られた磁気テープについて、抗磁
力、耐蝕性及び耐摩耗性についてのテストを行つ
た所第1表に示される結果を得た。
又、比較のため、上記で用意した蒸着テープに
なんら保護層を設けなかつたもの(比較例1)及
び上記蒸着テープに第1図に示される装置の電子
ビーム蒸着源3のみの作動により約500Åのクロ
ム蒸着層を設けたもの(比較例2)についても上
記テスト結果を第1表に併記する。
The present invention relates to a method of manufacturing a magnetic recording medium using a ferromagnetic metal thin film layer as a magnetic recording layer. Conventionally, magnetic recording media have been widely used in which acicular magnetic powder such as iron oxide or chromium oxide or ultrafine powder of ferromagnetic metal is dispersed in a resin binder and coated on a non-magnetic base material. has been used. However, in recent years, as a result of the strong demand for high-density recording of information on magnetic recording media,
Various improvements have been made, but in the conventional coating-type magnetic recording media described above, there is a limit to the size of the ferromagnetic powder particles used as the smallest unit of the recording element, and it is necessary to increase the recording density beyond that limit. Since this is theoretically impossible, it was difficult to meet the request for high-density recording. For this reason, recently, with the aim of dramatically increasing recording density, magnetic recording media that do not use a resin binder and have a ferromagnetic metal thin film layer as a magnetic recording layer have been developed using wet plating methods, vacuum evaporation methods, sputtering methods, ion plating methods, etc. Research and development has been carried out vigorously using thin film formation methods such as the Teing method, and some of them have been put into practical use. However, the ferromagnetic metal thin film layer has a fatal defect as a recording storage medium in that it is easily oxidized even under normal storage conditions, and its magnetic performance deteriorates over time. In addition, even if the surface is touched with fingers, the portion will rapidly corrode, and furthermore, during recording and reproduction, the magnetic layer is likely to peel off, wear out, be damaged, fall off, etc. due to contact scanning with the head. There was a drawback. In order to improve the above drawbacks, various proposals have been made to provide various protective layers on the surface of the ferromagnetic metal thin film. For example, a polymer film can be formed by a solution coating method, a metal film can be formed by a wet plating method such as electrolytic plating or electroless plating method, or a metal film can be formed by a chromic acid treatment using an aqueous solution such as chromic acid. Although many methods have been proposed, such as forming a reaction film or forming an oxide film on the surface of a ferromagnetic metal thin film by heating the recording medium at high temperature in an oxidizing atmosphere, there is still no sufficient protective layer. However, the method for forming the same has many problems that need to be solved. That is, the method of forming a polymer film by coating requires a coating process, requires large-scale incidental equipment for solvent recovery or pollution prevention, and also requires sufficient corrosion resistance. This requires a film thickness of several microns or more, which has the disadvantage of lowering the recording density. Furthermore, the method of forming a film by chromic acid treatment has the same drawbacks as above in wastewater treatment due to the toxicity of hexavalent chromium.
In the method of forming a corrosion-resistant metal coating by wet plating, the resulting coating has low wear resistance and is easily damaged. Attempts have been made to form the above-mentioned corrosion-resistant metal coating by vacuum evaporation, but this method has the drawback of insufficient wear resistance. Furthermore, in the method of forming an oxide film by subjecting the recording medium to high temperature heat treatment in an oxidizing atmosphere, recording media whose base material is a polymeric material such as polyethylene terephthalate,
It has the disadvantage that it undergoes thermal deformation, and the ferromagnetic metal thin film itself also undergoes a change in crystal structure and other properties due to heat treatment, resulting in changes in its magnetic properties. An object of the present invention is to eliminate the above-mentioned drawbacks and provide a method for manufacturing a magnetic recording medium that is excellent in wear resistance, corrosion resistance, and magnetic properties. B, C,
Al, Si, P, Ti, V, Cr, Mn, Fe, Co, Ni,
It is characterized by imparting kinetic energy in the range of 10eV to 15KeV to ions of an element selected from the group of Cu, Ag, Mo, Au, and Sm, and making them incident together with neutral evaporated particles of the material forming the protective layer. A method of manufacturing a magnetic recording medium is provided. In the present invention, conventionally known vapor deposition methods such as vacuum vapor deposition, sputtering, ion plating, and cluster ion beam methods are employed to provide a ferromagnetic metal thin film on a base material made of nonmagnetic material by vapor deposition. However, in order to increase the adhesion strength with the base material and maintain good magnetic properties,
