JPS63184307A - Stabilization of ferromagnetic metal powder - Google Patents
Stabilization of ferromagnetic metal powderInfo
- Publication number
- JPS63184307A JPS63184307A JP62198253A JP19825387A JPS63184307A JP S63184307 A JPS63184307 A JP S63184307A JP 62198253 A JP62198253 A JP 62198253A JP 19825387 A JP19825387 A JP 19825387A JP S63184307 A JPS63184307 A JP S63184307A
- Authority
- JP
- Japan
- Prior art keywords
- metal powder
- metal
- ferromagnetic metal
- compound
- ferromagnetic
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 115
- 239000002184 metal Substances 0.000 title claims abstract description 115
- 239000000843 powder Substances 0.000 title claims abstract description 82
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 65
- 230000006641 stabilisation Effects 0.000 title 1
- 238000011105 stabilization Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000013522 chelant Substances 0.000 claims abstract description 12
- -1 alkoxide compound Chemical class 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 45
- 238000000151 deposition Methods 0.000 abstract description 17
- 239000002904 solvent Substances 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002736 metal compounds Chemical class 0.000 abstract description 8
- 239000002923 metal particle Substances 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000005291 magnetic effect Effects 0.000 description 26
- 230000006866 deterioration Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 150000004703 alkoxides Chemical class 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 10
- 230000005415 magnetization Effects 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910001872 inorganic gas Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/061—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder with a protective layer
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、高密度記録に適した磁気記録媒体に於ける磁
性素材としての強磁性金属粉微粒子の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing fine ferromagnetic metal powder particles as a magnetic material in a magnetic recording medium suitable for high-density recording.
狐米茨±
磁気記録用磁性素材については、広い記録波長域での高
出力・低ノイズを計る為に、均一性の高い微細形状粒子
で、高い保磁力（Ｈｃ）を有し、飽和磁化（σＳ）・残
留磁化（σｒ）共に大きく、かつ角形比（Ｒｓ＝σｒ／
σＳ）も可及的に大きい磁気特性が基本的に要求される
。このうち、磁性素材としての磁性粉については、強磁
性金属粉が、その優れた磁気特性から、まずオーディオ
用磁気テープの素材として実用化され、又、８ｍｍビデ
オ用素材として実用化されている。鉄を主要成分とした
針状性金属粉微粒子の場合、Ｈｅ値及びσＳ値の充分な
高さに基づく優れた磁気的ポテンシャリティが利用され
ている事となる訳であるが、通常は１μｍ以下の微粒子
である事から、空気に対する酸化活性が極めて強く、磁
気記録媒体としての適用性を確保し、かつ信転性を付与
せしめる為の安定性が重要な物性として位置づけられて
いる。従来この種の安定性を確保する手段として、
（１）微粒子表層部に酸化層を設ける方法、（２）微粒
子表面に特殊な保護層を被膜形成させる方法、
（３）微粒子表層部に酸化層を設けた後加熱処理を加え
ることにより酸化被膜層の緻密化をはかる方法等が公知
である。Kitsunebeibara ± Magnetic materials for magnetic recording are made of highly uniform fine particles, have high coercive force (Hc), and have saturation magnetization ( Both σS) and residual magnetization (σr) are large, and the squareness ratio (Rs=σr/
σS) is also basically required to have as large a magnetic property as possible. Among these, regarding magnetic powder as a magnetic material, ferromagnetic metal powder was first put to practical use as a material for audio magnetic tapes due to its excellent magnetic properties, and was also put into practical use as a material for 8 mm videos. In the case of acicular metal powder particles whose main component is iron, excellent magnetic potential based on sufficiently high He value and σS value is utilized, but usually magnetic particles with a diameter of 1 μm or less are utilized. Since they are fine particles, they have extremely strong oxidizing activity against air, and stability is considered an important physical property to ensure applicability as a magnetic recording medium and to provide reliability. Conventionally, methods for ensuring this kind of stability include (1) a method of forming an oxide layer on the surface layer of the fine particles, (2) a method of forming a special protective layer on the surface of the fine particles, and (3) a method of forming an oxide layer on the surface layer of the fine particles. A method of densifying the oxide film layer by applying heat treatment after providing the oxide film is known.
（１）に属する方法としては、酸化層を気相接触反応で
行なう方法、及び液相反応で行なう方法等があり、例え
ば特開昭５５−１２５２０５．５６−６９３０１．５６
−１２７７０ｆ 、 ５２−８５０５４ 、５５−１６
４００１ 、５７−８５９０１ 、５７−９３５０４
、５８−１１０４３３．５８−１５９３１１等が挙げら
れる。Methods belonging to (1) include a method in which the oxidation layer is formed by a gas phase contact reaction and a method in which the oxidation layer is formed by a liquid phase reaction.
-12770f, 52-85054, 55-16
4001, 57-85901, 57-93504
, 58-110433.58-159311, etc.
更に（２）に属する方法としては、有機物の保護層を被
着する方法としてシリコーンに代表される特殊な界面活
性剤的性格の強い低分子量有機物を被着する方法、例え
ば特開昭４６−５０５７．５０−１０４１６４．５１−
１２２６５５ 、５１−１４０８６０ 、５２−１５５
３９８ 、５３−５７９８ 、５３−７６９５８、５４
−２４０００ 、５５−３９６６０ 、５５−３９６６
１ 、５５−３９６６２ 、５６−２９８４１．５６−
５４０１３．５６−１４８７２６等が挙げられる。Furthermore, as a method belonging to (2), a method of depositing a protective layer of an organic material is a method of depositing a low molecular weight organic material with strong surfactant properties, typified by silicone, such as JP-A-46-5057. .50-104164.51-
122655, 51-140860, 52-155
398, 53-5798, 53-76958, 54
-24000, 55-39660, 55-3966
1, 55-39662, 56-29841.56-
54013.56-148726 and the like.
また更に樹脂類の保護層を被着する方法として、特開昭
５３４３９０６．５３−７８０９９．５４−１３９５０
８．５６−１３０８３１等がある。また無機塩を被着す
る方法として、特開昭５３−８７９８．５６−９８４０
１．５７−９８０２．５７−６３６０１．５８−１５９
３０６、５８−１５９３０７ 、５８−１５９３０８
、５８−１６１７０８ 、５８−１６１７０９ 。Furthermore, as a method of applying a protective layer of resin, Japanese Patent Application Laid-Open No. 5343906.53-78099.54-13950
8.56-130831 etc. In addition, as a method of depositing inorganic salt, Japanese Patent Application Laid-Open No. 53-8798.56-9840
1.57-9802.57-63601.58-159
306, 58-159307, 58-159308
, 58-161708, 58-161709.
５８−１６１７２５等が挙げられる。58-161725 and the like.
