JPS62196308A - Magnetic metallic powder and its production - Google Patents
Magnetic metallic powder and its productionInfo
- Publication number
- JPS62196308A JPS62196308A JP61036889A JP3688986A JPS62196308A JP S62196308 A JPS62196308 A JP S62196308A JP 61036889 A JP61036889 A JP 61036889A JP 3688986 A JP3688986 A JP 3688986A JP S62196308 A JPS62196308 A JP S62196308A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- iron
- aluminum oxide
- aluminum
- particle surface
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002245 particle Substances 0.000 claims abstract description 48
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 45
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 23
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract 2
- 239000006247 magnetic powder Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000725 suspension Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 229910052598 goethite Inorganic materials 0.000 description 14
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 14
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000005837 radical ions Chemical class 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 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、金属磁性粉末およびその製造方法に関し、
さらに詳しくは磁気特性に優れた鉄を主体とする金属磁
性粉末およびその製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a metal magnetic powder and a method for producing the same.
More specifically, the present invention relates to a metal magnetic powder mainly composed of iron having excellent magnetic properties and a method for producing the same.
鉄を主体とする金属磁性粉末は、通常、オキシ水酸化鉄
粉末または酸化鉄粉末を加熱還元してつくられ、高い飽
和磁化量を有しているが、加熱還元時に粒子相互間で焼
結が生じたりして粒子の均−件や形状が損なわれやすく
、充分に磁気特性に優れたものが得られにくい。Metal magnetic powder, mainly made of iron, is usually made by heating and reducing iron oxyhydroxide powder or iron oxide powder, and has a high saturation magnetization, but sintering occurs between particles during heating and reduction. As a result, the uniformity and shape of the particles are likely to be impaired, making it difficult to obtain particles with sufficiently excellent magnetic properties.
このため、従来から加熱還元時の粒子相互間の焼結を防
止する目的で、加熱還元前の被還元物粉末の粒子表面に
種々の焼結防止剤を被着することが行われており、たと
えば、アルミン酸塩を溶解したアルカリ水溶液中にオキ
シ水酸化鉄粉末または酸化鉄粉末を分散させ、アルミン
酸塩を加水分解して、酸化アルミニウム被膜などのアル
ミニウム化合物被膜を被着形成することが行われている
。（特公昭５６−２８９６７号）
〔発明が解決しようとする問題点〕
ところが、アルミン酸塩の加水分解によって被還元物粉
末の粒子表面に酸化アルミニウム被膜を形成する従来の
方法では、酸化アルミニウム被膜中にアルカリ金属イオ
ン、硫酸イオンなどの酸根イオンが混入し、洗浄が極め
て難しい。このため、これを加熱還元して得られる金属
磁性粉末の粒子表面の酸化アルミニウム被膜中にこれら
の不純物が含まれ、酸化アルミニウム被膜が化学的に不
安定になるとともに、酸化アルミニウム被膜の構造にも
欠陥が生じやすく、焼結防止効果に支障をきたす。また
このような酸化アルミニウム被膜を形成した金属磁性粉
末を使用して磁性塗料を調製すると、酸化アルミニウム
被膜中に含まれるアルカリ金属イオン、硫酸イオンなど
の酸根イオンが、結合剤樹脂と反応して磁性塗料をゲル
化し、充分に良好な磁気特性および耐久性を有する磁気
記録媒体が得られない。For this reason, in order to prevent sintering between particles during thermal reduction, various sintering inhibitors have been applied to the particle surfaces of the reductant powder before thermal reduction. For example, an aluminum compound coating such as an aluminum oxide coating can be formed by dispersing iron oxyhydroxide powder or iron oxide powder in an alkaline aqueous solution containing an aluminate and hydrolyzing the aluminate. It is being said. (Japanese Patent Publication No. 56-28967) [Problems to be Solved by the Invention] However, in the conventional method of forming an aluminum oxide film on the particle surface of the reductant powder by hydrolyzing an aluminate, a Acid radical ions such as alkali metal ions and sulfate ions are mixed in, making cleaning extremely difficult. For this reason, these impurities are included in the aluminum oxide coating on the particle surface of the metal magnetic powder obtained by heating reduction, making the aluminum oxide coating chemically unstable and causing damage to the structure of the aluminum oxide coating. Defects are likely to occur, impeding the sintering prevention effect. Furthermore, when a magnetic paint is prepared using metal magnetic powder that has formed an aluminum oxide film, acid radical ions such as alkali metal ions and sulfate ions contained in the aluminum oxide film react with the binder resin and become magnetic. The paint gels, and a magnetic recording medium with sufficiently good magnetic properties and durability cannot be obtained.
