JPS59138312A - Manufacture of magnetic ferrous oxide powder containing cobalt - Google Patents
Manufacture of magnetic ferrous oxide powder containing cobaltInfo
- Publication number
- JPS59138312A JPS59138312A JP58012450A JP1245083A JPS59138312A JP S59138312 A JPS59138312 A JP S59138312A JP 58012450 A JP58012450 A JP 58012450A JP 1245083 A JP1245083 A JP 1245083A JP S59138312 A JPS59138312 A JP S59138312A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- cobalt
- oxide powder
- magnetic
- ferrous
- 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
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/706—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material
- G11B5/70626—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances
- G11B5/70642—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances iron oxides
- G11B5/70652—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances iron oxides gamma - Fe2 O3
- G11B5/70668—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances iron oxides gamma - Fe2 O3 containing a dopant
- G11B5/70673—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material containing non-metallic substances iron oxides gamma - Fe2 O3 containing a dopant containing Co
Abstract
Description
【発明の詳細な説明】
本発明は、磁気テープとして用騒た時の角形比、配向性
などの磁気特性に優れたコバルト含有磁性酸化鉄粉末の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cobalt-containing magnetic iron oxide powder that has excellent magnetic properties such as squareness and orientation when used as a magnetic tape.
磁性酸化鉄粉末にコバルト化合物を被着したコバルト含
有磁性酸化鉄粉末は高保磁力を有していることから、ビ
デオ用、オーディオ用などの磁気記録分野でさかんに利
用されているが、近年磁気記録媒体の高密度化への要求
は著しく諸性能の向上が一層要求されてきてしる。Cobalt-containing magnetic iron oxide powder, which is made by coating magnetic iron oxide powder with a cobalt compound, has a high coercive force and is therefore widely used in magnetic recording fields such as video and audio. The demand for higher densities of media has led to a significant demand for further improvements in various performances.
コバルト含有磁性酸化鉄粉末は、各種バインダーと混練
して磁性塗料を調整する際、バインダーへの濡れがわる
く、またそれ自体の磁性のため粒子相互の磁気凝集があ
って、バインダー中に均一に分散されに〈ｂという欠点
があった。When cobalt-containing magnetic iron oxide powder is kneaded with various binders to prepare magnetic paints, it is difficult to wet the binder, and due to its own magnetism, magnetic agglomeration of particles occurs, resulting in uniform dispersion in the binder. However, it had the disadvantage of <b>.
この対策として、機械的分散手段を用いて、凝集塊をほ
ぐす方法（特開昭５０−２２２９７゜特開昭５５〜１５
７２１６．特開昭５６−１０９０３）が試みられている
。しかし、この方法も機械的分散操作を止めると凝集が
はじまるため、根本的解決にはさらない。磁性酸化鉄粉
末の表面を無機化合物で処理する方法としては％Ｚｎ＃
Ｃ１ｌなどの無機塩の溶液に浸漬する方法（特開昭５５
−９６７１．特開昭５５−３９６５６．特開昭５５−３
９６５４）やＣＯイオン、 Ｍｎイオン、’ Ｆｅ （
＃）イオン及びアルカリの存在下に６０℃以上、沸点以
下の温度で加熱する方法（特開昭５３−１３２７９９）
が試みられている。さらに、磁性粉末の粒子表面を有機
バインダーとなじみのよ込界面活性剤などで磁性塗料調
製前に被覆する方法（特公昭５３−１９１２０．特開昭
５４−３７２９７゜特開昭５３−１４１１９６．特開昭
５４−８２３５４゜特開昭５４−８５３９７ ）や磁性
塗料調製時に分散剤として界面活性剤を添加する方法（
特開昭５５−１５１０６８ 、特開昭５５−１５１０６
９）が試みられている。As a countermeasure to this problem, a method of loosening the agglomerates using mechanical dispersion means (JP-A-50-22297°, JP-A-55-15
7216. JP-A-56-10903) has been attempted. However, this method does not provide a fundamental solution since aggregation begins when the mechanical dispersion operation is stopped. %Zn# is a method for treating the surface of magnetic iron oxide powder with an inorganic compound.
A method of immersion in a solution of an inorganic salt such as C1l (Japanese Patent Application Laid-open No. 1983
-9671. Japanese Patent Publication No. 55-39656. JP-A-55-3
9654), CO ions, Mn ions, 'Fe (
#) A method of heating in the presence of ions and alkali at a temperature of 60°C or higher and lower than the boiling point (Japanese Patent Application Laid-Open No. 132799/1983)
is being attempted. Furthermore, there is a method of coating the particle surface of the magnetic powder with a surfactant that is compatible with an organic binder before preparing the magnetic paint (Japanese Patent Publication No. 53-19120. 1985-82354゜ JP-A-54-85397) and a method of adding a surfactant as a dispersant during the preparation of magnetic paint (
JP-A-55-151068, JP-A-55-15106
9) has been attempted.