また気化性防錆剤を保護層形成の為に使用する方法とし
て、特公昭６０−４５６５に記載の方法が挙げられ、ま
たアミン、鉱物油を保護層の形成に使用する方法として
、特開昭５３−７８０９６．５３−７８０９や本発明者
等が提案した、特願昭６０−２９２８７５等が挙げられ
る。In addition, as a method of using a volatile rust preventive agent to form a protective layer, there is a method described in Japanese Patent Publication No. 4565/1983, and as a method of using an amine or mineral oil to form a protective layer, there is a method described in 53-7809 and Japanese Patent Application No. 60-292875 proposed by the present inventors.
さらに無機ガスを利用する方法として本発明者等が提案
した、特願昭６０−２９２８７等が挙げられる。Further, as a method of utilizing an inorganic gas, there is a method proposed by the present inventors, such as Japanese Patent Application No. 60-29287.
（３）に属する方法としては本発明者等が提案した特願
昭５９−２７３７１１に記載の方法が挙げられる。Examples of methods belonging to (3) include the method proposed by the present inventors and described in Japanese Patent Application No. 59-273711.
本発明が解決しようとする問題点
強磁性金属粉微粒子の表面に、前記の方法により安定性
に付与することが行なわれてきたわけであるが、（１）
の方法として挙げられる、強磁性金属粉微粒子表層部に
金属粉自身の酸化物を設ける方法では、酸化物層を持た
ない金属粉に比較して安定性は高いが、これだけでは充
分な酸化防止効果を持つことが出来なかった。又（２）
の方法例えばシリコーンに代表される特殊な低分子量の
界面活性剤等を被着する方法は、劣化の原因となる酸素
及び水分を有機層により遮断する事を特徴とするもので
あり、強磁性金属微粒子の劣化を防止する効果は、上記
の酸化被膜だけに比較して著しく向上するし、又同様な
一例として樹脂等を被着する方法が挙げられる。しかし
ながら、低分子量の界面活性剤及び樹脂等は、酸素及び
水藤気の分子に比較して大きい為に、比較的多量に使用
する必要性があった。又、磁気記録媒体として使用する
場合、強磁性金属粉末は、常にバインダー樹脂と混合し
て使用する。この場合、上記の方法同様にバインダー樹
脂に強磁性金属粉末が覆われる訳であり、この様な有機
物及び樹脂処理の効果は低減して仕舞うのである。Problems to be Solved by the Invention The above method has been used to impart stability to the surface of ferromagnetic metal powder particles, but (1)
The method of providing the metal powder's own oxide on the surface layer of the ferromagnetic metal powder fine particles is more stable than metal powder without an oxide layer, but this method alone is not sufficient to prevent oxidation. I couldn't have it. Also (2)
For example, the method of depositing a special low-molecular-weight surfactant such as silicone is characterized by blocking oxygen and moisture, which cause deterioration, with an organic layer. The effect of preventing the deterioration of fine particles is significantly improved compared to the above-mentioned oxide film alone, and a similar example is a method of applying a resin or the like. However, since low molecular weight surfactants, resins, etc. are larger than the molecules of oxygen and hydrogen gas, it is necessary to use them in relatively large amounts. Furthermore, when used as a magnetic recording medium, ferromagnetic metal powder is always mixed with a binder resin. In this case, as in the above method, the ferromagnetic metal powder is covered with the binder resin, and the effects of such organic substance and resin treatment are reduced.
また無機塩を被着する方法として、金属石鹸及び金属ア
ルコキシド及び金属水酸化物を被着する方法等が挙げら
れるが、この場合は、その分子量が前記の有機物のそれ
より小さいため、酸素、水蒸気等の劣化原因となる分子
を比較的透過せしめ難いのではあるが、強磁性金属微粒
子との結合力が弱い為に安定性を向上する効果はやはり
低いものでしかない。In addition, methods for depositing inorganic salts include methods for depositing metal soaps, metal alkoxides, and metal hydroxides. Although it is relatively difficult for molecules that cause deterioration to pass through, the effect of improving stability is still low because the bonding force with the ferromagnetic metal fine particles is weak.
また特開昭５８−１２０７０４記載の方法として、強磁
性金属粉末に対して不活性で且つ金属アルコキシドを溶
解し、得られた溶液を用いて強磁性金属粉末を湿潤し１
１次いで該金属粉末の表面またはその附近に存在する金
属アルコキシドを徐々に加水分解することにより、該金
属アルコキシドの完全または不完全加水分解物の被膜を
該金属粉末の表面に形成し、次いで溶媒を基数またはろ
別する強磁性金属粉末の安定化方法が提案されている。Furthermore, as a method described in JP-A-58-120704, a metal alkoxide which is inert to ferromagnetic metal powder is dissolved and the obtained solution is used to wet the ferromagnetic metal powder.
1. Next, by gradually hydrolyzing the metal alkoxide present on or near the surface of the metal powder, a film of complete or incomplete hydrolysis of the metal alkoxide is formed on the surface of the metal powder, and then the solvent is removed. Methods for stabilizing ferromagnetic metal powders by radix or filtration have been proposed.
この方法においては、強磁性金属粉末表面に金属水和物
の被膜が形成されるわけであるが、かかる方法では、後
記比較例３に示すように、金属水和物の被膜が強磁性粉
末との結合力を持たない為に安定性を向上する効果は少
なかった。また、強磁性金属の表面にＡＩ”、Ｔｉ”、
Ｚｎ”等の水酸化物を有機極性溶媒に溶解し被着する
方法も特開昭６１−４０００５に提案されているように
公知である。この方法は、金属水酸化物を有機極性溶媒
に溶解し、極性溶媒を蒸発して該金属水酸化物を析出せ
しめ被着するのであるが、かかる方法では、有機極性溶
媒蒸発後析出残留したこれら金属の水酸化物と強磁性金
属とは、もともと強い結合力を持たない為に、酸化安定
性を向上する被膜としての効果は少なかった。In this method, a metal hydrate film is formed on the surface of the ferromagnetic metal powder. Since it does not have the binding force of , the effect of improving stability was small. In addition, on the surface of ferromagnetic metal, AI", Ti",
A method of dissolving a hydroxide such as Zn'' in an organic polar solvent and depositing it is also known, as proposed in Japanese Patent Laid-Open No. 61-40005. Then, the polar solvent is evaporated to precipitate and deposit the metal hydroxide, but in this method, the ferromagnetic metal and the metal hydroxide that precipitate and remain after evaporation of the organic polar solvent are originally strong. Since it did not have binding strength, it had little effect as a coating for improving oxidation stability.
また気化性防錆剤を使用する方法は、前記の有機物の利
用と同様に基本的な安定性向上とはならない。またアミ
ン、鉱物油を使用する方法に於いても前記の有機物の利
用と同様に基本的な安定性向上とはならない。また無機
ガスを利用する方法として５（ｌｚは結合力は強いので
あるが、水蒸気による酸化に対する安定性付与に難点が
あり、ＣＯ□は、酸化速度を低下せしめる効果はあるが
、結合力か弱い為に酸素及び水蒸気と置換してやはり安
定性に難点があった。Furthermore, the method of using a volatile rust preventive agent does not fundamentally improve stability, similar to the use of organic substances described above. Also, in the method of using amine or mineral oil, the basic stability cannot be improved like the above-mentioned use of organic substances. In addition, as a method of using inorganic gas, 5(lz has a strong bonding force, but it has a difficulty in imparting stability against oxidation by water vapor, and CO□ has the effect of reducing the oxidation rate, but has a weak bonding force. However, there were still problems with stability when replacing with oxygen and water vapor.