Particularly preferred is the ion plating method or the cluster ion beam method, which is carried out under a high vacuum at a pressure lower than 10 -4 torr. The base material made of non-magnetic material used in the present invention includes polyvinyl chloride, polyvinyl fluoride, cellulose acetate, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, polyether sulfon, Polymer materials such as polyvalabanic acid, non-magnetic metal materials such as aluminum, copper, and copper-zinc alloys, ceramic materials such as sintered materials, porcelain, earthenware, and glass are used. In the present invention, the shape of the base material made of the non-magnetic material may be appropriately determined depending on the usage method of the magnetic recording medium, and for example, it may be a tape, a film, a
Used in the form of disks, drums, etc. Examples of the ferromagnetic metal in the present invention include single metals such as iron, nickel, and cobalt, and alloys or mixtures containing one or more metals selected from the group of iron, nickel, and cobalt. Iron alloys include iron and cobalt, nickel, manganese, chromium, copper, gold, and titanium, and cobalt alloys include cobalt and phosphorus, chromium,
Alloys with copper, nickel, manganese, gold, titanium, yttrium, samarium, bismuth, etc.; Alloys of nickel include alloys with nickel, copper, zinc, manganese, etc.; As a mixture with other elements,
Examples include mixtures in which the other element is one or more of phosphorus, chromium, copper, zinc, gold, titanium, yttrium, samarium, bismuth, and the like. As the ferromagnetic metal, it is preferable to use cobalt or a ferromagnetic material containing cobalt. Also, the thickness of the ferromagnetic metal thin film layer to be formed is
The range of 200 Å to 50000 Å is preferable, more preferably
It ranges from 500 Å to 5000 Å. In the present invention, a protective layer is formed on the magnetic thin film made of the above-mentioned ferromagnetic metal, and materials for forming the protective layer include noble metals such as platinum and gold, and passive materials such as aluminum, nickel, and chromium. metals, aluminum, silicon, chromium,
Oxides and nitrides such as titanium are used, and to form the protective layer, neutral evaporated particles obtained by evaporating these protective layer forming materials under vacuum conditions are deposited on the magnetic thin film. It will be done. In the present invention, in addition to the neutral evaporated particles of the protective layer forming material, B (boron), C (carbon), Si (silicon), P (phosphorus), Ti (titanium), V
(vanadium), Cr (chromium), Mn (manganese), Fe
(iron), Co (cobalt), Ni (nickel), Cu (copper),
High-speed ions of an element selected from the group consisting of Ag (silver), Mo (molybdenum), Au (gold), and Sm (samarium) are charged with kinetic energy in the range of 10 eV to 15 KeV onto the magnetic thin film. A protective layer is formed by allowing the light to enter the room. By forming a protective layer on the surface of the ferromagnetic metal thin film as described above, it is possible to obtain a magnetic recording medium which not only has excellent wear resistance and corrosion resistance, but also has excellent basic magnetic properties, particularly coercive force. At present, it is not clear how the irradiation of high-velocity ions of the above-mentioned specific elements will affect the fine structure of the ferromagnetic metal thin film and the protective layer during the formation of the protective layer, but the ion implantation effect and continuous ion bombardment during vapor deposition may affect the deposited film. It is thought that the fine structure suitable for a magnetic recording medium was brought about by the influence of nucleation on nucleation and film growth, the migration effect on the surface of the deposited object, etc. Next, the present invention will be explained in more detail using the drawings. FIG. 1 is a diagram showing an example of a method for manufacturing a magnetic recording medium according to the present invention. The inside of the vacuum chamber 1 is heated to 10 -7 torr by a non-gas system device (consisting of an oil rotary pump, an oil diffusion pump, etc., not shown) connected to the exhaust port 2.
It is designed so that it can be evacuated to high vacuum levels. Inside the vacuum chamber 1, there is an electron beam evaporation source 3 supplied with the main material for forming the protective layer by vapor deposition, a vapor shielding plate 4, an ion source 5 for irradiating accelerated ions of a specific element, and a negative evaporation source 3 for accelerating the ions. An accelerating electrode 6 to which a DC high voltage is applied and its power source 7, a film 8 on which a ferromagnetic metal thin film is deposited, a supply roll 9 for the film, a take-up roll 10, and guide rolls 11 and 12 are arranged. . However, the power supply circuit for operating the electron beam evaporation source 3 and the ion source 5 and the roll drive system required for running the film 8 are not shown. Electron beam evaporation source 3 is 180
It is composed of a deflection E gun 13, a crucible 14, and a material 15 for forming a protective layer. FIG. 2 is a cross-sectional view showing the configuration of the ion source 5, which consists of an evaporation source section 15 for generating atomic particles with uniform directionality and an ionization section 16 for ionizing the evaporated particles. ing. The evaporation source part 15 is a heater crucible 1 that is heated by electricity.