界面活性剤を粒子表面に被覆する方法として、水系、非
水系での浸漬処理、または粉末に直接スプレーする方法
があるが、この場合、有機バインダーとの混線中に被覆
された界面活性剤の脱着が起って効果が持続できなかっ
たシ、酢ビ塩ビ系樹脂での分散性は改良されても・ウレ
タン樹脂では効果が少なしといった樹脂選択性の問題が
ある。Methods for coating the surface of particles with surfactant include immersion treatment in aqueous or non-aqueous systems, or direct spraying on the powder, but in this case, the coated surfactant is desorbed during crosstalk with the organic binder. However, even though dispersibility with vinyl acetate and vinyl chloride resins has been improved, there are problems with resin selectivity, such as poor effectiveness with urethane resins.
また、有機バインダー中における磁性粉末の語れ全よく
するため、磁性塗料調製時に多量の界面活性剤を添加す
ると、テープの強度低下、ブリーディング、粉落ち等の
欠点がある。Furthermore, if a large amount of surfactant is added during the preparation of a magnetic coating material in order to improve the adhesion of the magnetic powder in the organic binder, there are disadvantages such as decreased strength of the tape, bleeding, and powder falling off.
本発明者等は、以前、コバルト含有磁性酸化鉄粉末の性
能の改善において、第１鉄化合物の存在が磁気特性の改
善、例えばＨｃの向上をもたらすが、同時に保磁力の経
時安定性の低下やこのものを用いて作成された磁気テー
プの角形比、配向性などの低下をもたらすことに注目し
て、上記欠点を解決すべく磁性酸化鉄粉末にコバルト化
合物と第１鉄化合物とを被着する方法の検討を重ねた結
果、磁性酸化鉄粉末に、まずｍｌ鉄化合物を被着し１次
込でこのものにコバルト化合物を被着したところ、保磁
力の経時安定性をはじめ、角形比、配向性１反転磁界分
布などの磁気特性が著しく改善されるという知見を樽、
特許部Ｈ（特願昭５７−２１５１７２）を行った。そこ
で前記方法において、更に検討を重ねた結果■第１鉄化
合物の被着時、■第１鉄化合物の被着後でコバルト化合
物を被着する前、■コバルト化合物の被着時、のいずれ
かの段階で特定の金属化合物を磁性酸化鉄粉末に含有さ
せると、有機バインダー中における分散性の指標ともな
る角形比、配向性などの磁気特性が更に改善されるとい
う知見を得た。また、磁性酸化鉄粉末に、まずコバルト
化合物を被着し、次いでこのものに第１鉄化合物を被着
する方法においても、■コバルト化合物の被九時、■コ
バルト化合物の被着後で第１鉄化合物を被着する前、■
第１鉄化合物の被着時、のいずれか段階で特定の金属化
合物を磁性酸化鉄粉末に含有させると、それを含有させ
ない場合に比べて角形比、配向性などの磁気特性が改善
されるという知見を得、これらの知見に基づいて本発明
を完成した。すなわち、本発明は、磁性酸化鉄粉末に、
まず第１鉄化合物を被着し、次いでこのものにコバルト
化合物を被着するか、或はまずコバルト化合物を被着し
、次いでこのものに第１鉄化合物を被着するかしてコバ
ルト含有磁性酸化鉄粉末を製造する方法において、Ｃｓ
ｓ Ｃｕ ＃Ａｇ、Ｍｇ、Ｃａ＊Ｓｒ、ＢａｅＺｎ、
ＡＡ！ ｓｓｃ、５ｉＴｉ ｅ Ｚｒ ｍ Ｓｎ ｍ
Ｐ ＃ Ｖ 、 Ｎｂ ＊ Ｓｂ ＃ Ｔａ ｍ Ｂｉ
＃ Ｃｒ、、 Ｍｏ・＊ Ｗ ｔ Ｍｌｌ 、 Ｆｅ
（１） ｓ Ｎｉ及びαの金属化合物の少くともｌ徨を
、の前記第１鉄化合物、コバルト化合物のうち前段で被
着するものについては、その被着時、■前記両化合物の
うち前段で被着するものについては、その被着後で後段
の化合物を被着する前、■前記両化合物のうち後段で被
着するものについては、その被着時、のいずれかの段階
で磁性酸化鉄粉末に含有させることヲ菅徴とするコバル
ト含有磁性酸化鉄粉末の製造方法である。In improving the performance of cobalt-containing magnetic iron oxide powder, the present inventors have previously found that the presence of ferrous compounds improves magnetic properties, for example, increases Hc, but at the same time reduces the stability of coercive force over time. Taking note of the fact that magnetic tapes made using this material deteriorate in squareness ratio, orientation, etc., a cobalt compound and a ferrous compound were coated on magnetic iron oxide powder in order to solve the above-mentioned drawbacks. As a result of repeated studies on the method, we found that by first coating a ml iron compound on magnetic iron oxide powder and then coating this with a cobalt compound in the first step, we were able to improve the stability of coercive force over time, squareness ratio, and orientation. The knowledge that the magnetic properties such as the magnetic field distribution and the reversal magnetic field distribution are significantly improved.