（３）の方法として微粒子表層部に酸化層を設けた後加
熱処理を加えて酸化被膜層の緻密化をはかる方法は、微
粒子表層部が緻密な酸化被膜となる為に有効な手段であ
るが、強磁性金属の酸化物膜はこれを緻密化したとして
もそれ自身だけではまだ完全に酸素及び水蒸気による腐
食を防止することは出来なかった。As method (3), the method of forming an oxide layer on the surface layer of the fine particles and then applying heat treatment to make the oxide layer denser is an effective method for forming a dense oxide layer on the surface layer of the fine particles. Even if the ferromagnetic metal oxide film was made denser, it was still not able to completely prevent corrosion by oxygen and water vapor by itself.
なお、その他、還元前にＡＩ化合物を被着し強磁性金属
粉末を製造する、特公昭５６−２８９６７記載の方法が
知られている。この場合は、還元工程以前に被着する為
に、水素等の還元性ガスにより金属表面に被膜としての
ＡＩ化合物は、必然的に実質上均一には存在出来ず、安
定性を向上する効果は劣っていた。In addition, a method described in Japanese Patent Publication No. 56-28967 is known in which a ferromagnetic metal powder is produced by depositing an AI compound before reduction. In this case, since the AI compound is deposited before the reduction process, the AI compound formed as a film on the metal surface by reducing gas such as hydrogen cannot exist substantially uniformly, and the effect of improving stability is not effective. It was inferior.
問題点を”する為の手段
本発明者等は上記の問題点の解決を図る為に、鋭意検討
を加えた結果、強磁性金属粉末の粒子表面に有機金属化
合物を被着し、その後不活性ガス雰囲気下で又は水素若
しくは水素を主体とする還元性ガス雰囲気下で熱処理す
ることにより極めて安定性の高い強磁性金属粉末が得ら
れることを見い出し本発明に到達した。Means to Solve the Problems In order to solve the above problems, the inventors of the present invention have made extensive studies and have found that an organic metal compound is coated on the particle surface of ferromagnetic metal powder, and then an inert The present invention has been achieved by discovering that extremely stable ferromagnetic metal powder can be obtained by heat treatment in a gas atmosphere or in an atmosphere of hydrogen or a reducing gas mainly composed of hydrogen.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に於いて使用する有機金属化合物とは、熱分解に
より酸化安定性の高い金属酸化物を形成しうる金属を有
することが好ましく、かがる金属としてはＡｌ、Ｓｔ、
Ｂ、Ｔｉ、Ｚｎ及びＺｒが特に好ましいものとして挙げ
られる。加えて、例えばトルエン。The organometallic compound used in the present invention preferably has a metal that can form a metal oxide with high oxidation stability by thermal decomposition, and examples of the metal include Al, St,
Particularly preferred are B, Ti, Zn and Zr. In addition, for example toluene.
ヘプタン等の如く、強磁性金属粒子と結合しにくい一般
的な有機溶媒に簡単に溶解する化合物、例えば、金属ア
ルコキシド化合物、金属キレート化合物が特に好ましい
。Particularly preferred are compounds such as heptane that are easily dissolved in common organic solvents that are difficult to bond with ferromagnetic metal particles, such as metal alkoxide compounds and metal chelate compounds.
このような金属アルコキシド化合物として、八ｌ （Ｏ
Ｃ２Ｈ５） ３、ＡＩ（ｉｓｏ−ＯＣＪ、）ｘ、ＡＩ
（ｓｅｃ−ＯＣ４Ｈｑ） ３、Ｓｉ （ＯＣＨｉ） ａ
、Ｓｉ （ＯＣｚＨｓ） ａ、Ｓｉ （ｉｓｏ−ＱＣ
：＋Ｔｏ） ａ、Ｓｉ （ｓｅｃ−ＯＣＪｑ） ４、Ｂ
（ＯＣＨ３）＋、Ｂ（ＯＣ２Ｈ５）３、Ｂ（ｉｓｏ−Ｏ
ＣｚＨｗ） ３、Ｂ（ｓｅｅ−ＯＣＪ、）３、Ｔｉ （
ＯＣＨ３） ａ、Ｔｉ （ＯＣｚＨｓ） ４、Ｔｉ（ｉ
ｓｏ−ＯＣＪｔ） ｓ、Ｔｉ （ｓｅｃ−ＯＣＪ、）ａ
、Ｚｎ（ＯＣＨ３）ｓ 、ＺｎＣ０ＣｚＨｓ）ｓ、Ｚｎ
（ｊｓｏ−ＱＣ：＋）ＩＪ ｓ、Ｚｎ （ｓｅｅ−ＯＣ
４Ｈｑ） ３、Ｚｒ（ＯＣＨｓ＞ａ 、Ｚｒ（ＯＣＪｓ
）ｎ、Ｚｒ（ｉｓｏ−ＱＣ３）１．） ａ、Ｚｒ（ｓｅ
ｃ−ＯＣ４Ｈｑ） ４等が挙げられ、又金属キレート化
合物としてはＡＩ （Ｃ５１１７０２） ３、Ｔｉ（Ｃ
ｓＨＪ□）ｚ（ＱＣ：＋Ｈｙ）ｚ 、 Ｚｎ（Ｃ５Ｈ
１ｏｚ）ｚ 、Ｚｒ （ＣｓＬＯｚ） ４等が挙げら
れる。なお、Ａｌ（Ｃ）Ｉ３）ａ、ＡＩ＜ＣｚＨｓ＞ｓ
、ＡＩ（ｉｓｏ−ＣＪ、）ｔ 、ＡＩ（ｓｅｃ−ＣＪ
、）３等のアルキル金属化合物も使用可能である。また
、キレート化合物としては、特に、アルミニウムのキレ
ート化合物、例えば、エチルアセトアセテートアルミニ
ウムジイソプロピレート、アルミニウムトリス（エチル
アセトアセテート）、アルミニウムトリス（アセチルア
セトネート）等が好ましい。As such a metal alkoxide compound, 8l (O
C2H5) 3, AI (iso-OCJ,) x, AI
(sec-OC4Hq) 3, Si (OCHi) a
, Si (OCzHs) a, Si (iso-QC
:+To) a, Si (sec-OCJq) 4, B
(OCH3)+, B(OC2H5)3, B(iso-O
CzHw) 3, B(see-OCJ,)3, Ti (
OCH3) a, Ti (OCzHs) 4, Ti(i
so-OCJt) s, Ti (sec-OCJ,)a
, Zn(OCH3)s, ZnC0CzHs)s, Zn
(jso-QC:+)IJ s, Zn (see-OC
4Hq) 3, Zr(OCHs>a, Zr(OCJs
) n, Zr (iso-QC3)1. ) a, Zr(se
c-OC4Hq) 4, etc., and metal chelate compounds include AI (C511702) 3, Ti(C
sHJ□)z(QC:+Hy)z, Zn(C5H
1oz)z, Zr(CsLOz)4, etc. In addition, Al(C)I3)a, AI<CzHs>s
, AI(iso-CJ,) t , AI(sec-CJ
, ) 3, etc. can also be used. As the chelate compound, particularly preferred are aluminum chelate compounds, such as ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and the like.
