JPS63157314A - Magnetic recording medium and its production - Google Patents
Magnetic recording medium and its productionInfo
- Publication number
- JPS63157314A JPS63157314A JP30512586A JP30512586A JPS63157314A JP S63157314 A JPS63157314 A JP S63157314A JP 30512586 A JP30512586 A JP 30512586A JP 30512586 A JP30512586 A JP 30512586A JP S63157314 A JPS63157314 A JP S63157314A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- magnetic
- recording medium
- magnetic recording
- film
- 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 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 239000004065 semiconductor Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002985 plastic film Substances 0.000 claims abstract description 7
- 229920006255 plastic film Polymers 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000007747 plating Methods 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- 239000007791 liquid phase Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000013032 photocatalytic reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- -1 co/ilte Chemical compound 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
この発明は磁性層が鉄、コバルト、ニッケルなどの強磁
性金属の薄膜にて構成された磁気記録媒体とその製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a magnetic recording medium in which a magnetic layer is made of a thin film of a ferromagnetic metal such as iron, cobalt, or nickel, and a method for manufacturing the same.
この種の磁気記録媒体は、一般的に汎用されている非磁
性の基板上に磁性粉末を結合剤樹脂中に分散結着させて
なる磁性層を設けた構成の塗布型媒体に較べて、磁性層
の薄膜化が容易でかつ磁性層中に結合剤樹脂を含まない
ことから、高密度記録に適した媒体として近年特に注目
されている。This type of magnetic recording medium has a magnetic layer that is formed by dispersing and bonding magnetic powder in a binder resin on a generally used non-magnetic substrate. Since the layer can be easily made thin and the magnetic layer does not contain a binder resin, it has attracted particular attention in recent years as a medium suitable for high-density recording.
従来、このような磁性金属層を有してなる磁気記録媒体
は、ポリエステルフィルムなどのプラスチックフィルム
上に磁性金属層を真空蒸着法などの方法により気相中で
薄膜形成させるか、あるいは無電解メッキによる液相メ
ッキ法で析出被着させることによりつくられている。特
に、後者の液相メッキ法は、真空蒸着法などよりも生産
性にすぐれ、かつ均一な磁性金属層の形成が容易である
ことから、その実用化が古くから検討されている。Conventionally, magnetic recording media having such a magnetic metal layer have been produced by forming a thin film of the magnetic metal layer on a plastic film such as a polyester film in a gas phase using a method such as vacuum evaporation, or by electroless plating. It is made by depositing and depositing it using a liquid phase plating method. In particular, the latter liquid phase plating method has been considered for practical use for a long time because it has better productivity than vacuum evaporation methods and it is easier to form a uniform magnetic metal layer.
しかるに、上記従来の液相メッキ法は、上述の如き利点
を有しているものの、無電解メッキのため、メッキする
べきプラスチックフィルムに予めエツチング処理、感受
性化処理および活性化処理などの多くの前処理を施して
おく必要があり、このような前処理を施さなければ磁性
金属をうまく析出形成できないという難点があった。し
かも、上記前処理によると、たとえばエツチング処理で
はクロムが、感受性化処理ではスズが、また活性化処理
ではパラジウムが、プラスチックフィルム表面に残るこ
ととなるため、これら金属がその上に形成される磁性金
属層の磁気特性に悪影響をおよぼすおそれがあり、通常
では角型比（残留磁化／飽和磁化）の低下や保磁力が充
分に大きくならないといった問題を引きおこしていた。However, although the conventional liquid phase plating method has the above-mentioned advantages, because it is electroless plating, the plastic film to be plated must be subjected to many pretreatments such as etching treatment, sensitization treatment, and activation treatment. It is necessary to perform a pretreatment, and there is a problem in that the magnetic metal cannot be successfully deposited and formed unless such pretreatment is performed. Moreover, according to the above pretreatment, for example, chromium remains on the surface of the plastic film in the etching process, tin in the sensitization process, and palladium in the activation process. This may adversely affect the magnetic properties of the metal layer, and usually causes problems such as a decrease in squareness ratio (residual magnetization/saturation magnetization) and insufficient coercive force.