Patent Department H (Japanese Patent Application No. 57-215172). Therefore, as a result of further study on the above method, we found that either: ■ When the ferrous compound is deposited; ■ After the ferrous compound is deposited and before the cobalt compound is deposited; ■ When the cobalt compound is deposited. We have found that when a specific metal compound is incorporated into magnetic iron oxide powder at this stage, magnetic properties such as squareness ratio and orientation, which are indicators of dispersibility in an organic binder, are further improved. Also, in a method in which a cobalt compound is first applied to a magnetic iron oxide powder, and then a ferrous compound is applied to the powder, there is a method in which the cobalt compound is applied, and the first Before applying the iron compound,■
It is said that if a specific metal compound is included in the magnetic iron oxide powder at any stage during the deposition of the ferrous compound, the magnetic properties such as squareness ratio and orientation will be improved compared to when it is not included. The present invention was completed based on these findings. That is, the present invention provides magnetic iron oxide powder with
Cobalt-containing magnetism can be obtained by first depositing a ferrous compound and then depositing a cobalt compound thereon, or by first depositing a cobalt compound and then depositing a ferrous compound thereon. In the method of producing iron oxide powder, Cs
s Cu #Ag, Mg, Ca*Sr, BaeZn,
AA! ssc, 5iTi e Zr m Sn m
P#V, Nb*Sb#TamBi
#Cr,, Mo・* W t Mll, Fe
(1) When at least 1 of the Ni and α metal compounds are deposited in the first stage of the ferrous compounds and cobalt compounds, at the time of deposition, For those to be deposited, magnetic iron oxide is applied either after the deposition and before the subsequent compound is deposited, or for those to be deposited in the latter stage of both of the above compounds, at the time of deposition. This is a method for producing cobalt-containing magnetic iron oxide powder, the characteristic of which is to include it in the powder.
本発Ｂ月に用いられる磁性酸化鉄粉末としては、γ−ｐ
ｅ２０ｇ粉末、Ｆｅ５０＋粉末、γ−Ｆｅｚｅｓを適宜
の手段、例えば水素などの還元性気体中で部分還元する
ことで得られるベルトライド化合物粉末又はリンを含有
したこれらの粉末、例えばその前駆体である針状含水酸
化鉄（Ｌ、 ｌ：Ｉ、 １−Ｆｅ００Ｈ）の製造時に母
液中にオルトリン酸、メタリン酸、ボ１７ リン酸など
のり′ン酸類、亜１ノン酸類或はこれらのアルカリ金属
塩、アンモニウム塩などの水溶性塩を存在させる方法、
針状含水酸化鉄或はそれを加熱脱水したα−Ｆｅ２０．
に前述のＩＪン酸類、亜リン酸類或はそれらの水溶性塩
を被着処理中る方法などによシ得られるものに適宜通常
の熱処理を施した粉末が挙げられる。The magnetic iron oxide powder used in this issue is γ-p
Bertolide compound powder obtained by partially reducing e20g powder, Fe50+ powder, γ-Fezes in a reducing gas such as hydrogen, or these powders containing phosphorus, such as needles, which are precursors thereof. During the production of hydrated iron oxide (L, l:I, 1-Fe00H), phosphoric acids such as orthophosphoric acid, metaphosphoric acid, and boron-17 phosphoric acid, monononite acids, or alkali metal salts thereof, and ammonium are added to the mother liquor. A method of introducing water-soluble salts such as salt,
Acicular hydrated iron oxide or α-Fe20.
Examples include powders obtained by applying the above-mentioned IJ acids, phosphorous acids, or water-soluble salts thereof, and subjecting them to appropriate conventional heat treatment.
本発明方法におしては、磁性酸化鉄粉末にまず第１鉄化
合物を被着し、次いでとのもの（ニコバルト化合物を被
着するか、或はまずコ／（ルト化合物ｔ １１着し、次
いでこのものに第１鉄化合物を被着する。この方法とし
て、具体的には■磁性酸化鉄粉末をアルカリ水溶液に分
散させ、この中に第１鉄塩を添加し１次込でコバルト塩
を添加する方法、■前記粉末を第１鉄塩を含む水溶液に
分散させ、これにアルカリ水溶液を添加し１次いでコバ
ルト塩を添加する方法、■前記粉末を水或は弱アルカリ
水溶液に分散させ、この中にアルカリ水溶液と第１鉄塩
とを併行添加し、次いでコバルト塩を添加するか或はコ
バルト塩とアルカリ水溶液とを併行添加する方法、■前
記粉末をアルカリ水溶液に分散させ、この中にコバルト
塩を添加し、次いで第１鉄塩を添加する方法、■前記粉
末をコバルト塩を含む水溶液に分散させ、これにアルカ
リ水溶液を添加し、次込で第１鉄塩を添加する方法、■
前記粉末を水或は弱アルカリ水溶液に分散させ、この中
にアルカリ水溶液とコバルト塩とを併行添加し、次いで
第１鉄塩を添加するか或は第１鉄塩とアルカリ水溶液と
を併行添加する方法、などが挙げられる。また、これら
の方法において、アルカリ水溶液を必要に応じて適宜追
加添加してもよ−。In the method of the present invention, magnetic iron oxide powder is first coated with a ferrous compound and then coated with a nicobalt compound, or alternatively, a magnetic iron oxide powder is first coated with a ferrous compound and then coated with a ferrous compound. A ferrous compound is applied to the object.Specifically, this method is as follows: 1) Magnetic iron oxide powder is dispersed in an alkaline aqueous solution, a ferrous salt is added to this, and a cobalt salt is added as a primary addition. Method: (1) Dispersing the powder in an aqueous solution containing a ferrous salt, adding an alkaline aqueous solution thereto, and then adding a cobalt salt; (2) Dispersing the powder in water or a weak alkaline aqueous solution; A method of adding an alkaline aqueous solution and a ferrous salt in parallel, and then adding a cobalt salt, or a method of simultaneously adding a cobalt salt and an alkaline aqueous solution; (2) A method of dispersing the powder in an aqueous solution containing a cobalt salt, adding an aqueous alkali solution thereto, and then adding a ferrous salt;
The above powder is dispersed in water or a weak alkali aqueous solution, into which an aqueous alkali solution and a cobalt salt are simultaneously added, and then a ferrous salt is added, or a ferrous salt and an aqueous alkali solution are simultaneously added. methods, etc. In addition, in these methods, an alkaline aqueous solution may be additionally added as necessary.