このような有機金属化合物は、勿論単独でも充分効果を
発揮するが、所望により、これらは二種以上混合し使用
することを何ら妨げるものではない。Of course, such organometallic compounds exhibit sufficient effects even when used alone, but there is nothing to prevent them from being used in combination of two or more types, if desired.
本発明においては、まず、強磁性金属粒子表面に上記の
ごとき有機金属化合物を被着した後、特定の条件で熱処
理するが、この被着の方法としては種々の方法を採用し
うる。もっとも容易な方法は、該有機金属化合物をその
溶媒に溶解し、該溶液に金属粒子を浸漬し、好ましくは
溶媒を除去し、粒子に該有機金属化合物を被着させる方
法である。いずれにせよ、この際、次の熱処理工程での
取扱を容易にするためにも、濾過及び／または風乾等の
手段で溶媒を除去し乾燥しておくことが好ましい。In the present invention, first, the organometallic compound as described above is deposited on the surface of the ferromagnetic metal particles, and then heat-treated under specific conditions, and various methods can be employed for this deposition. The easiest method is to dissolve the organometallic compound in its solvent, immerse metal particles in the solution, preferably remove the solvent, and deposit the organometallic compound on the particles. In any case, in order to facilitate handling in the next heat treatment step, it is preferable to remove the solvent and dry by means such as filtration and/or air drying.
例えば具体的には、上記した金属アルコキシド化合物や
金属キレート化合物を、下記のごときトルエン、ヘプタ
ン等の溶媒に溶解し、これに該金属粒子を浸漬し、浸漬
の効果を確実ならしめるため、１０Ｍ１ｎ〜２４Ｈｒ程
度の適当な時間放置後、所望により、濾過して風乾する
か、望ましくは、該適当な時間放置後、さらにニーグー
等を使用して１０Ｍ１ｎ〜１ＯＨｒ程度の時間充分混練
し、風乾処理するのである。For example, specifically, the above-described metal alkoxide compound or metal chelate compound is dissolved in a solvent such as toluene or heptane as shown below, and the metal particles are immersed in this to ensure the effect of the immersion. After leaving for an appropriate time of about 24 hours, if desired, filter and air dry, or desirably, after leaving for an appropriate time, knead thoroughly for a time of about 10M1n to 1OHr using a Ni-gu, etc., and then air dry. be.
ここで使用しうる溶媒としては、例えば、ベンゼン、ト
ルエン、キシレンのごとき芳香族炭化水素類；ヘキサン
、ヘプタン、オクタン、ノナン、デカン、ウンデカンの
ごとき脂肪族炭化水素類；アセトン、ＭＥＫ 、 ＭＩ
ＢＫのごときケトン類；エタノール、イソプロパツール
のごときアルコール類；酢酸エチル、酢酸ブチルのごと
きエステル類等が好ましいものとして挙げられる。Examples of solvents that can be used here include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, and undecane; acetone, MEK, MI
Preferred examples include ketones such as BK; alcohols such as ethanol and isopropanol; and esters such as ethyl acetate and butyl acetate.
なお、これら金属（Ｍ）の被着量は、Ｍ／Ｆｅ＝０．０
５χ〜２０χ、好ましくは０．１χ〜１０χ（れχ）で
ある。The amount of these metals (M) deposited is M/Fe=0.0
It is 5χ to 20χ, preferably 0.1χ to 10χ (reχ).
引き続いて、熱処理を行うが、該熱処理方法としては、
本発明者等が提案した特願昭５９−１７３７１１の方法
で窒素、ヘリウム、アルゴン、メタン等鉄に対して不活
性な不活性ガス雰囲気下で熱処理を加える方法で行なう
ことが好ましい。また水素又は水素を主体とした還元性
ガス（水素と上記不活性ガスの混合ガス）雰囲気下で熱
処理を加えるのも好ましい実施の態様である。熱処理の
温度範囲しては、２００℃〜７００℃が好ましい。７０
０℃を越える温度でも安定性を向上する効果は発揮出来
るが粒子間の焼結が進行し、磁気記録用として好適に利
用出来る強磁性金属粉末とはならない。また、２００℃
未満の温度では有機金属化合物の熱分解が実質的に進行
しないためか、本発明の目的、特に長期間の安定性確保
と云う目的を達することが出来ない。処理時間は温度に
よって変わりうるが、３０分〜１０時間程度である。Subsequently, heat treatment is performed, and the heat treatment method is as follows:
It is preferable to carry out heat treatment in an atmosphere of an inert gas inert to iron, such as nitrogen, helium, argon, or methane, as proposed by the present inventors in Japanese Patent Application No. 59-173711. It is also a preferred embodiment to perform heat treatment in an atmosphere of hydrogen or a reducing gas mainly composed of hydrogen (a mixed gas of hydrogen and the above-mentioned inert gas). The temperature range for the heat treatment is preferably 200°C to 700°C. 70
Although the effect of improving stability can be exhibited even at temperatures exceeding 0° C., sintering between particles progresses, and the result is not a ferromagnetic metal powder that can be suitably used for magnetic recording. Also, 200℃
At a temperature lower than that, the purpose of the present invention, particularly the purpose of ensuring long-term stability, cannot be achieved, probably because the thermal decomposition of the organometallic compound does not substantially proceed. The treatment time may vary depending on the temperature, but is approximately 30 minutes to 10 hours.
なお、本発明に利用出来る強磁性金属粉末としては、従
来公知のいかなる方法で作成された強磁性金属粉末でも
良く、さらに云えば、当業者が容易に入手することがで
きる、既に表面に酸化被膜を形成したものであっても良
いことは勿論である。The ferromagnetic metal powder that can be used in the present invention may be any ferromagnetic metal powder prepared by any conventionally known method.Moreover, it may be a ferromagnetic metal powder that has already been coated with an oxide film on the surface, which is easily available to those skilled in the art. Of course, it is also possible to form a .
かかる金属粉末としては、長軸の平均粒径２〜０．０５
μｍ好ましくは１〜０．１ μｍ程度、長軸／短軸比５
〜２０好ましくは１０〜１０程度のものが好ましい。Such metal powder has an average particle diameter of 2 to 0.05 along the major axis.