7. It consists of an electrode 19 with a water cooling jacket 18 and an evaporation material 20 fed into the crucible 17. The evaporation source section 15 is operated by applying a low voltage AC power source 21 installed outside the vacuum chamber 1. The ionization unit 16 includes a filament 22 for emitting thermionic electrons, a mesh electrode 23 for accelerating the emitted electrons with an electric field, and a guard 24 for controlling the electric field.
It is made up of. The operation of the ionization section 16 is performed by the filament 22 by the low voltage AC power supply 25.
is heated to emit thermoelectrons, and the electrons are accelerated by an electric field formed by applying a negative potential to the filament 22 by the DC high-voltage power supply 26 and grounding the mesh electrode 23, and generated in the evaporation source section 15. This is done by colliding with vapor particles and ionizing them. Next, an example of a method for manufacturing a magnetic recording medium according to the present invention will be described. First, cobalt is evaporated under a vacuum condition higher than 10 -5 Torr, and the evaporated particles are bombarded with accelerated electrons. Using the high-vacuum ion plating method, in which the ionized particles are accelerated by an electric field and made incident on the substrate surface, a vapor deposition tape with a 1500 Å thin cobalt film layer on a 15 μ thick polyethylene terephthalate film is created. This is prepared as a film 8 and wound onto the supply roll 9 shown in FIG. 1, and set as shown in the same figure. Next, the material for forming the protective layer is placed in crucible 1.
4, and an evaporation material made of an element selected from the group specified in the present invention is supplied to the heater crucible 17 shown in FIG. 2 of the ion source 5, and each is arranged as shown in FIG. do. Next, the inside of the vacuum chamber 1 is pumped 8× using the exhaust system device from the exhaust port 2.
Evacuate to high vacuum in the range of 10 -4 Torr to 10 -8 Torr. When the degree of vacuum is stabilized, the ion source 5, evaporation source 3, and accelerating electrode 6 are operated while the film 8 is traveling in the direction from the guide rolls 11 to 12.
An evaporation source 3 is placed on the ferromagnetic metal magnetic thin film of the film 8.
It is generated from the ion source 5 along with neutral evaporated particles generated from the
A protective layer is formed by injecting ions of a specific element that have been accelerated to have a kinetic energy in the range of . In the illustrated embodiment, the ion source 5 is located approximately in front of the surface of the film 8, and the evaporation source 3 is located obliquely to the surface of the film 8. However, the present invention is not limited to this, and the angle at which the ion source 5 and the evaporation source 3 are arranged with respect to the surface of the film 8 can be freely selected. Thus, the magnetic recording medium obtained according to the present invention has improved abrasion resistance among the protective layer functions, and especially improved coercive force among the basic magnetic properties, compared to one in which a protective layer is simply formed by vapor deposition. This results in a magnetic recording medium with improved properties. Examples and comparative examples of the present invention will be described below. Example While running a polyethylene terephthalate tape with a thickness of 15μ at a constant speed, cobalt evaporation particles ionized by accelerated electron collisions were applied to the tape surface under electric field acceleration in a high vacuum of 5×10 -6 Torr. A vapor deposition tape having a cobalt vapor deposition layer with a thickness of 1500 Å was prepared by making the light incident on the cobalt film. A protective layer with a thickness of about 500 Å was formed on the vapor-deposited tape using the apparatus shown in FIG. The types of neutral evaporation particles and ions used at that time were
The table shows the conditions for ion deposition: ion kinetic energy: 1KeV, ion current:
It was set to 150μA. The thus obtained magnetic tape was tested for coercive force, corrosion resistance, and abrasion resistance, and the results shown in Table 1 were obtained. In addition, for comparison, the vapor deposition tape prepared above without any protective layer (Comparative Example 1) and the vapor deposition tape prepared above were coated with approximately 500 Å by operating only the electron beam evaporation source 3 of the apparatus shown in FIG. The above test results are also listed in Table 1 for the product with a chromium vapor deposited layer (Comparative Example 2).