この発明はかかる問題点を解消するため種々検討を行っ
た結果なされたもので、オキシ水酸化鉄または酸化鉄を
主体とする粉末の粒子表面にアルミニウムアルコキシド
の蒸気を接触させて被着させ、次いで、水蒸気を接触さ
せ、粒子表面で加水分解させて、酸化アルミニウム被膜
をオキシ水酸化鉄または酸化鉄を主体とする粉末の粒子
表面に形成するか、あるいはオキシ水酸化鉄または酸化
鉄を主体とする粉末の水懸濁液に、アルミニウムアルコ
キシドを溶解した溶液を添加し、オキシ水酸化鉄または
酸化鉄を主体とする粉末の粒子表面でアルミニウムアル
コキシドを加水分解させて、酸化アルミニウム被膜もし
くは含水酸化アルミニウム被膜をオキシ水酸化鉄または
酸化鉄を主体とする粉末の粒子表面に形成し、しかる後
、これらを加熱還元し、粒子表面に純度が９９％以上の
高純度の酸化アルミニウム被膜を形成した鉄を主体とす
る金属磁性粉末とすることによって、アルカリ金属イオ
ン、硫酸イオンなどの酸根イオンなどの不純物を全く含
まず、化学的に安定で、均一性の良好な酸化アルミニウ
ム被膜を鉄を主体とする金属磁性粉末の粒子表面に形成
し、この種の金属磁性粉末の磁気特性を向上させるとと
もに、この種の金属磁性粉末を使用して調製される磁性
塗料のゲル化を良好に防止し、得られる磁気記録媒体の
磁気特性および耐久性を充分に向上させたものである。This invention was made as a result of various studies to solve these problems. The surface of powder particles mainly composed of iron oxyhydroxide or iron oxide is coated with vapor of aluminum alkoxide, and then , contact with water vapor and hydrolyze on the particle surface to form an aluminum oxide film on the particle surface of a powder mainly composed of iron oxyhydroxide or iron oxide, or a powder mainly composed of iron oxyhydroxide or iron oxide. A solution containing aluminum alkoxide is added to an aqueous suspension of the powder, and the aluminum alkoxide is hydrolyzed on the surface of the particles of iron oxyhydroxide or iron oxide-based powder to form an aluminum oxide coating or a hydrated aluminum oxide coating. is formed on the particle surface of a powder mainly composed of iron oxyhydroxide or iron oxide, and then heated and reduced to form a high-purity aluminum oxide coating with a purity of 99% or more on the particle surface. By creating a metal magnetic powder that contains no impurities such as alkali metal ions, acid radical ions such as sulfate ions, and is chemically stable and has a good uniformity, the aluminum oxide coating can be applied to a metal magnetic powder mainly made of iron. Formed on the surface of the powder particles, it improves the magnetic properties of this type of metal magnetic powder, and also effectively prevents gelation of the magnetic paint prepared using this type of metal magnetic powder, resulting in magnetic recording. The magnetic properties and durability of the medium are sufficiently improved.