μm preferably about 1 to 0.1 μm, long axis/short axis ratio 5
-20, preferably about 10-10.
溌泗！は口旧処果
本発明の作用効果につき詳細に説明する。本発明は、強
磁性金属粒子表面にＡ１．Ｓｉ、Ｂ、Ｔｉ、Ｚｎ及びＺ
ｒの有機金属化合物特に金属アルコキシド化合物又は金
属キレート化合物を被着処理し、その後不活性ガス雰囲
気下で又は水素ガス若しくは水素ガスを主体とする還元
性ガス雰囲気下で加熱処理するものであるが、金属アル
コキシド化合物又は金属キレート化合物を使用した場合
は、強磁性粒子に被着後加熱することにより、熱分解し
容易に金属酸化物を形成する為に、強磁性粒子表面に安
定性が高く、かつ緻密な酸化物層が形成される。この安
定性の高い金属の酸化物層が強磁性金属粒子の酸化に対
する安定性を著しく向上せしめる効果を奏するのである
。Vibrant! Hereinafter, the effects of the present invention will be explained in detail. In the present invention, A1. Si, B, Ti, Zn and Z
The organic metal compound of r, especially a metal alkoxide compound or a metal chelate compound, is deposited and then heat treated in an inert gas atmosphere or in an atmosphere of hydrogen gas or a reducing gas mainly composed of hydrogen gas, When a metal alkoxide compound or a metal chelate compound is used, it thermally decomposes easily to form a metal oxide when heated after being deposited on the ferromagnetic particles, so it has high stability on the surface of the ferromagnetic particles, and A dense oxide layer is formed. This highly stable metal oxide layer has the effect of significantly improving the stability of the ferromagnetic metal particles against oxidation.
災施炭
以下実施例比較例により更に詳細に本発明の方法及び効
果を説明する。EXAMPLES The method and effects of the present invention will be explained in more detail with reference to Examples and Comparative Examples below.
実施例１
一次粒子の長袖の平均粒径０．１５μｍ軸比１０の鉄を
主体とした強磁性金属粉末を１００ｇ用意した。振動試
料型磁力計（ＶＳＭ）により外部磁場１０ｋＯｅ Ｔ：
磁気特性を測定したところ、Ｈｃ＝１３８００ｅ、
σｓ＝１６８ｅｍｕ／ｇ、 Ｒｓ＝０．４９３であった
。ＡＩ（ｉｓｏ−ＯＣＪ７）３２２．７ｇをトルエン１
５０ｇに溶解し、該金属粉末を上記の溶媒に浸漬し一晩
放置した（ＡＩ／Ｆｅ＝３／１００ Ｗｔ比）。Example 1 100 g of a ferromagnetic metal powder mainly composed of iron having a long-sleeved primary particle average particle size of 0.15 μm and an axial ratio of 10 was prepared. External magnetic field of 10 kOe T:
When the magnetic properties were measured, Hc=13800e,
σs=168emu/g, Rs=0.493. 322.7 g of AI (iso-OCJ7) to 1 toluene
The metal powder was immersed in the above solvent and left overnight (AI/Fe=3/100 Wt ratio).
ニーダ−により４時間混練を行い空気中で風乾処理した
。磁気特性を測定したところＨｃ＝１４９５ ０ｅ、
σｓ＝１３２ｅｍｕ／ｇ、 Ｒｓ＝０．５０２であっ
た。該被着した処理金属粉末を特願昭５９−２７３７１
１記載の方法に従って窒素ガス雰囲気下で、４００℃で
２時間熱処理を加え、該熱処理金属粉末の磁気特性を測
定したところ、Ｈｃ＝１５５００ｅ、 σｓ ＝１３
０ｅｍｕ／ｇ＋Ｒｓ＝０．５０３であった。該熱処理金
属粉末をトルエンに浸漬し更に風乾を行った。その後、
該処理金属粉末を、５０℃１８０χＲＨの恒温恒湿器に
放置して、劣化試験を行った。６０時間経過後、該処理
金属粉末を恒温恒温器から取り出し磁気特性を測定した
ところ、飽和磁化（σＳ）は、１１２ｅｍｕ／ｇであっ
た。また−週間経過後、該処理金属粉末の飽和磁化（σ
Ｓ）を測定したところ同様に１１２ｅｍｕ／ｇであった
。この結果、磁気記録用金属磁性粉末として充分な安定
性を持つ事がわかった。The mixture was kneaded for 4 hours using a kneader and air-dried in the air. When the magnetic properties were measured, Hc = 1495 0e,
σs=132emu/g, Rs=0.502. The deposited treated metal powder is used in patent application No. 59-27371
Heat treatment was performed at 400°C for 2 hours in a nitrogen gas atmosphere according to the method described in 1, and the magnetic properties of the heat-treated metal powder were measured, Hc = 15500e, σs = 13
0 emu/g+Rs=0.503. The heat-treated metal powder was immersed in toluene and then air-dried. after that,
The treated metal powder was left in a constant temperature and humidity chamber at 50°C and 180χRH to conduct a deterioration test. After 60 hours had elapsed, the treated metal powder was taken out of the thermostatic chamber and its magnetic properties were measured, and the saturation magnetization (σS) was found to be 112 emu/g. After another week, the saturation magnetization (σ
S) was similarly measured and found to be 112 emu/g. As a result, it was found that the powder had sufficient stability as a metal magnetic powder for magnetic recording.
実施例２ 実施例１と同様の強磁性金属粉末を使用した。Example 2 The same ferromagnetic metal powder as in Example 1 was used.
ＡＩ（ｉｓｏ−ＯＣ３Ｈｔ） ３をトルエン中に溶解し
、強磁性金属粉末に被着処理する迄は実施例１と同様の
方法で行なった。The same method as in Example 1 was followed until AI (iso-OC3Ht) 3 was dissolved in toluene and coated on the ferromagnetic metal powder.
該処理金属粉末を水素雰囲気下で４００℃１２時間熱処
理を加えた。該処理金属粉末の磁気特性を測定したとこ
ろＨｃ＝１３８００ｅ、 σｓ＝１５８ｅｍｕ／ｇ、
Ｒｓ＝０．４９５であった。該処理金属粉末をトル
エンに浸漬後風乾して粉体として空気中に取り出した。The treated metal powder was heat treated at 400° C. for 12 hours in a hydrogen atmosphere. When the magnetic properties of the treated metal powder were measured, Hc=13800e, σs=158emu/g,
Rs=0.495. The treated metal powder was immersed in toluene, air-dried, and taken out into the air as a powder.
該金属粉末の磁気特性を測定したところＨｃ・１４６０
０ｅ、 ａ ｓ＝１３８ｅｍｕ／ｇ、 Ｒｓ＝０．５
００であった。実施例１と同様の方法で劣化試験を行っ
た。６０時間経過後該金属粉末のσＳ値はｌｌｌｅｍｕ
／ｇであった。また−週間経過後のσＳ値は同様にｌｌ
ｌｅｍｕ／ｇであった。この結果、水素雰囲気下での熱
処理によっても安定性を増加することがわかる。When the magnetic properties of the metal powder were measured, it was found to be Hc・1460.