したがって、この発明は、気相中薄膜形成法よりも生産
性などの面ですぐれる液相メッキ法の上述の問題点を克
服して、角型比や保磁力の大きい磁気特性にすぐれる磁
気記録媒体を上記液相メッキ法で得ることを目的として
いる。Therefore, the present invention overcomes the above-mentioned problems of the liquid phase plating method, which is superior to the vapor phase thin film forming method in terms of productivity, etc. The purpose is to obtain a recording medium by the liquid phase plating method described above.
［問題点を解決するための手段］
この発明者らは、上記の目的を達成するために鋭意検討
した結果、液相メッキ法により磁性金属層を形成するに
あたり、メッキ形成するべき基板として従来用いられた
ことのない特定のものを使用し、かつメッキ形成を光触
媒反応を利用して行うことにより、角型比や保磁力の大
きい磁気特性にすぐれる磁気記録媒体を生産性良好に得
ることができることを知った。[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors found that when forming a magnetic metal layer by liquid phase plating, the present inventors found that, when forming a magnetic metal layer by liquid phase plating, By using a specific material that has never been used before, and by forming the plating using a photocatalytic reaction, it is possible to obtain magnetic recording media with excellent magnetic properties such as a large squareness ratio and coercive force with good productivity. I learned that I can do it.
この発明は、上記知見に基づく改良された液相メッキ法
とこの方法にてつくられる磁気特性にすぐれ、その基板
構成が従来とは全（異なる磁気記録媒体を提供しようと
するものである。すなわち、この発明は、半導体特性を
有する基板とこの基板表面に形成された磁性金属層とか
らなることを特徴とする磁気記録媒体に係る第１′の発
明と、磁性金属イオンおよび還元剤を含む溶媒中に半導
体特性を有する基板を浸し、上記基板を構成する半導体
物質のバンドギャップのエネルギーより大きなエネルギ
ーを有する光を照射することにより、上記基板の表面に
磁性金属イオンを還元析出させて〔発明の構成・作用］
この発明においては、既述のとおり、液相メッキ法に光
触媒反応を応用したものであるが、この光触媒反応とは
、一般に半導体物質を水などの溶媒に浸してこれに上記
物質の価電子帯から伝導帯までのバンドギャップのエネ
ルギーより大きなエネルギーを有する光を照射したとき
に、伝導帯に電子を、価電子帯に正孔を生じ、これら電
子および正孔は半導体物質の中でただちに拡散して物質
表面に達し、その囲りに存在する溶媒がたとえば水であ
って上記伝導帯の電位が水素還元電位より高ければ上記
電子は表面に存在する水分子（またはプロトン）を還元
して水素を発生させ、また上記正孔は価電子帯の電位に
応じて周囲の水や万機物の電子を奪い酸化分解をおこす
ものであり、このように酸化還元反応を酸化剤や還元剤
を用いることなく効率的に行わせつるものとして近年特
に注目をあびているものである。The present invention aims to provide an improved liquid phase plating method based on the above findings, and a magnetic recording medium that has excellent magnetic properties produced by this method, and whose substrate structure is completely different from that of the conventional one. The present invention relates to a first aspect of the present invention relating to a magnetic recording medium characterized by comprising a substrate having semiconductor properties and a magnetic metal layer formed on the surface of the substrate, and a solvent containing magnetic metal ions and a reducing agent. A substrate having semiconductor properties is immersed in the medium and irradiated with light having an energy greater than the band gap energy of the semiconductor material constituting the substrate, thereby reducing and precipitating magnetic metal ions on the surface of the substrate. Structure/Operation] As mentioned above, the present invention applies a photocatalytic reaction to the liquid phase plating method. Generally speaking, this photocatalytic reaction involves soaking a semiconductor material in a solvent such as water and then adding the above-mentioned material to the liquid-phase plating method. When irradiated with light having an energy greater than the energy of the band gap from the valence band to the conduction band, electrons are generated in the conduction band and holes are generated in the valence band, and these electrons and holes are released into the semiconductor material. If the surrounding solvent is water, for example, and the potential of the conduction band is higher than the hydrogen reduction potential, the electrons will reduce the water molecules (or protons) present on the surface. In addition, depending on the potential of the valence band, the holes take away electrons from surrounding water and other objects, causing oxidation and decomposition. This method has attracted particular attention in recent years as it can be carried out efficiently without the use of chemicals.
