JPS633402A - Manufacture of highly filled and highly oriented magnetic iron powder - Google Patents
Manufacture of highly filled and highly oriented magnetic iron powderInfo
- Publication number
- JPS633402A JPS633402A JP61146122A JP14612286A JPS633402A JP S633402 A JPS633402 A JP S633402A JP 61146122 A JP61146122 A JP 61146122A JP 14612286 A JP14612286 A JP 14612286A JP S633402 A JPS633402 A JP S633402A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- zirconium
- iron powder
- magnetic
- magnetic iron
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000000151 deposition Methods 0.000 claims description 11
- -1 titanium alkoxide Chemical class 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、磁気記録用磁性鉄粉の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing magnetic iron powder for magnetic recording.
［従来の技術］
２ 磁気記録は高密度化が強く指向され、磁性材に対す
る要求もこれに対応してますます厳しくなっている。８
Ｍビデオ用途について概観すると、磁気テープは出力ア
ップ及びノイズ低減につき改良が続けられており、磁性
粉としては、高いσＳの：求から、従来の酸化鉄系磁性
粉と異なり、高い還元度のいわゆる磁性鉄粉が使用され
ている。[Prior Art] 2. There is a strong trend toward higher density magnetic recording, and the demands on magnetic materials are becoming increasingly strict in response. 8
An overview of M-video applications shows that magnetic tape continues to be improved to increase output and reduce noise.As magnetic powder, due to the requirement for high σS, unlike conventional iron oxide-based magnetic powder, so-called high reduction degree magnetic powder is used. Magnetic iron powder is used.
磁性鉄粉は、−般に、針状のオキシ水酸化鉄を加熱還元
する方法によって製造されているが、加熱還元の際に出
発物質であるオキシ水酸化鉄が形崩れしたり焼結したり
するのを防止するための形状保持成分や最終的に得られ
る磁性鉄粉の磁気特性を調整する成分を、オキシ水酸化
鉄の加熱還元の前にオキシ水酸化鉄の表面に′ｇ１着さ
せる処理を行なうことが、通常行なわれている。Magnetic iron powder is generally produced by heating and reducing acicular iron oxyhydroxide, but the starting material iron oxyhydroxide may lose its shape or sinter during heating reduction. A treatment in which a shape-retaining component to prevent the formation of particles and a component to adjust the magnetic properties of the finally obtained magnetic iron powder are deposited on the surface of the iron oxyhydroxide before the iron oxyhydroxide is thermally reduced. It is usually done.
被着処理について述べると、形状保持成分としては、Ｐ
％５ｉＳＡｌ、Ｂ、Ｃｒ、Ｔｉ、Ｚｒ、Ｍｎ等の酸化物
、水酸化物、＠酸塩、炭酸塩等が用いられており、また
、磁気ｓ！４ＮＭ成分としてはＮ ｒ ｓ Ｃｕ 。Regarding the adhesion treatment, as a shape-retaining component, P
%5iSAl, B, Cr, Ti, Zr, Mn, etc. oxides, hydroxides, acid salts, carbonates, etc. are used, and magnetic s! The 4NM component is N r s Cu .
、Ｃｏ、Ｚｎ等の酸化物、水酸化物、硝酸塩、炭酸塩等
が用いられている。これらの化合物をオキシ水酸化鉄の
表面に被着させる方法としては、捕潰機等の混練機を用
いてオキシ水酸化鉄を含水ペースト状にして前記した被
着成分を添加混合する方法、或いは、オキシ水酸化鉄を
スラリー状態として該スラリーに被着成分の水可溶塩を
添加したのち苛性ソーダや酸でｐＨを調節して水可溶性
塩を酸化物又は水酸化物としてオキシ水酸化鉄の表面に
沈着させる方法、或いは、両者を組み合せた方法などが
知られている。, Co, Zn, etc., oxides, hydroxides, nitrates, carbonates, etc. are used. As a method for depositing these compounds on the surface of iron oxyhydroxide, there is a method in which iron oxyhydroxide is made into a water-containing paste using a kneader such as a crusher, and the above-mentioned depositing components are added and mixed. After making iron oxyhydroxide into a slurry state and adding a water-soluble salt as an adhering component to the slurry, the pH is adjusted with caustic soda or an acid, and the water-soluble salt is converted into an oxide or hydroxide to form the surface of iron oxyhydroxide. A method of depositing it on the surface of an organic material, or a method of combining both methods is known.