0e, a s=138emu/g, Rs=0.5
It was 00. A deterioration test was conducted in the same manner as in Example 1. After 60 hours, the σS value of the metal powder is llemu
/g. Similarly, the σS value after -weeks is ll
lemu/g. As a result, it can be seen that the stability is also increased by heat treatment under a hydrogen atmosphere.
実施例３
実施例１記載の強磁性金属粉末を使用し、有機金属化合
物としてＴｉアルコキシドを使用して実施例１と同様に
して、被着処理を行った。ＴｉアルコキシドはＴｉ （
０ＣＨ（ＣＨ＋）ｚ） ａを使用し、添加量はＴｉと強
磁性金属との比で３／１００とした。被着処理後実施例
１記載の方法により熱処理を加えた。該熱処理金属粉末
の磁気特性を測定したところＨｃ＝１５５００ｅ、
σｓ＝１２９ｅｍｕ／ｇ、 Ｒｓ＝０．５０３であった
。更にトルエンに浸漬後風乾処理を行ない空気となじま
せた後、実施例１記載の方法により劣化試験を行なった
。６０時間後の飽和磁化値は、１１０ｅｍｕ／ｇであっ
た。また−週間経過後のびＳ値は１０１０９ｅ／ｇであ
った。この結果、Ｔｉのアルコキシドも安定性を増す効
果があることが分かった。Example 3 A deposition treatment was performed in the same manner as in Example 1 using the ferromagnetic metal powder described in Example 1 and using Ti alkoxide as the organometallic compound. Ti alkoxide is Ti (
0CH(CH+)z)a was used, and the amount added was 3/100 in terms of the ratio of Ti to ferromagnetic metal. After the adhesion treatment, heat treatment was applied by the method described in Example 1. When the magnetic properties of the heat-treated metal powder were measured, Hc=15500e,
σs=129emu/g, Rs=0.503. Furthermore, after being immersed in toluene and air-drying to blend with air, a deterioration test was conducted using the method described in Example 1. The saturation magnetization value after 60 hours was 110 emu/g. Moreover, the S value after lapse of -week was 10109e/g. As a result, it was found that Ti alkoxide also has the effect of increasing stability.
実施例４
実施例１記載の強磁性金属粉末を使用し、有機金属化合
物として、Ｚｒアルコキシドを使用して実施例１と同様
にして被着処理を行った。ＺｒアルコキシドとしてＺｒ
（ＯＣ３Ｈ７） ：＋を使用し、添加量はＺｒと強磁性
金属との比で３／１００とした。被着処理後実施例１記
載の方法により熱処理を加えた。該熱処理金属粉末の磁
気特性を測定したところＨｃ＝ １５５００ｅ、 ａ
ｓ＝１２８ｅｍｕ／ｇ、 Ｒｓ＝０．５０３であった
。更にトルエンに浸漬後風乾処理を行ない空気となじま
せた後、実施例１記載の方法により劣化試験を行なった
。６０時間経過後の飽和磁化値は、１０１０９ｅ／ｇで
あった。また−週間経過後のσＳ値は１０１０８ｅ／ｇ
であった。この結果Ｚｒのアルコキシドについても安定
性を増す効果があることがわかる。Example 4 A deposition treatment was carried out in the same manner as in Example 1 using the ferromagnetic metal powder described in Example 1 and using Zr alkoxide as the organometallic compound. Zr as Zr alkoxide
(OC3H7) :+ was used, and the amount added was 3/100 in terms of the ratio of Zr to ferromagnetic metal. After the adhesion treatment, heat treatment was applied by the method described in Example 1. When the magnetic properties of the heat-treated metal powder were measured, Hc = 15500e, a
s=128 emu/g, Rs=0.503. Furthermore, after being immersed in toluene and air-drying to blend with air, a deterioration test was conducted using the method described in Example 1. The saturation magnetization value after 60 hours was 10109e/g. Also, the σS value after -weeks is 10108e/g
Met. As a result, it can be seen that Zr alkoxide also has the effect of increasing stability.
実施例５
実施例１記載の強磁性金属粉末を使用し、有機金属化合
物として、ＡＩキレート化合物を使用して、実施例１と
同様にして被着処理を行なった。ＡＩキレート化合物と
してΔ１トリスエチルアセトアセテートを使用し添加量
は、ＡＩと強磁性金属との比で３／１００とした。被着
処理後実施例１記載の方法により熱処理を加えた。該熱
処理金属粉末の磁気特性を測定したところＨｃ＝１５５
５０ｅ、 ｉｒｓ＝１２９ｅｍｕ／ｇ。Example 5 A deposition treatment was carried out in the same manner as in Example 1, using the ferromagnetic metal powder described in Example 1 and using an AI chelate compound as the organometallic compound. Δ1 trisethyl acetoacetate was used as the AI chelate compound, and the amount added was 3/100 in terms of the ratio of AI to ferromagnetic metal. After the adhesion treatment, heat treatment was applied by the method described in Example 1. When the magnetic properties of the heat-treated metal powder were measured, Hc=155
50e, irs=129emu/g.
Ｒｓ＝０．５０３であった。更にトルエンに浸漬後風乾
処理を行ない空気となじませた後、実施例１記載の方法
により劣化試験を行なった。６０時間後の飽和磁化値は
、１１０ｅｍｕ／ｇであった。また−週間経過後のびＳ
値は同様に１１０ ｅｍｕ／ｇであった。この結果、Ａ
Ｉキシレート化合物についても安定性を増す効果を発揮
することが確認された。Rs=0.503. Furthermore, after being immersed in toluene and air-drying to blend with air, a deterioration test was conducted using the method described in Example 1. The saturation magnetization value after 60 hours was 110 emu/g. Again - After a week S
The value was also 110 emu/g. As a result, A
It was confirmed that the I-xylate compound also exhibits the effect of increasing stability.
実施例６ 実施例１記載の強磁性金属粉末を使用した。Example 6 The ferromagnetic metal powder described in Example 1 was used.
ＡＩ （ｉｓｏ−ＯＣＪ７） ３の量を変化した以外は
、実施例１の方法で被着処理した。窒素雰囲気下で４０
０ ’Ｃ１２時間熱処理した金属粉末の劣化試験結果を
第１図に示す。図において、○は６０時間経過後、△は
一週間経過後の値を示す。The deposition process was carried out in the same manner as in Example 1, except that the amount of AI (iso-OCJ7) 3 was varied. 40 under nitrogen atmosphere
Figure 1 shows the results of a deterioration test on metal powder heat treated for 12 hours at 0'C. In the figure, ◯ indicates the value after 60 hours, and △ indicates the value after one week.
実施例７ 実施例１記載の強磁性金属粉末を使用した。Example 7 The ferromagnetic metal powder described in Example 1 was used.