この発明者らは、上記の光触媒反応を液相メッキ法にお
ける磁性金属の析出に応用するべく、メッキ形成用の基
板として従来用いられたことのない半導体特性を有する
もの、たとえばプラスチックフィルム上に半導体物質と
してＴｉＯ□の膜を形成してなるものを用い、この基板
を磁性金属イオンとともに還元剤を含ませてなる溶媒中
に浸すようにしてみたところ、光照射により生じて上記
基板（のＴｉＯ２膜）の表面に拡散した電子および正孔
のうち後者の正孔は周囲の還元剤と反応して消滅し、電
子のみが基板表面に残存する結果、この基板は周囲の磁
性金属イオンの還元電位より高くなってこの金属イオン
を強く引きつけるとともにこれを金属に還元し、これに
よって基板表面に極めて密着の良い磁性金属層が形成さ
れた磁気記録媒体が得られることを見い出したものであ
る。In order to apply the above-mentioned photocatalytic reaction to the deposition of magnetic metal in liquid phase plating, the inventors developed a substrate for plating that has semiconductor characteristics that has not been previously used, such as a plastic film. When we tried to use a TiO□ film as a substance and immerse this substrate in a solvent containing magnetic metal ions and a reducing agent, the TiO2 film formed on the substrate (the TiO2 film on the substrate) was formed by light irradiation. ) Of the electrons and holes diffused on the surface of the substrate, the latter holes react with the surrounding reducing agent and disappear, leaving only the electrons on the substrate surface. It was discovered that the metal ions can be strongly attracted to the metal ions and reduced to metal, thereby producing a magnetic recording medium in which a magnetic metal layer with extremely good adhesion is formed on the substrate surface.
そして、このようにして形成された磁性金属層は、従来
の無電解メッキにて形成されたものに比しより均一であ
り、しかもメッキ形成するべき基板に前記したような前
処理を施す必要が全くないため、メッキ形成作業の容易
化を図れるとともに、前処理金属の残存に起因した磁気
特性の劣化をきたすことがなく、角型比や保磁力の向上
に大きく寄与させることができる。そのうえ、上記方法
にあっては、光照射時の光の強さおよび光照射時間をコ
ントロールすることにより、磁性金属の析出をコントロ
ールできるため、得られる磁気記録媒体の磁気特性を正
確かつ確実にコントロールすることが可能となる。The magnetic metal layer formed in this way is more uniform than that formed by conventional electroless plating, and it is not necessary to perform the above-mentioned pretreatment on the substrate to be plated. Since there is no metal at all, the plating work can be facilitated, and there is no deterioration of magnetic properties due to residual pre-treated metal, which can greatly contribute to improving the squareness ratio and coercive force. Furthermore, in the above method, the precipitation of magnetic metal can be controlled by controlling the light intensity and light irradiation time during light irradiation, so the magnetic properties of the resulting magnetic recording medium can be controlled accurately and reliably. It becomes possible to do so.
以下、上記の光触媒反応を利用したこの発明の磁気記録
媒体の製造方法につき、上記媒体の構成要素とともに詳
しく説明する。Hereinafter, a method for manufacturing a magnetic recording medium of the present invention using the above-mentioned photocatalytic reaction will be explained in detail together with the constituent elements of the above-mentioned medium.