オキシ水酸化鉄もしくは被着処理を施したオキシ水酸化
鉄の加熱還元処理について述べると、オキシ水酸化鉄も
しくは被着処理を施したオキシ水酸化鉄を水素を用いて
３００〜５００°Ｃで直接還元しても良いが、水素によ
る還元の前に非還元性雰囲気下でオキシ水酸化鉄もしく
は被着処理を施したオキシ水酸化鉄を３００〜９００℃
で焼成したα−Ｆｅｚｅｓを主成分とする酸化物にして
から水素を用いて３００〜５００°Ｃで還元する方法が
焼きしまった磁性鉄粉を得やすいために好ましい。Regarding the thermal reduction treatment of iron oxyhydroxide or iron oxyhydroxide that has been subjected to a deposition treatment, iron oxyhydroxide or iron oxyhydroxide that has been subjected to a deposition treatment is directly heated at 300 to 500°C using hydrogen. However, before reduction with hydrogen, iron oxyhydroxide or iron oxyhydroxide that has been subjected to adhesion treatment is heated at 300 to 900°C in a non-reducing atmosphere.
A preferred method is to convert the fired α-Fezes into an oxide as a main component and then reduce it using hydrogen at 300 to 500°C because it is easy to obtain fired magnetic iron powder.
・［発明が解決すべき問題点］
磁性鉄粉としては、テープの出力アップの要請に対応し
て、高い配向性、充てん性を有すること、即ちテープに
した時に高いＢｒ値と高いＢｒ７８ｍ値をもたらす様な
粉が要求されている。また、テープの低ノイズ化の要請
に対応して、磁性鉄粉の微細化も要求されている。これ
を磁性鉄粉の比表面積で表わすと、現在の市販８ＩＩＩ
１１テープには約５０ｓ２／ｇの磁性鉄粉が使用されて
いるが、低ノイズ化の要求から６０＋＊”／ｇ曲後の微
細な磁性鉄粉が望まれている。また、低ノイズ化のため
には、微細化するだけでは十分でなく、微細化した磁性
鉄粉を高い充てん度でテープの磁性層に充てんせねばな
らない。・[Problems to be solved by the invention] In order to meet the demand for increased tape output, magnetic iron powder must have high orientation and filling properties, that is, it must have a high Br value and a high Br78m value when made into a tape. There is a demand for powder that yields In addition, in response to the demand for lower noise tapes, there is also a demand for finer magnetic iron powder. Expressing this in terms of the specific surface area of magnetic iron powder, the current commercially available 8III
11 tape uses magnetic iron powder of approximately 50s2/g, but due to the demand for low noise, fine magnetic iron powder of 60+*"/g is desired after being played. In order to achieve this, it is not enough to simply make the magnetic iron powder fine, but it is also necessary to fill the magnetic layer of the tape with a high degree of filling with fine magnetic iron powder.
以上の様に、磁性鉄粉に対する高配向性、商売てん性賦
与はテープ性能の向上にとってきわめて重要な特性であ
る。As described above, imparting high orientation and commercial tenacity to magnetic iron powder are extremely important characteristics for improving tape performance.
［問題点を解決するための手段］
本発明者は、磁性鉄粉に高配向性、商売てん性を賦与す
べく鋭意検討して本発明を完成させた。[Means for Solving the Problems] The present inventor has completed the present invention through intensive studies to impart high orientation and commercial viability to magnetic iron powder.