この発明において、鉄を主体とする金属磁性粉末の粒子
表面に酸化アルミニウム被１１’ｌを形成するのに使用
するアルミニウムアルコキシドとしては、たとえば、ア
ルミニウムイソプロポキシド、アルミニウムトリエトキ
シド、アルミニウムトリエトキシド、アルミニウムトリ
ーｎ−ブトキシド、アルミニウムｌ□ ’Ｊ −５ｅｃ
−ブトキシドなどが好適なものとして使用される。こ
の種のアルミニウムアルコキシドは、従来のアルミン酸
塩とは異なり、分子中にアルカリ金属イオン、硫酸イオ
ンなどの酸根イオンを持たず、５０〜２００ ’Ｃの温
度で加熱すると熱分解することもなく容易に蒸気化され
る。また、アルコール、ケトン、エステルなどの溶剤に
容易に溶解し、さらに潮解性で水により分解する。In this invention, examples of the aluminum alkoxide used to form the aluminum oxide coating 11'l on the particle surface of the metal magnetic powder mainly composed of iron include aluminum isopropoxide, aluminum triethoxide, and aluminum triethoxide. , aluminum tri-n-butoxide, aluminum l□ 'J -5ec
-Butoxide and the like are preferably used. Unlike conventional aluminates, this type of aluminum alkoxide does not have acid radical ions such as alkali metal ions and sulfate ions in its molecules, and does not decompose easily when heated at a temperature of 50 to 200'C. vaporized into It also dissolves easily in solvents such as alcohols, ketones, and esters, and is deliquescent and decomposes in water.
しかして、このようなアルミニウムアルコキシドを加熱
藤発し、アルミニ・シムアルコキシドの蒸気を、オキシ
水酸化鉄または酸化鉄を主体とする粉末の粒子表面に接
触させて被着し、次いで、水蒸気を接触させると、粒子
表面でアルミニウムアルコキシドが加水分解されて酸化
アルミニウムとなり、オキシ水酸化鉄または酸化鉄を主
体とする粉末の粒子表面に、アルカリ金属イオン、硫酸
イオンなどの酸根イオンなどの不純物を全く含まない極
めて高純度の酸化アルミニウム被膜が被着形成される。Thus, such an aluminum alkoxide is heated and heated, the vapor of the aluminum shim alkoxide is brought into contact with the surface of particles of powder mainly composed of iron oxyhydroxide or iron oxide, and then water vapor is brought into contact with the surface of the particles. Then, aluminum alkoxide is hydrolyzed on the particle surface to become aluminum oxide, and the particle surface of the powder mainly composed of iron oxyhydroxide or iron oxide does not contain any impurities such as alkali metal ions or acid radical ions such as sulfate ions. A very high purity aluminum oxide coating is deposited.
また、アルミニウムアルコキシドを適当な溶剤に溶解し
、このアルミニウムアルコキシドの溶液を、オキシ水酸
化鉄または酸化鉄を主体とする粉末の水懸濁液に添加し
て攪拌すると、オキシ水酸化鉄または酸化鉄を主体とす
る粉末の粒子表面で、アルミニウムアルコキシドが加水
分解されて酸化アルミニウムもしくは含水酸化アルミニ
ウムとなり、アルカリ全屈イオン、硫酸イオンなどの酸
根イオンなどの不純物が混入されることもなく、極めて
高純度の酸化アルミニウム被膜もしくは含水酸化アルミ
ニウム被膜が、オキシ水酸化鉄または酸化鉄を主体とす
る粉末の粒子表面に被着形成される。In addition, when aluminum alkoxide is dissolved in a suitable solvent, and this aluminum alkoxide solution is added to an aqueous suspension of powder mainly composed of iron oxyhydroxide or iron oxide and stirred, iron oxyhydroxide or iron oxide can be obtained. Aluminum alkoxide is hydrolyzed on the particle surface of the powder, which is mainly made of An aluminum oxide film or a hydrous aluminum oxide film is formed on the surface of particles of iron oxyhydroxide or iron oxide-based powder.
このような気相反応あるいは液相反応によって、オキシ
水酸化鉄または酸化鉄を主体とする粉末の粒子表面に被
着形成される酸化アルミニウム被膜もしくは含水酸化ア
ルミニウム被膜は、もっばら粒子表面にのみ被着し、多
量に被着する場合でも粒子表面にのみ被着して、極めて
高純度の酸化アルミニウム被膜もしくは含水酸化アルミ
ニウム被膜が形成される。オキシ水酸化鉄または酸化鉄
を主体とする粉末の粒子表面への被着量は、ＡＩ／Ｆｅ
の原子換算重量比で０．１〜２０重量％の範囲内にする
のが好ましく、少なすぎると酸化アルミニウム被膜もし
くは含水酸化アルミニウム被膜が良好に形成されず、多
すぎると均一な厚みのアルミニウム化合物被膜を形成し
にくり、また、表面以外にアルミニウム化合物が析出し
始める。The aluminum oxide film or hydrated aluminum oxide film that is formed on the particle surface of iron oxyhydroxide or iron oxide-based powder by such a gas phase reaction or liquid phase reaction is coated only on the particle surface. Even when a large amount is deposited, it is deposited only on the particle surface, forming an extremely high purity aluminum oxide film or a hydrous aluminum oxide film. The amount of powder mainly composed of iron oxyhydroxide or iron oxide deposited on the particle surface is
It is preferable that the atomic weight ratio is within the range of 0.1 to 20% by weight. If it is too small, the aluminum oxide film or hydrous aluminum oxide film will not be formed well, and if it is too large, the aluminum compound film will not have a uniform thickness. In addition, aluminum compounds begin to precipitate on surfaces other than the surface.