この発明において用いられる半導体特性を有する基板と
しては、磁気記録媒体の用途目的に応じて、プラスチッ
クフィルムを代表例とする絶縁フィルム上に半導体物質
の膜を形成してなるものか、あるいは半導体物質単独か
らなる基板のいずれかが用いられる。これらの厚み構成
は、その用途に応じて決められるが、たとえば前者の例
では絶縁フィルムの厚みが５〜１００戸程度でこの上に
設けられる半導体物質の膜が０．００５〜５ｐｎ程度の
ものが可撓性を有する基板として特に好ましく用いられ
る。なお、上記半導体物質の膜は、上記物質の種類に応
じて真空蒸着法、スパッタリング法、塗布法またはこれ
と熱分解法とを組み合わせた方法などにて形成すること
ができる。Depending on the purpose of the magnetic recording medium, the substrate having semiconductor properties used in this invention may be one formed by forming a film of a semiconductor material on an insulating film, typically a plastic film, or one made of a semiconductor material alone. Either one of the following substrates is used. These thickness structures are determined depending on the application, but for example, in the former example, the thickness of the insulating film is about 5 to 100 pn, and the semiconductor material film provided on it is about 0.005 to 5 pn. It is particularly preferably used as a flexible substrate. Note that the film of the semiconductor material can be formed by a vacuum evaporation method, a sputtering method, a coating method, or a method combining these with a thermal decomposition method, depending on the type of the material.
ここに使用する半導体物質としては、半導体特性を有す
るものであれば公知のものをいずれも使用でき、場合に
よっては磁性体の使用も可能である。その具体例として
は、Ｓ ｉ、ＧａＡｓ、ＧａＰ。As the semiconductor material used here, any known material can be used as long as it has semiconductor properties, and in some cases, it is also possible to use a magnetic material. Specific examples include Si, GaAs, and GaP.
ＣｄＳ、５ｎＴｉ０３ 、Ｉｎｋ、ＣｄＳｅ、ＴｉＯ，
２、ＭｏＳ２、Ｆ ｅ２０．、 Ｉ ｎ２０ａ、ＷＯ２
などが挙げられ、これらの中でも成膜や成形上などの面
でも有利なＳｉ、ＴｉＯ２、Ｆｅ２Ｏ３、ＧａＡｓなど
が特に好ましい。CdS, 5nTi03, Ink, CdSe, TiO,
2, MoS2, Fe20. , I n20a, WO2
Among these, Si, TiO2, Fe2O3, GaAs, etc., which are advantageous in terms of film formation and molding, are particularly preferred.
この発明においては、まず上記の半導体特性を有する基
板を磁性金属イオンおよび還元剤を含ませた溶媒中に浸
漬する。上記溶媒としては通常水を用いるが、還元剤を
溶解できまた磁性金属塩を金属イオンとして溶存させる
ときができさらに光触媒反応に不活性なものであれば、
水以外の極性溶媒を用いてもよい。還元剤としては無’
ＭＬ ｆＮメッキに用いられているものがいずれも使用
可能であり、たとえば次亜リン酸ソーダ、ヒドラジン、
ホルマリン、エタノール、ギ酸、ギ酸ナトリウムなどが
挙げられる。磁性金属イオンは、鉄、コ／イルトおよび
ニッケルの中から選ばれた少なくとも一種の金属からな
るイオンが一般的であるが、これらにさらに他種の金）
４イオンを加えたものであってもよい。これらイオンは
、相当する金（４の硫酸塩、塩化物、硝酸塩などを溶媒
に溶解させることにより、溶媒中に含ませることができ
る。In this invention, first, a substrate having the above semiconductor properties is immersed in a solvent containing magnetic metal ions and a reducing agent. Water is usually used as the solvent, but water can be used as long as it can dissolve the reducing agent, dissolve the magnetic metal salt as metal ions, and is inert to the photocatalytic reaction.
Polar solvents other than water may also be used. Nothing as a reducing agent
Any of those used for ML fN plating can be used, such as sodium hypophosphite, hydrazine,
Examples include formalin, ethanol, formic acid, and sodium formate. Magnetic metal ions are generally ions made of at least one metal selected from iron, co/ilte, and nickel, but in addition to these, other types of gold are also used.