こζで用いる第１鉄塩としては、硫酸第１鉄、硝酸第１
鉄、塩化第１鉄などの鉱酸の第１鉄塩が誉げられ、工業
的には硫酸第１鉄が好ましく、コバルト塩としては、コ
バルトの無機酸塩又は有機酸塩、例えば硫酸コバルト、
塩化コバルト、酢酸コバルトなどが挙げられ、工業的に
は硫酸コバルトが好ましい。アルカリとしてはアルカリ
金属文はアルカリ土類金属の水酸化物、酸化物或は炭酸
塩などが用いられ、例えば水酸化ナトリウム、水酸化カ
リウム、酸化ナトリウム、炭酸カルシウムなどが挙げら
れ、工業的には水酸化ナトＩＪウム、水酸化力ＩＪウム
が好ましい。The ferrous salts used in this ζ include ferrous sulfate and ferrous nitrate.
Ferrous salts of mineral acids such as iron and ferrous chloride are preferred, and ferrous sulfate is preferred industrially, and cobalt salts include inorganic or organic acid salts of cobalt, such as cobalt sulfate,
Examples include cobalt chloride and cobalt acetate, with cobalt sulfate being industrially preferred. As alkali metals, alkaline earth metal hydroxides, oxides, or carbonates are used, such as sodium hydroxide, potassium hydroxide, sodium oxide, and calcium carbonate. Sodium hydroxide and IJium hydroxide are preferred.
塩とアルカリとによって形成される第１鉄化合物又はコ
バルト化合物としては１例えば水利水酸化物、水利酸化
物、水オロオキシ水酸化物などが埜げらも、この第１鉄
化合物及びコバルト化合物の被着量は、商記磁性酸化鉄
粉末の佇ｅ量に対して前者はＦｅとして０．５〜３０重
量％、望ましくは１〜２０重量％であシ、後者はＣｏと
して０．１〜２０重量％、望ましくは０．５〜１０重号
％である。Examples of ferrous compounds or cobalt compounds formed by salts and alkalis include water hydroxides, water oxides, and water oxyhydroxides. The amount of the former is 0.5 to 30% by weight as Fe, preferably 1 to 20% by weight as Fe, and the latter is 0.1 to 20% by weight as Co, based on the appearance amount of the commercial magnetic iron oxide powder. %, preferably 0.5 to 10%.
本発明方法の第１鉄化合物とコバルト化合物の被着にお
いて、前記磁性酸化鉄粉末の懸濁スラリー濃度は１通常
２０〜２００ ｇ／１３ 、望ましくは５０〜１５０ｇ
／７であ）、被着反応温度は、通常沸点以下、望ましく
は５０℃以下であシ、被着時の雰囲気は通常第１鉄化合
物が実質的に酸化されなりような非酸化性である。雰囲
気を非酸化性にするためには、例えば反応容器を不活性
ガスで置換したシ１反応容器の溶液中に不活性ガスをバ
ブリングさせたシする。被着時の原料の添加時間は、被
着方法、ＯＨ基のモル濃度、被着反応温度などの条件の
違いにより異なシ（こいえなりが、一般的には１５分以
上必要であシ、望ましくは１〜２時間である。前記第１
鉄化合物或はコバルト化合物被着後の溶液中のＯＨ基濃
度（中和当量以上の遊離Ｏ■Ｉ基濃度）は通常０〜３モ
ル／ｌであシ、望ましくは０．５〜２モル／ｌである。In the deposition of the ferrous compound and cobalt compound in the method of the present invention, the suspension slurry concentration of the magnetic iron oxide powder is usually 20 to 200 g/13, preferably 50 to 150 g/13.
/7), the deposition reaction temperature is usually below the boiling point, preferably below 50°C, and the atmosphere during deposition is usually non-oxidizing so that the ferrous compound is not substantially oxidized. . In order to make the atmosphere non-oxidizing, for example, the reaction vessel is replaced with an inert gas.1 The inert gas is bubbled into the solution in the reaction vessel. The addition time of raw materials during deposition varies depending on the deposition method, molar concentration of OH groups, deposition reaction temperature, etc. The time period is preferably 1 to 2 hours.