すなわち、本発明によれば、オキシ水酸化鉄の粒子表面
に酸化チタン及Ｖ／又は酸化ジルコニウムを被着させた
のち水素を用いて還元して磁性鉄粉を製造する方法にお
いて、被着に際して、チタン及び／又はジルコニウムの
金属アルコキシドをオキシ水酸化鉄の存在下に加水分解
して被着せしめることを特徴とする磁性鉄粉の製造方法
が提供される。That is, according to the present invention, in a method for producing magnetic iron powder by depositing titanium oxide and V/or zirconium oxide on the surface of iron oxyhydroxide particles and then reducing the particles using hydrogen, upon deposition, A method for producing magnetic iron powder is provided, which comprises hydrolyzing and depositing titanium and/or zirconium metal alkoxide in the presence of iron oxyhydroxide.
本発明において、チタンのアルコキシドは式Ｔｉ（ＯＲ
）４［式中、Ｒはアルキル残基］で表わされるアルキル
チタネートであって、Ｒがイソプロピル基、１１−ブチ
ル基又は２−エチルヘキシル基であるものが市場で入手
しやすいが、ＴｉＣ１，や１’ ｉ（Ｎ Ｏｘ）−をエ
チレングリコールに添加して８０°Ｃ以上に加熱するこ
とにより得られる′ｒｉのエチレングリフラードを用い
ても良い、−方、ジルコニウムのフルフキシトは式Ｚ
ｒ（ＯＲＬ［式中、Ｒはアルキル残基］で表わされるア
ルキルチタネートであって、Ｒがプロピル基のもの即ち
Ｚ ｒ（ｎ −Ｃ２Ｈ’ｔ Ｏ）４が市場で入手できる
が、Ｔｉの賜金と同様な処理で得られるＺｒのエチレン
グリフラードを用いることもできる。これらのチタンの
アルコキシド及びノルコニウムのアルコキシドは、それ
ぞれ単独でも使用できるが、チタン及びジルコニウムの
複合酸化物となるように両者を併用すると、特に効果的
である。In the present invention, the alkoxide of titanium is of the formula Ti(OR
) 4 [wherein R is an alkyl residue] Alkyl titanates in which R is an isopropyl group, 11-butyl group, or 2-ethylhexyl group are easily available on the market, but TiC1, 1 Ethylene glyfuride of 'ri obtained by adding 'i(NOx)- to ethylene glycol and heating to 80°C or above may be used.
An alkyl titanate represented by r(ORL [wherein R is an alkyl residue], in which R is a propyl group, that is, Z r(n -C2H't O)4) is available on the market, It is also possible to use Zr ethylene glyfuride obtained by the same treatment as .These titanium alkoxides and norconium alkoxides can be used alone, but they can be used in combination to form a composite oxide of titanium and zirconium. This is particularly effective.
Ｉ’ｌｌ化チタン及び酸化ツルコニツムは、鉄に対して
、鉄１００原子当りチタン及びジルコニウムの総和が１
０原子以下となるような量で被着せしめるのが良く、１
０原子より多いと、Ｂｒ値及びＢｒ７８ｍ値が小さくな
り好ましくない。これは、チタン及び／又はジルコニウ
ムのアルコキシドの加水分解によって生ずる酸化チタン
、酸化ジルコニウム及び／又はその複合酸化物を被着し
たオキシ水酸化鉄同志が凝集し、そのような被着オキシ
酸化鉄を出発原料として得られる磁性鉄粉が分散性や充
てん性に劣るためであろうと思われる。Titanium chloride and turconium oxide have a total of 1 titanium and zirconium per 100 atoms of iron.
It is best to deposit in an amount that is 0 atoms or less, and 1
If there are more than 0 atoms, the Br value and Br78m value become small, which is not preferable. This is because iron oxyhydroxides coated with titanium oxide, zirconium oxide, and/or their composite oxides, which are produced by hydrolysis of titanium and/or zirconium alkoxides, aggregate, and the deposited iron oxyhydroxides start to aggregate. This is probably because the magnetic iron powder obtained as a raw material has poor dispersibility and filling properties.