4 ions may be added. These ions can be included in a solvent by dissolving the corresponding gold (sulfate, chloride, nitrate, etc. of 4) in the solvent.
なお、上記還元剤の使用量としては、溶媒中５〜３０’
ｊ／ｌ程度とすればよい。また、磁性金属イオンは、形
成するべき磁性金属層の厚みなどに応じてその使用層が
決められるが、一般には前記の如き磁性金属塩が溶媒中
５〜４０ｙ／ｌ程度となるようにするのが望ましい。The amount of the reducing agent used is 5-30' in the solvent.
It may be about j/l. In addition, the layer to be used for magnetic metal ions is determined depending on the thickness of the magnetic metal layer to be formed, but in general, the amount of the magnetic metal salt as described above in the solvent is about 5 to 40 y/l. is desirable.
なおまた、上記溶媒中には必要に応じて適宜の錯化剤や
ＰＨ調整剤を含ませてもよい。錯化剤としては磁性金属
イオンを有効に錯化して磁性金属の均一かつ安定な析出
を補助しうるものが用いられ、具体的にはクエン酸ソー
ダ、酒石酸ソーダなどが挙げられる。使用ｌは、溶媒中
１０〜８０ｙ／ｌ程度とすればよい。また、ＰＨ調整剤
としては、ホウ酸、硫酸アンモニウム、苛性ソーダ、苛
性カリ、アンモニアなどが用いられ、溶媒のＰＨが７５
〜１０．５、好適には８．５〜９５の範囲となるように
その使用量を決めるのが望ましい。Furthermore, the above-mentioned solvent may contain an appropriate complexing agent or pH adjuster, if necessary. As the complexing agent, one that can effectively complex magnetic metal ions and assist in uniform and stable precipitation of the magnetic metal is used, and specific examples thereof include sodium citrate and sodium tartrate. The amount of liter used may be about 10 to 80 y/l in the solvent. In addition, as a pH adjuster, boric acid, ammonium sulfate, caustic soda, caustic potash, ammonia, etc. are used, and the pH of the solvent is 75.
It is desirable to determine the amount to be used so that it is in the range of 10.5 to 10.5, preferably 8.5 to 95.
溶媒の温度は、これが高すぎると磁性金属の均一な析出
付着を難しくするため、還元剤などの種須に応じた適切
な温度に設定するのが好ましい。If the temperature of the solvent is too high, it will be difficult to uniformly deposit and adhere the magnetic metal, so it is preferable to set the temperature appropriately depending on the source of the reducing agent or the like.
一般には、用いる還元剤が熱的に分解しない温度、通常
９０°Ｃ以下、好適には６０〜８５°Ｃの温度とするの
がよい。Generally, the temperature is preferably set at a temperature at which the reducing agent used does not decompose thermally, usually 90°C or less, preferably 60 to 85°C.
この発明においてはこのような溶媒に前記基板を浸した
状態で光を照射する。この光は既述のとおり基板を構成
する半導体物質のバンドギャップのエネルギーより大き
いエネルギーを有するものであり、通常は２００〜８０
０ｎｍの波長を有する光が適している。また、照射光は
単色光である必要は特になく、キセノンランプまたは水
銀ランプを光源とした多色光を適用することができる。In the present invention, light is irradiated while the substrate is immersed in such a solvent. As mentioned above, this light has an energy greater than the bandgap energy of the semiconductor material constituting the substrate, and usually has an energy of 200 to 80
Light with a wavelength of 0 nm is suitable. Further, the irradiation light does not need to be monochromatic light, and polychromatic light using a xenon lamp or a mercury lamp as a light source can be applied.