The OH group concentration in the solution after the iron compound or cobalt compound has been deposited (concentration of free O and I groups above the neutralization equivalent) is usually 0 to 3 mol/l, preferably 0.5 to 2 mol/l. It is l.
両化合物の被着が終了した磁性酸化鉄粉末は、通常沸点
以下、例えば５０℃以下の温度でかつ非酸化性雰囲気で
熟成が行なわれるが、所望によシ５０〜９０℃で熟成す
ると磁気特性に良す影響金与える場合もある。The magnetic iron oxide powder that has been coated with both compounds is usually aged at a temperature below the boiling point, for example below 50°C, in a non-oxidizing atmosphere, but if desired, aging at 50 to 90°C improves the magnetic properties. It can also have a positive impact on money.
熟成時間は通常０１〜１０時間である。Aging time is usually 01 to 10 hours.
本発明方法におして、第１鉄化合物とコバルト化合物の
被着工程の間に、所望により非酸化性雰囲気中で熱処理
を施してもより、前記固化合物の被着が終了し、スラリ
ーを熟成した後には通常熱処理が施される。これらの熱
処理の方法としては、例えば■被着スラリーをオートク
レーブ中で１００〜２５０℃、望ましくは１００〜−２
００℃で湿式加熱処理する方法、■被着スラリーを濾過
、水洗して湿ケーキを再び水中に分散させてスラリーと
し、このスラリーをオートクレーブ中で１００〜２５０
℃、望ましくはｉｏｏ〜２００℃で湿式加熱処理する方
法、■前記湿ケーキを６０〜ｂ
で水蒸気の存在下に加熱処理する方法、■前記湿ケーキ
を３０〜２００℃で乾燥する方法、■前記乾燥品を１０
０〜３００℃、望ましくは１００〜２００℃で乾式加熱
処理する方法などが挙げられる。In the method of the present invention, if desired, heat treatment may be performed in a non-oxidizing atmosphere between the steps of depositing the ferrous compound and the cobalt compound, so that the deposition of the solid compound is completed and the slurry is aged. This is usually followed by heat treatment. As a method for these heat treatments, for example,
A method of wet heat treatment at 00°C. ■Filter the adhered slurry, wash it with water, disperse the wet cake in water again to make a slurry, and put this slurry in an autoclave to a temperature of 100 to 250°C.
1. A method of wet heat treatment at a temperature of 60 to 200 °C, preferably 200 °C, 2) A method of drying the wet cake at a temperature of 30 to 200 °C, 2) A method of drying the wet cake at a temperature of 30 to 200 °C; 10 dried items
Examples include a dry heat treatment method at 0 to 300°C, preferably 100 to 200°C.
本発明方法においては、■第１鉄化合物、コバルト化合
物のうち前段で被着するものについて、その被着時、■
前記両化合物のうち前段で被Ｍ＋るものについて、その
被着後で後段の化合物を被Ｍする前、■前記両化合物の
うち後段で被着するものについて、その被着時のｂずれ
かの段階で前述の特定の金属化合物を磁性酸化鉄粉末に
含有させる。この方法として具体的には、前述のコバル
ト化合物、第１鉄化合物の具体的被着方法■〜■におい
て、■被着方法■〜■の第１鉄化合物を被着するとき特
定の金属化合物を共存させる方法或は被着方法■〜■の
コバルト化合物を被着するとき特定の金属化合物を共存
させる方法、＠被着方法■〜■の第１鉄化合物を被着・
熟成した後熱処理を施し、このものに特定の金属化合物
を被着する方法或は被着方法■〜■のコバルト化合物を
被着・熟成した後熱処理ｔ−施し、このものに特定の金
属化合物を被着する方法、θ被着方法■〜■のコバルト
化合物を被着するとき特定の金属化合物全共存させる方
法或は被着方法■〜■の第１鉄化合物を被着するとき特
定の金属化合物を共存させる方法、な、どが挙げられる
。上記■〜θの方法において少くとも１つの方法を採用
すればよ−が、望ましくは２〜３の方法を組合せる。こ
こでｂう特定の金属化合物としては、水利水酸化物、水
利酸化物、水和オキシ水酸化物などが挙げられ、この特
定の金属化合物の含有量は、磁性酸化鉄粉末の全鉄量に
対して通常ｏ、ｏｉ〜２゜重量％、望ましくは０．０５
〜５重量％である。In the method of the present invention, (1) among the ferrous compounds and cobalt compounds to be deposited in the previous step, (1)
For the compound to be M+ applied in the first stage of both of the above compounds, before applying M+ to the compound in the latter stage; In this step, the above-mentioned specific metal compound is incorporated into the magnetic iron oxide powder. Specifically, in the above-mentioned specific methods for depositing cobalt compounds and ferrous compounds ■ to ■, when depositing the ferrous compounds of ■deposition methods ■ to ■, a specific metal compound is used. Co-existence method or deposition method When depositing the cobalt compound of ■~■, method of coexisting a specific metal compound, @deposition method of depositing the ferrous compound of ■~■
A method of applying a heat treatment after ripening, and then applying a specific metal compound to this product, or a method of applying a cobalt compound according to method ① to ① and aging, then applying a heat treatment to this product, and applying a specific metal compound to this product. Deposition method, θDeposition method When depositing a cobalt compound according to ■~■, a method in which all of the specific metal compounds coexist, or when depositing a ferrous compound according to deposition methods ■~■, a specific metal compound Examples include ways to coexist. At least one of the methods (1) to (theta) above may be employed, but two or three methods are preferably combined. Specific metal compounds mentioned here include water-use hydroxides, water-use oxides, hydrated oxyhydroxides, etc., and the content of this specific metal compound is determined based on the total iron content of the magnetic iron oxide powder. Usually o, oi to 2% by weight, preferably 0.05
~5% by weight.