本発明においてチタン及び／又はジルコニウムのアルコ
キシドのオキシ水酸化鉄への被着方法としては、種々の
方法が採用できるが、簡便には、水を含んだオキシ水酸
化鉄のケーキとチタン及び／又はノルコニウムのアルコ
キシドを混練することで加水分解が同時に進行し、酸化
チタン及び酸化ノルコニウムを被着せしめることができ
る。また、チタン及び／又はシルコニツムのアルコキシ
ドをアルコールに希釈して上述の混練を行なうことによ
っても、或いは、多量のアルコール中にオキシ水酸化鉄
を分散せしめ、チタン及１／又はジルコニウムのアルコ
キシドと混合し加水分解のために適量の水を添加した後
にアルコールを濾過又は蒸発除去することによっても、
達成される。In the present invention, various methods can be adopted for adhering titanium and/or zirconium alkoxide to iron oxyhydroxide, but a simple method is to attach a cake of iron oxyhydroxide containing water and titanium and/or By kneading norconium alkoxide, hydrolysis proceeds simultaneously, allowing titanium oxide and norconium oxide to be deposited. Alternatively, by diluting titanium and/or silconium alkoxide with alcohol and performing the above-mentioned kneading, or by dispersing iron oxyhydroxide in a large amount of alcohol and mixing it with titanium and/or zirconium alkoxide. Also by adding an appropriate amount of water for hydrolysis and then removing the alcohol by filtration or evaporation.
achieved.
本発明においは、オキシ水酸化鉄を製造する方法、或い
は、被着後にオキシ水酸化鉄を焼成還元して磁性鉄粉と
する方法については特に制限がなく、公知の種々の方法
が採用できる０例えば、オキシ水酸化鉄の製法としては
、実施例に記載したデーサイトの合成例が、また、焼ａ
、ａ元については同じ（実施例に記載した処理例が、そ
れぞれ例示できる。In the present invention, there are no particular restrictions on the method of producing iron oxyhydroxide or the method of baking and reducing iron oxyhydroxide after deposition to obtain magnetic iron powder, and various known methods can be employed. For example, as a method for producing iron oxyhydroxide, the dacite synthesis example described in the Examples is also used.
, a element is the same (the processing examples described in the examples can be exemplified respectively).
［作用］
本発明においては、チタン及１／／又はジルコニウムの
金属アルコキシＶをオキシ水酸化鉄の存在下に加水分解
することによって被着せしめるので、オキシ水酸化鉄に
均一に酸化チタン及び／又は酸化ジルコニウムが被着さ
れ、特に特定の量の酸化チタン及Ｖ／又は酸化ジルコニ
ウムを被着せしめた場合′にはオキシ水酸化鉄同志が凝
集することがなく、従って、磁性鉄粉としたときに大き
なりｒ値及び大きなりｒ／Ｂｍ値をもつものが得られる
。[Function] In the present invention, since the metal alkoxy V of titanium and/or zirconium is deposited by hydrolyzing it in the presence of iron oxyhydroxide, titanium oxide and/or zirconium is uniformly applied to the iron oxyhydroxide. When zirconium oxide is deposited, especially when a specific amount of titanium oxide and V/or zirconium oxide is deposited, the iron oxyhydroxides do not aggregate together, so when made into magnetic iron powder, A large r value and a large r/Bm value are obtained.
［実施例１ 以下に、実施例を示し、本発明をさらに説明する。[Example 1 The present invention will be further explained below with reference to Examples.