上記の光照射により、溶媒中の半導体特性を有する基板
は半導体物質のバンドギャップ以上の光を吸収して励起
され、伝導帯に電子を、価電子帯に正孔を生じるととも
に、これら電子および正孔は基板表面に速やかに拡散し
、そのうちの正孔は周囲の還元剤によって還元消滅する
一方、還元剤は酸化分解される。正孔が消滅した基板表
面は電子のみが存在することによってその４位が周囲に
存在する磁性金属イオンの還元電位より高くなると、こ
れら金属イオンを容易に引きつけてこれを相当する金属
に還元する。By the above light irradiation, the substrate with semiconductor properties in the solvent is excited by absorbing light that is larger than the band gap of the semiconductor material, producing electrons in the conduction band and holes in the valence band. The holes quickly diffuse to the substrate surface, and while the holes are reduced and annihilated by the surrounding reducing agent, the reducing agent is oxidized and decomposed. Since only electrons exist on the surface of the substrate where holes have disappeared, when the 4th position becomes higher than the reduction potential of the surrounding magnetic metal ions, it easily attracts these metal ions and reduces them to the corresponding metal.
上記還元剤の酸化分解および磁性金属イオンの還元反応
は、基板表面に光触媒的に形成された正孔および電子に
よっておこるものであって、その際の液温を低く設定で
きるため、光照射を１〜６０分間程度続けることにより
、基板表面に非常に均一で従来の如き前処理金属に起因
した磁気特性の劣化が全くみられない磁性金属層を形成
することができる。この磁性金属層の厚みは、用途目的
に応じて広範囲に設定できるものであるが、一般には０
．１〜５声程度とするのが望ましい。The oxidative decomposition of the reducing agent and the reduction reaction of the magnetic metal ions occur using holes and electrons photocatalytically formed on the substrate surface, and since the liquid temperature at that time can be set low, the light irradiation is reduced to 1. By continuing the treatment for about 60 minutes, it is possible to form a very uniform magnetic metal layer on the surface of the substrate, with no deterioration in magnetic properties caused by conventional pretreatment metals. The thickness of this magnetic metal layer can be set over a wide range depending on the purpose of use, but it is generally 0.
．． It is desirable to have about 1 to 5 voices.
なお、このようにして磁性金属層を形成したのち、不活
性ガス雰囲気中あるいは真空中で１００〜４００°Ｃ５
好適には２００〜３００°Ｃの温度で熱処理するように
してもよい。これにより磁性金属の結晶化が促進されて
保磁力や飽和磁化量さらには角型比の向上を図れる場合
がある。In addition, after forming the magnetic metal layer in this way, it is heated at 100 to 400°C5 in an inert gas atmosphere or in vacuum.
The heat treatment may preferably be carried out at a temperature of 200 to 300°C. This may promote the crystallization of the magnetic metal and improve the coercive force, saturation magnetization, and squareness ratio.
かくして得られるこの発明の磁気記録媒体は、半導体特
性を有する基板とこの基板表面に形成された磁性金属層
とからなるものであって、角型比や保磁力が大きく、従
来の媒体に比し磁気特性にすぐれるという特徴を有して
おり、上記基板の材質構成などに応じて磁気テープ、磁
気ディスク、磁気ドラムなどの各種形態で利用すること
ができる。The thus obtained magnetic recording medium of the present invention is composed of a substrate having semiconductor properties and a magnetic metal layer formed on the surface of this substrate, and has a large squareness ratio and coercive force, and has a large squareness ratio and a large coercive force compared to conventional media. It is characterized by excellent magnetic properties, and can be used in various forms such as magnetic tapes, magnetic disks, and magnetic drums depending on the material composition of the substrate.
以上のように、この発明においては、半導体特性を有す
る基板を用いてかつ光触媒反応を利用することにより、
気相中での薄膜形成法に比し生産性などの面で有利な液
相メッキ法によって角型比や保磁力が大きくて磁気特性
にすぐれる磁気記録媒体を製造容易に得ることができる
という格別の効果が得られるものである。As described above, in this invention, by using a substrate having semiconductor properties and utilizing a photocatalytic reaction,
The liquid-phase plating method, which is advantageous in terms of productivity compared to thin film formation methods in the gas phase, makes it possible to easily produce magnetic recording media with large squareness ratios, high coercive force, and excellent magnetic properties. This is something that gives you an exceptional effect.