前記方法に＞ｌｘで、特定の金属化合物を含有させるに
は、特定の金属塩を酸或はアルカリで中和した）、加水
分解したシして行うことができ、これらの場合スラＩＪ
ｉよく攪拌し、被着対象物の分散状態を良好にして
おくことが好ましｌのはもちろんのことである。またス
ラリーの温度、ＰＨ％便用するアルカリ土類金属塩の濃
度、添加速度などは含有させる方法に応じて適宜調整す
ればよい。In order to incorporate a specific metal compound at >lx into the above method, it can be carried out by neutralizing the specific metal salt with an acid or alkali) or hydrolyzing it; in these cases, sura IJ
It goes without saying that it is preferable to stir well and keep the object to be well dispersed. Further, the temperature of the slurry, the concentration of the alkaline earth metal salt (PH%), the addition rate, etc. may be adjusted as appropriate depending on the method of containing the slurry.
本発明方法における特定の金属化合物を含有させる方法
において、特定の金属化合物を含有させた後前述のよう
な熱処理を施しても施さ彦くてもよい。これらの熱処理
は、特定の企画化合物、第１鉄化合物、コバルト化合物
が磁性酸化鉄の粒子内部に拡散しないように配慮する必
要がある。In the method of incorporating a specific metal compound in the method of the present invention, the above-described heat treatment may or may not be performed after incorporating the specific metal compound. In these heat treatments, it is necessary to take care to prevent specific planned compounds, ferrous compounds, and cobalt compounds from diffusing inside the particles of magnetic iron oxide.
本発明方法によってあられる特定の金属化合物全含有す
るコバルト含有磁性酸化鉄粉末は、磁気特性が改善され
、この酸化鉄粉末を用いて作成された磁気テープは、一
層角形比、配向性などの磁気特性が改善さｎる。The cobalt-containing magnetic iron oxide powder containing all of the specific metal compounds produced by the method of the present invention has improved magnetic properties, and magnetic tapes made using this iron oxide powder have better magnetic properties such as squareness and orientation. The characteristics are improved.
本発明方法により有機バインダー中における分散性の指
標ともなる角形比、配向性などの磁気特性が改善−され
る理由は必ずしも明確でな−か、■特定の金属化合物を
磁性酸化鉄粉末に含有させることによシ、有機バインダ
ー中における磁気凝集が生じにくくなる、■磁性酸化鉄
粉木と有機バインダーとの親和性が高まり、濡れがよぐ
なる、ことなどが推定される。The reason why magnetic properties such as squareness ratio and orientation, which are indicators of dispersibility in an organic binder, are improved by the method of the present invention is not necessarily clear. In particular, it is presumed that magnetic aggregation in the organic binder becomes less likely to occur, and (1) the affinity between the magnetic iron oxide powder wood and the organic binder increases, resulting in better wetting.
以下の実施例及び比較例によシ、本発明をよシ詳しく理
解できるであろう。The invention will be understood in more detail from the following examples and comparative examples.
実施例１〜９
出発物質として保磁力Ｈｅ ｐ ３９９０ ｅ ｈ Ｐ
含有ｉ０．６３重景％のｒ−Ｆｅ２０ｓｔ−用い、該γ
−Ｆｅ、０３１００ｇ全水１１に分散させてスラリーと
し、室温（３０℃）で液中にＮ２ガスを吹き込みながら
、下記第１表に示す所定量の１０モルΔのＮａＯＨ水溶
液を加え、次いで０．９０モル／ｌの硫酸第１鉄水溶液
１６８ゴ或はこのものと下記に示す所定量の金属塩との
混合溶液を加えて攪拌し、さらに下記に示す所定分の１
０モル４のＮａＯＨ水溶液を加え、或はさらに下記に示
す所定量の金属塩を加えた。次いで０．８５モル４の硫
酸コバルト水溶液７０ｍ１或はこのものと下記に示す所
定量の金属塩を加えて室温（３０℃）で５時間攪拌した
。このスラリー′ｆｒ、瀘過、水洗し、得られた湿ケー
キを別容器に入れた水と共にオートクレーブに入れて％
Ｎ、ガスで置換した後密閉し、１３０℃で６時間水蒸気
の存在下に加熱処理した。Examples 1-9 Coercive force He p 3990 e h P as starting material
Using r-Fe20st- containing i0.63%, the γ
-Fe, 03100g was dispersed in total water 11 to form a slurry, and while blowing N2 gas into the liquid at room temperature (30°C), a predetermined amount of 10 mol Δ NaOH aqueous solution shown in Table 1 below was added, and then 0. Add a 90 mol/l ferrous sulfate aqueous solution 168g or a mixed solution of this and a predetermined amount of a metal salt shown below, stir, and then add a predetermined amount of 168 g as shown below.