ス１■生
（デーサイトの合成）
ＦｅＳＯ＜ ・７ＨｚＯの５０ｋｇ及Ｃ７Ｎ１５Ｏ，・
６Ｈ２０の０ 、５ ｋｇを水１０００Ｊ２に溶解し、
液温を４０℃に調整した（これを溶液Ｉとする）、また
、ＮａＯＨ４５ｋｇを水５００２に溶解し、液温を３５
°Ｃに調整した（これを溶液■とする）。Raw material (synthesis of dacite) 50 kg of FeSO<・7HzO and C7N15O,・
Dissolve 0.5 kg of 6H20 in 1000 J2 of water,
The liquid temperature was adjusted to 40°C (this is called solution I). Also, 45kg of NaOH was dissolved in 5002°C of water, and the liquid temperature was adjusted to 35°C.
The temperature was adjusted to °C (this will be referred to as solution ■).
、・ 攪拌機付き内容積３Ｍ３の反応器に溶液Ｉを仕込
み、次いで溶液■を一括投入し、５分間攪拌混合して中
和反応を完結させた後、１２Ｍ’／ｗｉｎの供給速度で
空気を吹込み酸化を行なうことにより、黄褐色のデーサ
イトが沈澱粒子として得られた。,・ Pour solution I into a reactor with an internal volume of 3M3 equipped with a stirrer, then add solution II all at once, stir and mix for 5 minutes to complete the neutralization reaction, and then blow air at a feed rate of 12M'/win. By carrying out the mixed oxidation, yellowish brown dacite was obtained as precipitated particles.
該デーサイトを水洗、Ｍ’過し、ン濾過ケーキの一部を
分取して分析したところ、該デーサイトは軸比１Ｇ、比
表面積８０ｍ２／ｇの針状粒子であった（該デーサイト
をＧｆと呼」：）。The dacite was washed with water, filtered with M', and a part of the filtered cake was collected and analyzed, and it was found that the dacite was acicular particles with an axial ratio of 1G and a specific surface area of 80m2/g (the dacite is called Gf” :).
（被着処理）
デーサイ）（ＧＩ）の水洗濾過ケーキ１０ｋｇ（デーサ
イト２ 、２ ｋｇ 、水７ 、８ ｋｇから成る）を
襠潰磯に投入した。Ｔｉ（ｉ−ＣｚＨ７０）−８，３と
及びＺ ｒ（ｎ−Ｃ、Ｈ７０）＋５．０ｇをブタ／−ル
５０−で希釈した液を、デーサイトケーキに１０分間か
けて徐々に添加し、次いで５時間混練した。この過程で
、ＴｉＯ２とＺｒＣ）２の複合酸化物で表面が被覆され
たデーサイトが得られた。(Adhesion Treatment) 10 kg of water-washed filter cake (consisting of 2 kg of dacite and 7 kg of water and 8 kg of water) of Dacite (GI) was put into a gristle. A solution prepared by diluting Ti(i-CzH70)-8,3 and Zr(n-C,H70)+5.0g with 50-butol was gradually added to the dacite cake over 10 minutes. The mixture was then kneaded for 5 hours. In this process, dacite whose surface was coated with a composite oxide of TiO2 and ZrC)2 was obtained.
引き続き、該処理ケーキを１１０℃にセットした乾燥機
に入れて乾燥し、乾燥ケーキを乳鉢で粉砕して４８メツ
シユ径より小さい顆粒に調整した。Subsequently, the treated cake was dried in a dryer set at 110°C, and the dried cake was ground in a mortar to form granules with a diameter smaller than 48 mesh.
この顆粒の一部を分取して分析したところ、該被着粉は
、重量比で、Ｎｉ／Ｆｅ＝０．９５／１００、Ｚｒ／Ｆ
ｅ＝１．０／Ｉ ００、Ｔ ｉ／ Ｆ ｅ＝ １ 、０
／１００であった。When a part of this granule was separated and analyzed, it was found that the adhering powder had a weight ratio of Ni/Fe=0.95/100, Zr/F
e=1.0/I 00, T i/F e= 1, 0
/100.