以下に、この発明の実施例を記載してより具体的に説明
する。EXAMPLES Below, examples of the present invention will be described in more detail.
実施例１
塩化コバルト ２０５１’次亜リン酸ソー
ダ １５ｙクエン酸ンーダ
４（１ホ ウ 酸
２０ｇＩ水
１１上記の成分を溶解混合しこれにさら
に苛性ソーダを適量加えてＰＨを９．０に調整し、８０
°Ｃに加熱した。この液に、厚さ７０Ｐ、直径８．９側
のポリエチレンテレフタレートフィルムの表面にスパッ
タリング法により厚さ０．１ｐのＳｉの膜を形成してな
る基板を、浸漬したのち、出力ＩＫＩＩ／のキセノンラ
ンプを用いて５分間光照射した。その後、液中から上記
基板を取り出し、水洗乾燥することにより、上記基板の
Ｓｉ膜上に０．２声厚の磁性コバルト金属層が形成され
てなるこの発明に係る磁気記録媒体を得た。Example 1 Cobalt chloride 2051' Sodium hypophosphite 15y Sodium citric acid
4 (1 boric acid
20gI water
11 Dissolve and mix the above ingredients and add an appropriate amount of caustic soda to adjust the pH to 9.0.
Heated to °C. A substrate consisting of a 0.1p thick Si film formed by sputtering on the surface of a polyethylene terephthalate film with a thickness of 70p and a diameter of 8.9cm was immersed in this solution, and then a xenon lamp with an output of IKII/ was immersed. It was irradiated with light for 5 minutes. Thereafter, the substrate was taken out of the solution, washed with water, and dried to obtain a magnetic recording medium according to the present invention in which a magnetic cobalt metal layer with a thickness of 0.2 tone was formed on the Si film of the substrate.
実施例２
厚さ７０−９直径８．９ ａｍのポリエチレンテレフタ
レートフィルムの表面に有機チタネート（テトライソプ
ロピルチタネート）を塗布したのち、空気中８０ ’Ｃ
で加熱して上記チタネートを熱分解することにより、厚
さ０．０１−のＴｉＯ２の膜を形成した。これを半導体
特性を有する基板として用いた以外は、実施例１と同様
にしてこの発明に係る磁気記録媒体を作製した。Example 2 After applying organic titanate (tetraisopropyl titanate) to the surface of a polyethylene terephthalate film with a thickness of 70-9 and a diameter of 8.9 am, the film was heated at 80'C in air.
The titanate was thermally decomposed by heating to form a 0.01-thick TiO2 film. A magnetic recording medium according to the present invention was produced in the same manner as in Example 1 except that this was used as a substrate having semiconductor properties.
実施例３
厚さ０．５ ｒｍ 、直径５ｃｍの単結晶のＳｉからな
る基板を半導体特性を有する基板として用いた以外は、
実施例１と同様にしてこの発明に係る磁気記録媒体を作
製した。Example 3 Except that a substrate made of single crystal Si with a thickness of 0.5 rm and a diameter of 5 cm was used as a substrate having semiconductor properties.
A magnetic recording medium according to the present invention was produced in the same manner as in Example 1.
比較例
厚さ７ Ｑ ）ｔｙｎ 、直径８．９０のポリエチレン
テレフタレートフィルムを重クロム酸カリウムと硫酸と
の混合溶液中でエツチング処理したのち、５ｎＣＪ２溶
液中で感受性化処理し、さらにＰｄＣｌ２溶液中で活性
化処理を行った。これら前処理を施してなる上記フィル
ムを基板とし、この基板を実施例１と同様のコバルトイ
オンを含む液に浸漬し、９０°Ｃで３分間無電解メッキ
を行うことにより、上記基板上に０．２２厚の磁性コバ
ルト金属層が形成されてなる比較用の磁気記録媒体を得
た。Comparative Example A polyethylene terephthalate film with a thickness of 7 Q oxidation treatment was performed. The above film subjected to these pretreatments was used as a substrate, and this substrate was immersed in the same solution containing cobalt ions as in Example 1, and electroless plating was performed at 90°C for 3 minutes. A comparative magnetic recording medium was obtained in which a magnetic cobalt metal layer with a thickness of .22 mm was formed.