このようにして、極めて高純度の酸化アルミニウム被膜
もしくは含水酸化アルミニウム被膜が形成されたオキシ
水酸化鉄または酸化鉄は、次いで、水素気流中で１５０
〜６００℃の温度で加熱還元されると、極めて高純度の
酸化アルミニウム被膜もしくは含水酸化アルミニウム被
膜により焼結防止効果が充分に発揮されて、純度が９９
％以上の高純度の酸化アルミニウム被膜が形成された鉄
を主体とする金属磁性粉末が得られ、このようにして鉄
を主体とする金属磁性粉末の粒子表面に形成された酸化
アルミニウム被膜は、非常に箱書で、化学的に安定な上
、均一性もよいため、この種の金属磁性粉末の磁気特性
が向上されるとともに゛、この種の金泥磁性粉末を使用
して調製される磁性塗料のゲル化も良好に防止され、こ
の種の金属磁性粉末を使用して得られる磁気記録媒体の
磁気特性および耐久性が充分に向上される。The iron oxyhydroxide or iron oxide on which an extremely high-purity aluminum oxide film or hydrated aluminum oxide film has been formed in this way is then heated to 150°C in a hydrogen stream.
When heated and reduced at a temperature of ~600°C, the extremely high purity aluminum oxide coating or hydrated aluminum oxide coating fully exhibits the sintering prevention effect, resulting in a purity of 99%.
The aluminum oxide film formed on the particle surface of the iron-based metal magnetic powder in this way has a very high purity. In addition to being chemically stable and having good uniformity, the magnetic properties of this type of metal magnetic powder are improved, and the magnetic paint prepared using this type of gold mud magnetic powder is also improved. Gelation is also well prevented, and the magnetic properties and durability of the magnetic recording medium obtained using this type of metal magnetic powder are sufficiently improved.
オキシ水酸化鉄および酸化鉄を主体とする粉末としては
、ｃｔ −Ｆ ｅ ＯＯＨ粉末、β−ＦｅｏＯＨ粉末、
ｒ−ＦｅＯＯＩＩ粉末、ｔｘ−Ｆｅ２０３粉末、Ｆｅ５
０．粉末などの他、これらにＣ０１Ｃｒ、ＡＩ、Ｍｎ、
Ｚｎなどの種々の金属成分を含有させた粉末等が好適な
ものとして使用される。Examples of powders mainly composed of iron oxyhydroxide and iron oxide include ct-F e OOH powder, β-FeoOH powder,
r-FeOOII powder, tx-Fe203 powder, Fe5
0. In addition to powder etc., these include CO1Cr, AI, Mn,
Powders containing various metal components such as Zn are preferably used.
以上のように、鉄を主体とする金属磁性粉末の粒子表面
に純度が９９％以上の高純度の酸化アルミニウム被膜を
設けた金属磁性粉末は、酸化アルミニウム被膜の安定性
および均一・性がよく、その結果、金属磁性粉末の磁気
特性が向上されるとともに、この種の金属磁性粉末を使
用して磁気記録媒体を製造すると、磁気特性および耐久
性が充分に向上された磁気記録媒体が得られる。As described above, the metal magnetic powder, in which a highly purified aluminum oxide coating with a purity of 99% or more is provided on the particle surface of the metal magnetic powder mainly composed of iron, has good stability, uniformity, and properties of the aluminum oxide coating. As a result, the magnetic properties of the metal magnetic powder are improved, and when a magnetic recording medium is manufactured using this type of metal magnetic powder, a magnetic recording medium with sufficiently improved magnetic properties and durability can be obtained.