（１１元）
前記被着粉を空気中６５０℃で４時間加熱焼成し、その
１ ｋｇを攪拌流動床方式の反応器に仕込み、Ｎ２を３
ＯＮｍ’／Ｈで供給しつつ、反応器内の温度を４５０℃
に昇温しで３時ＩＩＶＩ維持した後、ガスをＮ２に切換
えて大気温度まで冷却した。(11 yuan) The adhered powder was heated and calcined in air at 650°C for 4 hours, 1 kg of it was charged into a stirred fluidized bed reactor, and N2 was added to the reactor for 3 hours.
While supplying at ONm'/H, the temperature inside the reactor was increased to 450℃.
After raising the temperature to 3:00 and maintaining it at 3:00, the gas was switched to N2 and the temperature was cooled to ambient temperature.
次に、還元粉を回収してトルエン中に浸漬した後、平皿
上に展開して空気と接触せしめ、還元粉末の表面に酸化
被膜を形１＆させて安定化し、最終的にドライの磁性鉄
粉約０ 、６ ｋｇを得た。Next, the reduced powder is collected and immersed in toluene, spread on a flat plate and brought into contact with air to form an oxide film on the surface of the reduced powder to stabilize it, and finally dry magnetic iron powder. Approximately 0.6 kg was obtained.
（磁性鉄粉の評価）
■ 粉体物性
粉体物性として、磁気特性及び比表面積にっき測定して
、次の値を得た。尚、磁気特性は振動試料型磁力計（Ｖ
ＳＭ）を用いて測定磁界１０ＫＯｅにて測定した。(Evaluation of magnetic iron powder) ■ Powder physical properties As powder physical properties, magnetic properties and specific surface area were measured and the following values were obtained. The magnetic properties were measured using a vibrating sample magnetometer (V
SM) at a measurement magnetic field of 10 KOe.
Ｈｅ １５３０ ００
σ３ １２６ ｅｍｕ／ｌｉｔσ「／σ
Ｓ Ｏ９５１
比表面積 ５３ ｍ”／ｇ
■ シート物性の測定
磁性鉄粉３００部、ＶＡＧＨ（塩・酸ビ系重合体、ＵＣ
Ｃ社製商品名）４５部、トルエン１７５部及びメチルイ
ソブチルケトン１７５ｆｆｌ！からなる混合物をボール
ミル中で２４時間攪拌分散した後、さらにタケネー）Ｌ
−１００７（ツレタンプレポリマー、武田薬品製商品名
）２部、トルエン１５部及びメチルイソブチルケトン１
５部をボールミル中に加え、１時間攪拌分散して磁性塗
料をｌ１１１！ｌ！シた。He 1530 00 σ3 126 emu/litσ "/σ
S O951 Specific surface area 53 m”/g ■Measurement of sheet properties 300 parts of magnetic iron powder, VAGH (salt/vinyl acid polymer, UC
(trade name manufactured by Company C) 45 parts, 175 parts of toluene, and 175 ffl of methyl isobutyl ketone! After stirring and dispersing the mixture in a ball mill for 24 hours,
2 parts of -1007 (Turethane prepolymer, trade name manufactured by Takeda Pharmaceutical Co., Ltd.), 15 parts of toluene, and 1 part of methyl isobutyl ketone
Add 5 parts to a ball mill and stir and disperse for 1 hour to form a magnetic paint. l! Shita.
得られた磁性塗料を、厚さ１６μ論のポリエステルフィ
ルムに乾燥厚が３μ鶴となる様に塗布し、磁界中で金属
粉末の配向を行なったのち乾燥し、次いで磁性層表面を
カレンダー処理により鏡面加工し、所定の幅に裁断して
検体を得た。The obtained magnetic paint was applied to a polyester film with a thickness of 16 μm so that the dry thickness was 3 μm, the metal powder was oriented in a magnetic field, and then dried. Then, the surface of the magnetic layer was calendered to a mirror finish. The samples were processed and cut to a predetermined width.
該検体をＶＳＭにて測定磁界１０ＫＯｅで測定して、次
のシート物性を得た。The sample was measured with a VSM at a measurement magnetic field of 10 KOe to obtain the following sheet properties.