以上の実施例１〜３および比較例の各媒体につき、その
保磁力および角型比を測定した結果は、下記の表に示さ
れるとおりであった。The coercive force and squareness ratio of each of the media of Examples 1 to 3 and Comparative Example were measured, and the results were as shown in the table below.
上表から明らかなように、この発明の磁気記録媒体は、
気相中での薄膜形成法に比し生産性などの面で有利な液
相メッキ法で得ることができるうえに、従来の液相メッ
キ法に係る比較例のものに比し保磁力や角型比が大きく
磁気特性によりすぐれたものであることが判る。As is clear from the above table, the magnetic recording medium of the present invention has
It can be obtained by liquid phase plating, which is more advantageous in terms of productivity than thin film formation in the gas phase, and also has lower coercive force and angle than comparative examples of conventional liquid phase plating. It can be seen that the type ratio is large and the magnetic properties are excellent.
Claims (6)
れた磁性金属層とからなることを特徴とする磁気記録媒
体。(1) A magnetic recording medium comprising a substrate having semiconductor properties and a magnetic metal layer formed on the surface of the substrate.
体物質の膜を形成してなるものからなる特許請求の範囲
第（１）項記載の磁気記録媒体。(2) A magnetic recording medium according to claim (1), wherein the substrate having semiconductor properties is formed by forming a film of a semiconductor material on an insulating film.
許請求の範囲第（２）項記載の磁気記録媒体。(3) The magnetic recording medium according to claim (2), wherein the insulating film is a plastic film.
るものである特許請求の範囲第（１）項記載の磁気記録
媒体。(4) The magnetic recording medium according to claim (1), wherein the substrate having semiconductor properties is made solely of a semiconductor material.
ら選ばれた少なくとも一種の金属からなる特許請求の範
囲第（１）〜（４）項のいずれかに記載の磁気記録媒体
。(5) The magnetic recording medium according to any one of claims (1) to (4), wherein the magnetic metal layer is made of at least one metal selected from iron, cobalt, and nickel.
体特性を有する基板を浸し、上記基板を構成する半導体
物質のバンドギャップのエネルギーより大きなエネルギ
ーを有する光を照射することにより、上記基板の表面に
磁性金属イオンを還元析出させて磁性金属層を形成する
ことを特徴とする磁気記録媒体の製造方法。(6) A substrate having semiconductor properties is immersed in a solvent containing magnetic metal ions and a reducing agent, and the surface of the substrate is irradiated with light having an energy greater than the energy of the band gap of the semiconductor material constituting the substrate. A method for manufacturing a magnetic recording medium, comprising forming a magnetic metal layer by reducing and precipitating magnetic metal ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30512586A JPS63157314A (en) | 1986-12-20 | 1986-12-20 | Magnetic recording medium and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30512586A JPS63157314A (en) | 1986-12-20 | 1986-12-20 | Magnetic recording medium and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63157314A true JPS63157314A (en) | 1988-06-30 |
Family
ID=17941396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30512586A Pending JPS63157314A (en) | 1986-12-20 | 1986-12-20 | Magnetic recording medium and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63157314A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314725A (en) * | 1992-02-17 | 1994-05-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photo-plating process |
| US5424252A (en) * | 1991-10-04 | 1995-06-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photo-plating solution and process |
-
1986
- 1986-12-20 JP JP30512586A patent/JPS63157314A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5424252A (en) * | 1991-10-04 | 1995-06-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photo-plating solution and process |
| US5314725A (en) * | 1992-02-17 | 1994-05-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photo-plating process |
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