次に、この発明の実施例について説明する。 Next, embodiments of the invention will be described.
実施例１
平均長径０．４μｍ、軸比（長径／短径）１２／１のゲ
ータイト粉末１０ｇを、ガラスチューブで連結されたフ
ラスコの一方に入れて、真空ポンプで磁気した。一方、
他方のフラスコにアルミニウムイソプロポキシドを約２
０ｇ入れ、これを電気炉で加熱して蒸発させ、このアル
ミニウムイソプロポキシドの蒸気を、前記のゲータイト
粉末を入れたフラスコに送り込み、アルミニウムイソプ
ロポキシドの蒸気を吸着させた。しかる後、水蒸気を導
入してゲータイト粉末の粒子表面に吸着されたアルミニ
ウムイソプロポキシドを加水分解し、粒子表面に酸化ア
ルミニウム被膜を形成したゲータイト粉末を得た。Example 1 10 g of goethite powder having an average major axis of 0.4 μm and an axial ratio (major axis/minor axis) of 12/1 was placed in one side of a flask connected by a glass tube, and magnetized using a vacuum pump. on the other hand,
In the other flask, add approximately 2 ml of aluminum isopropoxide.
This was heated in an electric furnace to evaporate it, and the vapor of aluminum isopropoxide was sent into the flask containing the goethite powder, and the vapor of aluminum isopropoxide was adsorbed. Thereafter, water vapor was introduced to hydrolyze the aluminum isopropoxide adsorbed on the particle surfaces of the goethite powder, thereby obtaining goethite powder with an aluminum oxide coating formed on the particle surfaces.
次いで、得られたゲータイト粉末を、水素気流中、５０
０ ’Ｃで４時間加熱還元して、純度が９９％以上の高
純度の酸化アルミニウム被膜を設けた金属鉄磁性粉末を
得た。この金属鉄磁性粉末は、平均長径が０．３μｍで
、軸比（長径／短径）は１０／１であった。このように
して得られた金属鉄磁性粉末を使用し、
金属鉄磁性粉末 １００重量部■八ｃへ
ｉ ｃｕ、ｃ、ｃ社製、塩化ビ １０〃ニル−酢酸ビ
ニル−ビニルア
ルコール共重合体）
パンデソクスＴ−５２０１（大 ６ 〃日本インキ化
学工業社製、ポ
リウレタン、数平均分子量２
〜３万）
ミリスチン酸 ５ 〃１（Ｓ−５
００（旭電化社製、力 １ 〃−ボンブラック）
メチルイソブチルケトン ８５〃トルエン
８５〃の組成からなる組成物を３１！
容量のスチール製ボールミル中に入れ、これを７２時間
回転させ、よく分散させて磁性ペーストを調製した。そ
の後、この磁性ペーストに、トルエン４０重量部とコロ
ネートしく成田薬品工業社製、三官能性低分子量イソシ
アネート化合物）２重量部をさらに加え、磁性塗料を調
製した。この磁性塗料を厚さ１２μｍのポリエステルフ
ィルム上に、乾燥後の塗布厚が４μｍとなるように塗布
、乾燥し、鏡面加工処理を行った後、１／２インチ幅に
裁断して磁気テープをつ（った。Next, the obtained goethite powder was heated for 50 minutes in a hydrogen stream.
By heating and reducing at 0'C for 4 hours, a metal iron magnetic powder provided with a highly pure aluminum oxide coating having a purity of 99% or more was obtained. This metallic iron magnetic powder had an average major axis of 0.3 μm and an axial ratio (major axis/minor axis) of 10/1. Using the metal iron magnetic powder obtained in this way, 100 parts by weight of the metal iron magnetic powder (vinyl chloride-vinyl acetate-vinyl alcohol copolymer (manufactured by ICU, C, C Co., Ltd.)) Pandesox T-5201 (large 6, manufactured by Nippon Ink Chemical Industry Co., Ltd., polyurethane, number average molecular weight 20,000 to 30,000) Myristic acid 5 1 (S-5
00 (manufactured by Asahi Denka Co., Ltd., 1 - Bomb Black) Methyl isobutyl ketone 85 Toluene
A composition consisting of 85〃 composition is 31!