ＡＩ （ｉｓｏ−ＯＣＪ７） ３を１５．１ｇ とＴ
ｉ （０ＣＲ（ＣＨ３）２） ａ８．６ｇをトルエン１
５０ｇに溶解し、強磁性金属粉末１００ｇをこの溶液に
浸漬した。その他については、実施例１と同様の方法で
被着処理した。該被着処理金属粉末を実施例１の方法に
より熱処理を行った。該熱処理金属粉末の磁気特性を測
定したところＨｃ＝１５４００ｅ、 σｓ ＝１３０ｅ
ｍｕ／ｇ、Ｒｓ＝０．５０２であった。15.1g of AI (iso-OCJ7) 3 and T
i (0CR(CH3)2) a8.6g to toluene 1
100 g of ferromagnetic metal powder was immersed in this solution. The other parts were adhered in the same manner as in Example 1. The deposited metal powder was heat treated by the method of Example 1. When the magnetic properties of the heat-treated metal powder were measured, Hc = 15400e, σs = 130e
mu/g, Rs=0.502.
更にトルエンに浸漬後風乾処理を行った後実施例１記載
の方法により劣化試験を行った。６０時間後の飽和磁化
値は、ｌｌｌｅｍｕ／ｇであった。また−週間経過後の
σＳ値は、１１０ｅｍｕ／ｇであった。この結果、当然
のことながら、２種の金属アルコキシドの使用しても安
定性を向上する効果が奏されることが分かる。Furthermore, after being immersed in toluene and air-drying, a deterioration test was conducted using the method described in Example 1. The saturation magnetization value after 60 hours was llemu/g. Moreover, the σS value after -week had passed was 110 emu/g. As a result, it can be seen that even when two types of metal alkoxides are used, the effect of improving stability can be achieved.
実施例８
実施例１記載の強磁性金属粉末を使用した。窒素ガスに
よる熱処理温度を変化した以外は、実施例１の方法で行
った。処理後の強磁性金属粉末の劣化試験結果を第２図
に示す。図において、Ｏは６０時間後、△は一週間後の
値を示す。Example 8 The ferromagnetic metal powder described in Example 1 was used. The method of Example 1 was followed except that the heat treatment temperature with nitrogen gas was changed. Figure 2 shows the results of a deterioration test on the ferromagnetic metal powder after treatment. In the figure, O indicates the value after 60 hours, and Δ indicates the value after one week.
比較例１
実施例１記載の強磁性金属粉末をトルエンに浸漬し風乾
を行い強磁性金属粉末とした。該金属粉末の磁気特性を
測定した結果、Ｈｃ＝１５０００ｅ、 σｓ２１３１
ｅｍｕ／ｇ、 Ｒｓ＝０．５０２であった。実施例１と
同様の方法で劣化試験を行った。６０時間経過後のσＳ
値は９５ｅｍｕ／ｇであり、また−週間経過後のσＳ値
は９０ｅｍｕ／ｇであった。実施例に記載の方法によっ
て得られた強磁性金属粉末より安定性が著しく劣る結果
であった。Comparative Example 1 The ferromagnetic metal powder described in Example 1 was immersed in toluene and air-dried to obtain a ferromagnetic metal powder. As a result of measuring the magnetic properties of the metal powder, Hc=15000e, σs2131
emu/g, Rs=0.502. A deterioration test was conducted in the same manner as in Example 1. σS after 60 hours
The value was 95 emu/g, and the σS value after -week had passed was 90 emu/g. The stability was significantly inferior to that of the ferromagnetic metal powder obtained by the method described in the Examples.
比較例２ 実施例１記載の強磁性金属粉末を使用した。Comparative example 2 The ferromagnetic metal powder described in Example 1 was used.
ＡＩ （ｉｓｏ−ＯＣＪ７） ３を被着する迄は、実施
例１と同様の方法で被着処理したが、熱処理はおこなわ
なかった。該金属粉末の磁気特性を測定した結果、Ｈｃ
＝１４９５０ｅ、’ ｔｔ ｓ＝１３２ｅｍｕ／ｇ、
Ｒｓ＝０．５０２であった。８亥処理金属粉末を実施例
１記載の方法により劣化試験を行なった。６０時間後の
飽和磁化値は、９８ ｅｍｕ／ｇであった。また−週間
経過後の飽和磁化値は、９゜ｅｍｕ／ｇであった。この
結果、被着処理により劣化速度を低下する効果はわずか
にあるが、時間の経過と共に劣化が急激に進行してしま
い実施例記載の方法によって得られた強磁性金属粉末よ
り長期的な安定性が著しく劣る結果であった。The deposition treatment was carried out in the same manner as in Example 1 until the deposition of AI (iso-OCJ7) 3, but no heat treatment was performed. As a result of measuring the magnetic properties of the metal powder, Hc
=14950e,' tt s=132emu/g,
Rs=0.502. A deterioration test was conducted on the 8-treated metal powder using the method described in Example 1. The saturation magnetization value after 60 hours was 98 emu/g. The saturation magnetization value after -1 week was 9 emu/g. As a result, although the adhesion treatment has a slight effect of reducing the deterioration rate, the deterioration progresses rapidly over time and the long-term stability is lower than that of the ferromagnetic metal powder obtained by the method described in the example. The results were significantly inferior.
比較例３ 実施例１記載の強磁性金属粉末を使用した。Comparative example 3 The ferromagnetic metal powder described in Example 1 was used.
八］ （ｉｓｏ−ＯＣＪ７） ｙ ２２．７ｇをトル
エンた。該強磁性金属粉末を上記の溶媒に浸漬し一晩放
置した（ＡＩ／Ｆｅ＝３／１００ ｗｔ比）。該浸漬物
に純水を６．０ｇ （イソプロポキシドの３倍モル量）
添加し加水分解した後、ニーダ−により４時間混練を行
い空気中で風乾処理した。これの磁気特性を測定したと
ころＨｃ＝１４８５ ０ｅ， σｓ＝１３５ｅｍｕ／
ｇ，Ｒｓ＝０．５０１であった。該処理金属粉末を実施
例１記載の方法により劣化試験を行った。６０時間経過
後のσＳ値は、１０６ ｅｍｕ／ｇであり、また−週間
経過後のσＳ値は、９５ｅｍｕ／ｇであった。この結果
、アルミニウムアルコキシド溶解溶液に強磁性金属粉末
を湿潤し水を添加し加水分解し、水酸化アルミニウムを
強磁性金属粉末表面に堆積する方法は、初期の劣化速度
をある程度低下させることは出来るが、長期の劣化に対
しては有効な手段とはならない。その為に磁気記録用強
磁性金属粉末としては到底満足できない結果となった。8] (iso-OCJ7)y 22.7g was added to toluene. The ferromagnetic metal powder was immersed in the above solvent and left overnight (AI/Fe=3/100 wt ratio). Add 6.0g of pure water to the soaked product (3 times the molar amount of isopropoxide)
After the addition and hydrolysis, the mixture was kneaded for 4 hours using a kneader and air-dried in the air. When we measured the magnetic properties of this, Hc=1485 0e, σs=135emu/
g, Rs=0.501. The treated metal powder was subjected to a deterioration test using the method described in Example 1. The σS value after 60 hours was 10 6 emu/g, and the σS value after − weeks was 95 emu/g. As a result, the method of wetting ferromagnetic metal powder in an aluminum alkoxide solution, adding water to hydrolyze it, and depositing aluminum hydroxide on the surface of the ferromagnetic metal powder can reduce the initial deterioration rate to some extent. , it is not an effective measure against long-term deterioration. Therefore, the result was completely unsatisfactory as a ferromagnetic metal powder for magnetic recording.