【表】
但し、抗磁力は直流磁化測定装置(BHカーブ
トレーサ)による測定値、耐蝕性は温度60℃、相
対湿度100%の条件下で250時間放置した時の腐蝕
の存在の有無で評価し表示しており、又、耐摩耗
性は、セロテープでのピールテストによる剥離個
所の有無、サフアイヤボール(径0.1mm)での荷
重30gの条件によるひつかき試験でひつかきキズ
が残るかどうか、及び市販カセツトテープレコー
ダでのエンドレステープ状サンプルの1000回ヘツ
ド通過させた後の再生出力の減少率にて評価し、
これらの結果を表示している。[Table] However, coercive force is measured by a DC magnetization measuring device (BH curve tracer), and corrosion resistance is evaluated by the presence or absence of corrosion when left for 250 hours at a temperature of 60°C and a relative humidity of 100%. In addition, wear resistance is determined by whether or not there are any peeling points in a peel test with Sellotape, and whether scratches remain in a test using a Sapphire ball (diameter 0.1 mm) under a load of 30 g. and evaluated by the rate of decrease in playback output after passing an endless tape sample through the head of a commercially available cassette tape recorder 1000 times.
Displaying these results.
第1図は本発明方法の1例を示す態様図、第2
図は第1図のイオン源5の断面図である。
1…真空室、3…電子ビーム蒸発源、5…イオ
ン源、6…加速電極、8…フイルム、15…蒸発
源部、16…イオン化部。
FIG. 1 is a mode diagram showing one example of the method of the present invention, and FIG.
The figure is a cross-sectional view of the ion source 5 of FIG. 1. DESCRIPTION OF SYMBOLS 1... Vacuum chamber, 3... Electron beam evaporation source, 5... Ion source, 6... Accelerating electrode, 8... Film, 15... Evaporation source part, 16... Ionization part.
Claims (1)
けられた強磁性金属からなる磁性薄膜に、B,
C,Al,Si,P,Ti,V,Cr,Mn,Fe,Co,
Ni,Cu,Ag,Mo,Au、及びSmの群から選ば
れた元素のイオンに10eVから15KeVの範囲の運
動エネルギーを付与して、保護層を形成する材料
の中性蒸発粒子とともに入射せしめることを特徴
とする磁気記録媒体の製造方法。 2 強磁性金属がCoないしはCoを含有する強磁
性材料であ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。[Scope of Claims] 1. A magnetic thin film made of a ferromagnetic metal provided by a vapor deposition method on a base material made of a nonmagnetic material, containing B,
C, Al, Si, P, Ti, V, Cr, Mn, Fe, Co,
Imparting kinetic energy in the range of 10 eV to 15 KeV to ions of an element selected from the group of Ni, Cu, Ag, Mo, Au, and Sm, and making them incident together with neutral evaporated particles of the material forming the protective layer. A method of manufacturing a magnetic recording medium characterized by: 2. The method for manufacturing a magnetic recording medium according to claim 1, wherein the ferromagnetic metal is Co or a ferromagnetic material containing Co.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7555881A JPS57189340A (en) | 1981-05-18 | 1981-05-18 | Manufacture of magnetic recording medium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7555881A JPS57189340A (en) | 1981-05-18 | 1981-05-18 | Manufacture of magnetic recording medium |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57189340A JPS57189340A (en) | 1982-11-20 |
JPH0120490B2 true JPH0120490B2 (en) | 1989-04-17 |
Family
ID=13579623
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7555881A Granted JPS57189340A (en) | 1981-05-18 | 1981-05-18 | Manufacture of magnetic recording medium |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57189340A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59207031A (en) * | 1983-05-10 | 1984-11-24 | Hitachi Condenser Co Ltd | Manufacturing device of magnetic recording medium |
JPH0754584B2 (en) * | 1984-03-27 | 1995-06-07 | 三菱化学株式会社 | Method of manufacturing magnetic recording medium |
JPS61133030A (en) * | 1984-11-30 | 1986-06-20 | Sony Corp | Production of magnetic recording medium |
JPH0196822A (en) * | 1987-10-09 | 1989-04-14 | Mitsubishi Electric Corp | Magnetic recording medium |
-
1981
- 1981-05-18 JP JP7555881A patent/JPS57189340A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57189340A (en) | 1982-11-20 |
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