The magnetic paste was prepared by placing the magnetic paste in a high capacity steel ball mill and rotating it for 72 hours to ensure good dispersion. Thereafter, 40 parts by weight of toluene and 2 parts by weight of trifunctional low molecular weight isocyanate compound (manufactured by Narita Pharmaceutical Co., Ltd.) were further added to this magnetic paste to prepare a magnetic paint. This magnetic paint was applied onto a polyester film with a thickness of 12 μm so that the coating thickness after drying was 4 μm, dried, mirror-finished, cut into 1/2-inch pieces, and attached with magnetic tape. (It was.
実施例２
平均長径０．４μｍ、軸比（長径／短径）１２／１のゲ
ータイト粉末３ｇを、水４ Ｑ ０ｍｆｆ中に分散し、
分散液を分散機でよく攪拌しながら、別個にアルミニウ
ムイソプロポキシド５ｇをエタノール３０ｍ７！に溶解
して用意したアルミニウムイソプロポキシドのアルコー
ルン容ン皮を徐々に添カロし、ゲータイト粉末の粒子表
面にアルミニウムイソプロポキシドを被着さ−Ｕると同
時に、ゲータイト粉末の粒子表面に吸着されたアルミニ
ウムイソプロポキシドを加水分解し、粒子表面に酸化ア
ルミニウム破膜を形成したゲータイトわ）末を得た。Example 2 3 g of goethite powder with an average major axis of 0.4 μm and an axial ratio (major axis/minor axis) of 12/1 was dispersed in 4 Q 0 mff of water,
While stirring the dispersion liquid well with a dispersion machine, separately add 5 g of aluminum isopropoxide to 30 m7 of ethanol! Aluminum isopropoxide prepared by dissolving it in alcohol is gradually added to the surface of the goethite powder particles, and at the same time, the aluminum isopropoxide is adhered to the surface of the goethite powder particles. The resulting aluminum isopropoxide was hydrolyzed to obtain goethite powder with a broken aluminum oxide film formed on the particle surface.
次いで、得られたゲータイト粉末を、実施例１と同様に
して加熱還元して、平均長径が０．３μｍ、軸比（長径
／短径）が１０／１で、純度が９９％以上の高純度の酸
化アルミニウム被膜を設けた金属鉄磁性粉末を得、磁気
テープをつくった。Next, the obtained goethite powder was heated and reduced in the same manner as in Example 1 to obtain a highly purified product with an average major axis of 0.3 μm, an axial ratio (major axis/minor axis) of 10/1, and a purity of 99% or more. Metallic iron magnetic powder with an aluminum oxide coating was obtained and a magnetic tape was made.
比較例１
平均長径０．４μｍ、軸比（長径／短径）１２／１のゲ
ータイト粉末３ｇを、ＩＮの苛性ソーダ水溶液に懸濁し
、これをよく攪１１〉シながら、別個に用意した０、５
Ｍの硫酸アルミニウムの０．５Ｎ苛性ソ一ダ水溶液５ｍ
ｆｆを添加した。次いで、この）フ濁液に炭酸ガスを徐
々に通気して中和し、ｐ １１８以下にした後、濾過分
離して、純水で洗浄し、ゲータイト粉末の粒子表面に酸
化アルミニウム被膜を形成したゲータイト粉末を得た。Comparative Example 1 3 g of goethite powder with an average major axis of 0.4 μm and an axial ratio (major axis/minor axis) of 12/1 was suspended in an IN aqueous solution of caustic soda, and while stirring thoroughly,
5 m of 0.5N caustic soda aqueous solution of M aluminum sulfate
ff was added. Next, carbon dioxide gas was gradually passed through the suspension to neutralize it to a p value of 118 or less, followed by separation by filtration and washing with pure water to form an aluminum oxide film on the surface of the goethite powder particles. Goethite powder was obtained.
次いで、得られたゲータイト粉末を、実施例１と同様に
して加熱還元して、平均長径が０．３μｍ、軸比（長径
／短径）が６／１の酸化アルミニウム被膜を設けた金属
鉄磁性粉末を得、磁気テープをつくった。Next, the obtained goethite powder was heated and reduced in the same manner as in Example 1 to obtain a metal iron magnetic material provided with an aluminum oxide coating having an average major axis of 0.3 μm and an axial ratio (major axis/minor axis) of 6/1. The powder was obtained and magnetic tape was made.