A 0 mol 4 NaOH aqueous solution was added, or a predetermined amount of a metal salt as shown below was further added. Next, 70 ml of a 0.85 mol 4 cobalt sulfate aqueous solution or this solution and a predetermined amount of the metal salt shown below were added and stirred at room temperature (30° C.) for 5 hours. This slurry'fr was filtered, washed with water, and the resulting wet cake was placed in an autoclave with water in a separate container.
After purging with nitrogen and gas, the reactor was sealed and heat-treated at 130° C. for 6 hours in the presence of steam.
処理後Ｎ２ガス中で１２０℃で乾燥し、目的のそれぞれ
のコバルト含有磁性酸化鉄粉末（Ａ）〜（Ｉ）を得た。After the treatment, it was dried at 120° C. in N2 gas to obtain desired cobalt-containing magnetic iron oxide powders (A) to (I).
比較例１゜
実施例１〜９において、特定の金属塩を加えガいこと以
外は同様にして、コバルト含有磁性酸化鉄粉末（Ｊ）を
得た。Comparative Example 1 A cobalt-containing magnetic iron oxide powder (J) was obtained in the same manner as in Examples 1 to 9, except that a specific metal salt was added.
第１表
上記サンプル■〜（Ｊ）について、通常の方法によシ保
磁力盆側足し、結果を第２表（二示ｔさらに、サンプル
（４）〜（Ｊ）について、下記の配合割合に従って配合
物を調製し、ボールミルで混練して磁性塗料を製造した
。For the above samples (4) to (J) in Table 1, add the coercive force to the side of the coercive force basin in the usual manner, and record the results in Table 2 (2). A blend was prepared and kneaded in a ball mill to produce a magnetic paint.
（１）コバルト含有磁性酸化鉄粉末 ２４重量部（
２）ポリウレタン樹脂 ５ “（３）
塩ビー酢ビ共重合体 １．２〃（４）分散
剤 ０．５ “（５）混合
溶剤（トルエンＡＥＫ＝１／１）６９．５ “次い
で、各々の磁性塗料をポリエステルフィルムに通常の方
法により塗布、配向した後乾燥して約９μの磁性塗膜を
有する磁気テープを作成した。それぞれのテープについ
て通常の方法によシ、保磁力（Ｈｅ）、飽和磁束密度（
Ｂｍ）、角形比（Ｂ ｒ ／ Ｂ ｍ）、配向性（ＯＲ
）を測足した結果を第２表に示す。(1) Cobalt-containing magnetic iron oxide powder 24 parts by weight (
2) Polyurethane resin 5" (3)
Vinyl chloride-vinyl acetate copolymer 1.2 (4) Dispersant 0.5 (5) Mixed solvent (Toluene AEK = 1/1) 69.5 Next, apply each magnetic paint to a polyester film using the usual method. A magnetic tape having a magnetic coating film of approximately 9 μm was prepared by coating, orienting and drying the magnetic tape. For each tape, the coercive force (He), saturation magnetic flux density (
Bm), squareness ratio (B r / B m), orientation (OR
) are shown in Table 2.
・第２表
実施例１０〜１２
前記実施例１〜９で用込たものと同じ）−Ｆｅｚｅ３１
００ｇｉ水１１に分散させてスラリーとし、室温（３０
℃）で液中にＮ２ガスを吹き込みながら、 ０．８５
モル／Ｉｔの硫酸コバルト水溶液７０ｍ或はこのものと
下記第３表に示す所定量の金属塩との混合溶液を加えて
攪拌し、さらに下記ｉ二元す所定量の１０モル／ｌのＮ
ａＯＨ水溶液を加えて攪拌し、或はさらに下記に示す所
定量の金属塩を加えた。次すて０．９０モル刀の硫酸第
１鉄水溶液１６８ｄ或はこのものと下記に示す所定量の
金属塩を加えて室温（３０℃）で５時間攪拌した。この
スラリーをｒ過、水洗し、得られた湿ケーキを別容器に
入れた水と共にオートクレーブに入れて、Ｎ ２ガスで
置換した後密閉し、１３０℃で６時間水蒸気の存在下に
加熱処理した。処理後Ｎ２ガス中で１２０℃で乾燥し、
目的のそれぞれのコバルト含有磁性酸化鉄粉末■〜Ｍを
得た。・Table 2 Examples 10 to 12 Same as those used in Examples 1 to 9) -Feze31
Disperse in 110 g of water to make a slurry and keep it at room temperature (30 g
0.85 while blowing N2 gas into the liquid at
70 ml of cobalt sulfate aqueous solution of mol/It or a mixed solution of this and a prescribed amount of metal salt shown in Table 3 below was added and stirred, and further a prescribed amount of 10 mol/liter of N
An aOH aqueous solution was added and stirred, or a predetermined amount of metal salt shown below was further added. Next, 168 d of a 0.90 molar ferrous sulfate aqueous solution or this solution and a predetermined amount of the metal salt shown below were added and stirred at room temperature (30° C.) for 5 hours. This slurry was filtered and washed with water, and the resulting wet cake was placed in an autoclave with water in a separate container, purged with N2 gas, sealed, and heat-treated in the presence of steam at 130°C for 6 hours. . After treatment, dry at 120°C in N2 gas,
The desired cobalt-containing magnetic iron oxide powders (1) to (M) were obtained.