比較例４
実施例１記載の強磁性金属粉末を使用した。窒素による
熱処理の温度を１５０℃とした以外は、実施例と同様の
方法で行った。該処理金属粉末を実施例１記載の方法に
より劣化試験を行った。６０時間経過後のびＳ値は、１
０３ｅｍｕ／ｇであり、また−週間経過後のσＳ値は、
９５ｅｍｕ／ｇであった。この結果、熱処理温度が２０
０℃未満の場合、初期の劣化防止に対しては効果を発揮
するものの、時間と共に劣化が進行するため、長期の安
定性に難点があることが判明した。従って、長期安定性
を考慮した場合、実用的な観点から採用しうる熱処理温
度としては、２００℃以上が効果を発揮することが判っ
た。Comparative Example 4 The ferromagnetic metal powder described in Example 1 was used. The same method as in Example was carried out except that the temperature of the heat treatment with nitrogen was 150°C. The treated metal powder was subjected to a deterioration test using the method described in Example 1. After 60 hours, the S value is 1
03 emu/g, and the σS value after − weeks has passed.
It was 95 emu/g. As a result, the heat treatment temperature was 20
When the temperature is lower than 0°C, although it is effective in preventing initial deterioration, it has been found that there is a problem in long-term stability because deterioration progresses over time. Therefore, when long-term stability is considered, it has been found that a heat treatment temperature of 200° C. or higher is effective from a practical standpoint.
なお、結果を第２図にあわせて示した。The results are also shown in FIG.
上記実施例、比較例から明らかな様に、強磁性金属粒子
表面に金属アルコキシド化合物又は金属キレート化合物
の有機金属化合物を被着して被膜を形成し、更に該被着
処理金属粉末を不活性ガス雰囲気下又は水素又は水素を
主体とする還元性ガス雰囲気下で熱処理して、該被膜を
より強固・緻密な被膜とすることにより、極めて安定性
の高い磁気記録用強磁性金属粉末を提供する事が出来る
のである。As is clear from the above Examples and Comparative Examples, an organic metal compound such as a metal alkoxide compound or a metal chelate compound is deposited on the surface of the ferromagnetic metal particles to form a film, and the coated metal powder is further exposed to an inert gas. To provide extremely stable ferromagnetic metal powder for magnetic recording by making the film stronger and denser by heat treatment in an atmosphere or in an atmosphere of hydrogen or a reducing gas mainly composed of hydrogen. This is possible.
第１図は、ＡＩアルコキシドの被着量に対する強磁性金
属粉末の安定性を示すグラフである。又第２図は、ＡＩ
アルコキシド被着強磁性金属粉末を窒素ガス雰囲気下で
熱処理した場合の処理温度に対する安定性を示すグラフ
である。
なお、図において、Ｏは６０時間経過後、Δは一週間経
過後の値を示す。
特許出願人：三井東圧化学株式会社
第１図
被着量
第２図
０ １００ ３００ ５００ （’Ｃ）温
度FIG. 1 is a graph showing the stability of ferromagnetic metal powder with respect to the amount of AI alkoxide deposited. Also, Figure 2 shows the AI
2 is a graph showing stability with respect to processing temperature when alkoxide-coated ferromagnetic metal powder is heat-treated in a nitrogen gas atmosphere. In the figure, O indicates the value after 60 hours, and Δ indicates the value after one week. Patent applicant: Mitsui Toatsu Chemical Co., Ltd. Figure 1 Coating amount Figure 2 0 100 300 500 ('C) Temperature
Claims (4)
着し、その後不活性ガス雰囲気下で又は水素若しくは水
素を主体とする還元性ガス雰囲気下で熱処理する事を特
徴とする強磁性金属粉末の安定化方法。(1) A ferromagnetic metal characterized by coating an organometallic compound on the particle surface of a ferromagnetic metal powder and then heat-treating it in an inert gas atmosphere or in an atmosphere of hydrogen or a reducing gas mainly composed of hydrogen. Methods for stabilizing powders.
Ｂ、Ｔｉ、Ｚｎ及びＺｒから選択される少なくとも一種
類である特許請求の範囲第１項記載の強磁性金属粉末の
安定化方法。(2) The metal constituting the organometallic compound is Al, Si,
The method for stabilizing ferromagnetic metal powder according to claim 1, wherein the ferromagnetic metal powder is at least one selected from B, Ti, Zn, and Zr.
ート化合物からなる特許請求の範囲１項記載の強磁性金
属粉末の安定化方法。(3) The method for stabilizing ferromagnetic metal powder according to claim 1, wherein the organometallic compound is an alkoxide compound or a chelate compound.
許請求の範囲第１項記載の強磁性金属粉末の安定化方法
。(4) The method for stabilizing ferromagnetic metal powder according to claim 1, wherein the temperature range of the heat treatment is 200°C to 700°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22388286 | 1986-09-24 | ||
| JP61-223882 | 1986-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63184307A true JPS63184307A (en) | 1988-07-29 |
Family
ID=16805185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62198253A Pending JPS63184307A (en) | 1986-09-24 | 1987-08-10 | Stabilization of ferromagnetic metal powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63184307A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252380A (en) * | 1988-10-31 | 1993-10-12 | Hitachi Maxell, Ltd. | Acicular alloy containing magnetic recording medium |
| US5260132A (en) * | 1988-10-31 | 1993-11-09 | Hitachi Maxell, Ltd. | Acicular alloy magnetic powder |
| KR100503132B1 (en) * | 2002-11-08 | 2005-07-22 | 한국화학연구원 | Method for producing fine spherical particles of nickel metal |
-
1987
- 1987-08-10 JP JP62198253A patent/JPS63184307A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252380A (en) * | 1988-10-31 | 1993-10-12 | Hitachi Maxell, Ltd. | Acicular alloy containing magnetic recording medium |
| US5260132A (en) * | 1988-10-31 | 1993-11-09 | Hitachi Maxell, Ltd. | Acicular alloy magnetic powder |
| KR100503132B1 (en) * | 2002-11-08 | 2005-07-22 | 한국화학연구원 | Method for producing fine spherical particles of nickel metal |
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