各実施例および比較例で得られた酸化アルミニウム被膜
を存する金属鉄磁性粉末について、保磁力、飽和磁化量
、ＢＥＴ法による比表面積を測定し、また酸化アルミニ
ウム被膜のＡβ／ Ｆ ｅの原子換算重量比および酸化
アルミニウム被膜中の硫酸イオンおよびナトリウムイオ
ンの含有量を測定した。The coercive force, saturation magnetization, and specific surface area by BET method were measured for the metal iron magnetic powder containing the aluminum oxide film obtained in each example and comparative example, and the atomic weight of Aβ/Fe of the aluminum oxide film was measured. The ratio and the content of sulfate ions and sodium ions in the aluminum oxide coating were measured.
下記第１表はその結果である。Table 1 below shows the results.
第１表
また各実施例および比較例で得られた磁気テープについ
て、角型比、耐久性および残留磁束密度を測定した。耐
久性は市販ＶＴＲを使用し、−５℃の恒温室中で静止画
像再生を行った時の出力が３ｄＢ低下するまでの時間を
測定することにより判定した。Table 1 Also, the squareness ratio, durability, and residual magnetic flux density were measured for the magnetic tapes obtained in each Example and Comparative Example. Durability was determined by using a commercially available VTR and measuring the time until the output decreased by 3 dB when still images were reproduced in a constant temperature room at -5°C.
下記第２表はその結果である。Table 2 below shows the results.
第２表
〔発明の効果〕
上記第１表から明らかなように、この発明で得られた金
属鉄磁性粉末（実施例１および２）は、いずれも従来の
金属鉄磁性粉末（比較例１）に比し、保磁力が高くて、
不純物を全く含まず、また上記第２表から明らかなよう
に、この発明で得られた金属鉄磁性粉末を使用して得ら
れた磁気テープ（実施例１および２）は、いずれも比較
例１で得られた金属鉄磁性粉末を使用して得られた磁気
テープ（比較例１）に比し、角型比および残留磁束密度
が高くて、耐久性がよく、このことからこの発明の金属
磁性粉末は粒子表面に被着形成した酸化アルミニウム被
膜の安定性および均一性がよくて、磁気特性に優れ、そ
の結果、この金属磁性粉末を使用して得られる磁気記録
媒体は、磁気特性および耐久性が一段と向上されている
ことがわかる。Table 2 [Effects of the Invention] As is clear from Table 1 above, the metal iron magnetic powder obtained by this invention (Examples 1 and 2) is different from the conventional metal iron magnetic powder (Comparative Example 1). It has a higher coercive force compared to
The magnetic tapes (Examples 1 and 2) obtained using the metallic iron magnetic powder obtained in the present invention do not contain any impurities, and as is clear from Table 2 above, both Comparative Example 1 Compared to the magnetic tape obtained using the metal iron magnetic powder obtained in (Comparative Example 1), the squareness ratio and residual magnetic flux density are higher and the durability is better. The powder has good stability and uniformity of the aluminum oxide film formed on the particle surface, and has excellent magnetic properties.As a result, the magnetic recording medium obtained using this metal magnetic powder has excellent magnetic properties and durability. It can be seen that this has been further improved.