Ｈｅ １４２０ ０ｅＢｒ
２４４０ ＧａｕｓｓＢｒ／Ｂｎ
０．８０
比」（劣り一
デーサイト（Ｇ １ ）のｔ濾過ケーキ１０ｋｇ（デー
サイト２．２ ｋｇ、水７ 、８ ｋｇ ）を補ｉ宵機
に投入した９Ｔｉ（ＮＯ＝）−８５，６ｇとＺｒ０（Ｎ
Ｏり２・２ Ｈ２Ｏ４（Ｌｉ２．とを混合したものを
デーサイトケーキに１０分間かけて添加し、次いで３時
間混練し、アンモニア水でｐＨを８に調整し、引き続き
２時間混練した。He 1420 0eBr
2440 GaussBr/Bn
9Ti (NO =) - 85.6 g of 10 kg of filtered cake (2.2 kg of dacite, 7.8 kg of water) (2.2 kg of dacite, 7.8 kg of water) of 0.80 ratio (inferior 1 dacite (G 1 )) was put into the evening machine. and Zr0(N
A mixture of O2.2 H2O4 (Li2.) was added to the dacite cake over 10 minutes, then kneaded for 3 hours, the pH was adjusted to 8 with aqueous ammonia, and then kneaded for 2 hours.
該処理ケーキを１１０°Ｃにセットした乾燥機に入れて
乾燥し、乾燥ケーキを乳鉢で粉砕して４８メツシユ径よ
り小さい顆粒に調整した。The treated cake was dried in a dryer set at 110°C, and the dried cake was ground in a mortar to form granules with a diameter smaller than 48 mesh.
この顆粒の一部を分取して分析したところ、該被着粉は
、重量比で、Ｎｉ／Ｆｃ＝０．９５／１００、Ｚｒ／Ｆ
ｅ−０，９５／ １００、Ｔｉ／Ｆｅ＝１゜０８／１０
０であった。When a part of these granules was separated and analyzed, it was found that the adhering powder had a weight ratio of Ni/Fc=0.95/100 and Zr/Fc.
e-0,95/100, Ti/Fe=1°08/10
It was 0.
以下、実施例と同一条件の抛作により、磁性鉄粉約０
、６ ｋｇを得た。Below, the magnetic iron powder was approximately 0
, 6 kg was obtained.
実施例と同一条件で測定した磁性鉄粉の粉体物性は、
Ｈｅ １４９０ ０ｅ
σ３ １２５ ｅｍｕ／ｇσｒ／σｓ
０．４８
比表面積 ５０ ｍ２７ｇ
であり、シート物性は、
Ｈｅ １４００ ０ｅＢｒ
２１５０ ＧａｕｓｓＢｒ／Ｂｍ
０．７４
であった。The powder properties of the magnetic iron powder measured under the same conditions as in the example are: He 1490 0e σ3 125 emu/gσr/σs
0.48 Specific surface area 50 m27g, sheet physical properties are He 1400 0eBr
2150 GaussBr/Bm
It was 0.74.
友鷲ｊ［ζ
被着工程ニオイテ、Ｔｉ（＋−ＣｚＨｔＯＬを８３８に
、Ｚ ｒ（ｎ −Ｃ３Ｈ？ Ｏ）−を１ ｏ、ｏｇに、
ブタノールを３００ｅ１に、それぞれ使用量を変更した
以外は、実施例と同条件の抛作を行ない、ドライの磁性
鉄粉約０ 、 Ｇ ｋｇを得た。Tomowashi j[ζ Adhesion process nitrite, Ti (+-CzHtOL to 838, Zr(n-C3H?O)- to 1 o, og,
Approximately 0.0 G kg of dry magnetic iron powder was obtained by carrying out cultivation under the same conditions as in Example except that the amount of butanol used was changed to 300 e1.