Claims (1)
９％以上の高純度の酸化アルミニウム被膜を設けたこと
を特徴とする金属磁性粉末 ２、オキシ水酸化鉄または酸化鉄を主体とする粉末の粒
子表面にアルミニウムアルコキシドの蒸気を接触させて
被着させ、次いで、水蒸気を接触させ、粒子表面で加水
分解させて、酸化アルミニウム被膜をオキシ水酸化鉄ま
たは酸化鉄を主体とする粉末の粒子表面に形成し、しか
る後、これを加熱還元して、粒子表面に純度が９９％以
上の高純度の酸化アルミニウム被膜を形成した鉄を主体
とする金属磁性粉末とすることを特徴とする金属磁性粉
末の製造方法 ３、オキシ水酸化鉄または酸化鉄を主体とする粉末を、
アルミニウムアルコキシドを溶解した溶液に添加し、さ
らに適当量の水を添加しオキシ水酸化鉄または酸化鉄を
主体とする粉末の粒子表面でアルミニウムアルコキシド
を加水分解させて、酸化アルミニウム被膜もしくは含水
酸化アルミニウム被膜をオキシ水酸化鉄または酸化鉄を
主体とする粉末の粒子表面に形成し、しかる後、これを
加熱還元して、粒子表面に純度が９９％以上の高純度の
酸化アルミニウム被膜を形成した鉄を主体とする金属磁
性粉末とすることを特徴とする金属磁性粉末の製造方法[Claims] 1. The particle surface of metal magnetic powder mainly composed of iron has a purity of 9
Metal magnetic powder 2 characterized by having an aluminum oxide coating with a high purity of 9% or more, which is coated by bringing aluminum alkoxide vapor into contact with the particle surface of a powder mainly composed of iron oxyhydroxide or iron oxide. Next, water vapor is brought into contact with the particles to cause hydrolysis on the particle surfaces to form an aluminum oxide coating on the particle surfaces of iron oxyhydroxide or iron oxide-based powder, which is then heated and reduced to form particles. Method 3 for producing metal magnetic powder, characterized in that it is a metal magnetic powder mainly composed of iron, on which a high-purity aluminum oxide film with a purity of 99% or more is formed on the surface, mainly composed of iron oxyhydroxide or iron oxide. powder to
Adding aluminum alkoxide to a solution in which it is dissolved, and then adding an appropriate amount of water to hydrolyze the aluminum alkoxide on the surface of particles of iron oxyhydroxide or iron oxide-based powder to form an aluminum oxide coating or a hydrated aluminum oxide coating. is formed on the particle surface of a powder mainly composed of iron oxyhydroxide or iron oxide, and then heated and reduced to form a highly pure aluminum oxide film with a purity of 99% or more on the particle surface. A method for producing a metal magnetic powder, characterized in that the metal magnetic powder is mainly a metal magnetic powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61036889A JPH0765084B2 (en) | 1986-02-20 | 1986-02-20 | Metal magnetic powder and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61036889A JPH0765084B2 (en) | 1986-02-20 | 1986-02-20 | Metal magnetic powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62196308A true JPS62196308A (en) | 1987-08-29 |
| JPH0765084B2 JPH0765084B2 (en) | 1995-07-12 |
Family
ID=12482344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61036889A Expired - Lifetime JPH0765084B2 (en) | 1986-02-20 | 1986-02-20 | Metal magnetic powder and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0765084B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001510286A (en) * | 1997-07-18 | 2001-07-31 | ホガナス アクチボラゲット | Soft magnetic synthetic material and method for producing the same |
| WO2009057675A1 (en) * | 2007-11-02 | 2009-05-07 | Toyota Jidosha Kabushiki Kaisha | Powder for magnetic core, powder magnetic core, and their production methods |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5390151A (en) * | 1977-01-21 | 1978-08-08 | Hitachi Maxell | Magnetic powder manufacturing process |
| JPS575804A (en) * | 1980-06-11 | 1982-01-12 | Hitachi Maxell Ltd | Preparation of magnetic metal powder |
-
1986
- 1986-02-20 JP JP61036889A patent/JPH0765084B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5390151A (en) * | 1977-01-21 | 1978-08-08 | Hitachi Maxell | Magnetic powder manufacturing process |
| JPS575804A (en) * | 1980-06-11 | 1982-01-12 | Hitachi Maxell Ltd | Preparation of magnetic metal powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001510286A (en) * | 1997-07-18 | 2001-07-31 | ホガナス アクチボラゲット | Soft magnetic synthetic material and method for producing the same |
| JP4689038B2 (en) * | 1997-07-18 | 2011-05-25 | ホガナス アクチボラゲット | Soft magnetic synthetic material and manufacturing method thereof |
| WO2009057675A1 (en) * | 2007-11-02 | 2009-05-07 | Toyota Jidosha Kabushiki Kaisha | Powder for magnetic core, powder magnetic core, and their production methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0765084B2 (en) | 1995-07-12 |
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