この被で粉の一部を分取して分析したところ、該被着粉
は、重量比で、Ｎｉ／Ｆｅ＝０．９５／１００、Ｚｒ／
Ｆｅ＝ ２．０１ ／ １００、Ｔｉ／Ｆｅ＝１０．
１／１００であった。これは、Ｆｅｌ ００原子あたり
、Ｚｒが０．６原子、Ｔｉ力弓２原子に相当する。When a part of the coated powder was separated and analyzed, it was found that the coated powder had a weight ratio of Ni/Fe=0.95/100, Zr/
Fe=2.01/100, Ti/Fe=10.
It was 1/100. This corresponds to 0.6 atoms of Zr and 2 atoms of Ti per 00 atoms of Fel.
粉体物性は、
Ｈｅ １４２０ ０ｅ
σｓ １０４ ｅｍｕ／ｇＬ：！ｒ／
σＳ Ｏ，４４
比表面積 ６４ ｍ２７Ｂ
であり、シート物性は、
Ｈｃ １３９０ ０ｅＢｒ
１４５０ ＧａｕｓｓＢｒ／Ｂｎ＋
０．６８
であった。The powder physical properties are He 1420 0e σs 104 emu/gL:! r/
σS O,44 Specific surface area 64 m27B, sheet physical properties are Hc 1390 0eBr
1450 GaussBr/Bn+
It was 0.68.
［効果］
本発明の方法は、商売てん高配向性の磁性鉄粉を与える
ので、工業的に極めて価値がある。[Effect] The method of the present invention provides commercially highly oriented magnetic iron powder, and is therefore extremely valuable industrially.
Claims (1)
酸化ジルコニウムを被着させたのち水素を用いて還元し
て磁性鉄粉を製造する方法において、チタン及び／又は
ジルコニウムの金属アルコキシドをオキシ水酸化鉄の存
在下に加水分解して被着せしめることを特徴とする磁性
鉄粉の製造方法。 ２、チタンのアルコキシド及びジルコニウムのアルコキ
シドを併用する特許請求の範囲第１項記載の方法。 ３、チタン及びジルコニウムの総和が鉄１００原子に対
して１０原子以下となるように被着せしめる特許請求の
範囲第１項または第２項記載の方法。[Claims] 1. In a method for producing magnetic iron powder by depositing titanium oxide and/or zirconium oxide on the surface of particles of iron oxyhydroxide and then reducing the particles with hydrogen, titanium and/or zirconium A method for producing magnetic iron powder, which comprises hydrolyzing and depositing a metal alkoxide in the presence of iron oxyhydroxide. 2. The method according to claim 1, in which titanium alkoxide and zirconium alkoxide are used in combination. 3. The method according to claim 1 or 2, wherein the total amount of titanium and zirconium is 10 atoms or less per 100 atoms of iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61146122A JPS633402A (en) | 1986-06-24 | 1986-06-24 | Manufacture of highly filled and highly oriented magnetic iron powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61146122A JPS633402A (en) | 1986-06-24 | 1986-06-24 | Manufacture of highly filled and highly oriented magnetic iron powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS633402A true JPS633402A (en) | 1988-01-08 |
Family
ID=15400647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61146122A Pending JPS633402A (en) | 1986-06-24 | 1986-06-24 | Manufacture of highly filled and highly oriented magnetic iron powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS633402A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010230U (en) * | 1983-06-30 | 1985-01-24 | 株式会社フジクラ | flat cable |
| EP0609897A3 (en) * | 1993-02-05 | 1994-08-24 | Nittetsu Mining Co., Ltd. | Powder having at least one layer and process for preparing the same |
-
1986
- 1986-06-24 JP JP61146122A patent/JPS633402A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010230U (en) * | 1983-06-30 | 1985-01-24 | 株式会社フジクラ | flat cable |
| JPH0117771Y2 (en) * | 1983-06-30 | 1989-05-24 | ||
| EP0609897A3 (en) * | 1993-02-05 | 1994-08-24 | Nittetsu Mining Co., Ltd. | Powder having at least one layer and process for preparing the same |
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