比較例２゜
実施例１０〜１２におりて、特定の金属塩全加えないこ
と以外は同様にして、コバルト含有磁性酸化鉄粉末（へ
）を得た。Comparative Example 2 A cobalt-containing magnetic iron oxide powder was obtained in the same manner as in Examples 10 to 12, except that no specific metal salt was added.
第３表
上記サンプル■〜（ト）につ−て、通常の方法によ、シ
保磁力を測定し、結果を第４表に示ｔサラに、サンプル
（Ｋ）−／（Ｎ）について、前記と同様の方法によシ、
保磁力（Ｈｅ）、飽和磁束密度（Ｂｍ）、角形比（Ｂｒ
／Ｂｍ ）、配向性（ＯＲ）を測定した結果を第４表に
示す。Table 3 The coercive forces of the above samples (1) to (7) were measured using the usual method, and the results are shown in Table 4.For samples (K)-/(N), By the same method as above,
Coercive force (He), saturation magnetic flux density (Bm), squareness ratio (Br
/Bm) and orientation (OR) are shown in Table 4.
第４表
手続補正書（自発）
昭和５８年２月 ４日
特許庁長官 若 杉 和 夫 殿どツーＯ／
２す、ｒｏ
１、事件の表示 昭和５８年１月２８日提出の特許
願２、 発明の名称 コバルト含有磁性酸化鉄粉末
の製造方法３、補正をする者
事件との関係 特許出願人
５、補正の内容
（１）明細書中、ｔ５２頁第１５行「調整」を「調製」
と訂正する。Table 4 Procedural Amendment (Voluntary) February 4, 1981 Commissioner of the Patent Office Kazuo Wakasugi Tonodo 2 O/
2.RO 1. Indication of case: Patent application 2, filed on January 28, 1988. Title of invention: Process for producing cobalt-containing magnetic iron oxide powder 3. Person making the amendment. Relationship with the case: Patent applicant 5: Amendment. Contents (1) In the specification, page t52, line 15, "adjustment" is replaced by "preparation"
I am corrected.
（２）同、第２頁第１６行および第１７行「まだそれ自
体の磁性のため粒子相互の磁気凝集があって、」を［ま
たそれ自体の持つ磁性のため粒子相互ｌｊの磁゛気凝集
が生じて」と訂正する。(2) Ibid., page 2, lines 16 and 17, "There is still magnetic cohesion between the particles due to their own magnetism.""Agglomerationoccurs," he corrected.
（３）同、第１２頁第１８行［被着・熟成した後熱処理
を施し、」を「被着した後」と訂正する。(3) Same, page 12, line 18, ``After being applied and aged, heat treatment is applied'' is corrected to ``after being applied.''
（４）同、第１２頁第１９行「被着する方法」を「被着
し、次り１でコバルト化合物を被着する方法」と訂正す
る。(4) Same, page 12, line 19, "Method of depositing" is corrected to "Method of depositing and then depositing a cobalt compound in step 1."
（５）同、第１２頁第２０行および第１３頁第１行「被
着・熟成した後熱処理を施し、」を「被着した後」と訂
正する。(5) In the same article, page 12, line 20 and page 13, line 1, ``After being applied and aged, heat treatment is applied'' is corrected to ``after being applied.''
（６）同、第１３頁第２行「被着する方法」を「被着し
、次いで第１鉄化合物を被着する方法」と訂正する。(6) Same, page 13, line 2, "Method of depositing" is corrected to "Method of depositing and then depositing a ferrous compound."
Claims (1)
このものにコバルト化合物を被着するか、或はまずコバ
ルト化合物を被層し、次いでこのものに第１鉄化合物を
被着するかしてコバルト含有磁性酸化鉄粉末を製造する
方法において、Ｃｓ 、 Ｃｕ ＃ Ａｇ ＃ Ｍｇ
＃ Ｃａ 、 Ｓｒ、Ｂａ＃ Ｚｎ ａ Ａ７ ＃
Ｓｃ 、 Ｓｉ ＊ Ｔｉ ｔ Ｚｒ ｅ Ｓｎ ｊＰ
ｍ Ｖ ＃ Ｎｂ＊ Ｓｂ ＊ Ｔａ 、 Ｂｉ＃
Ｃｒ 、 ＩＶｌｏ。 Ｗ ＃ Ｍｎ ＃ Ｆｅ（ＩＩ） ｍ Ｎｉ及びＣｅの
金属化合物の少くとも１棟を、次のいずれかの段階で磁
性酸化鉄粉末に含有させることを特徴とするコバルト含
有磁性酸化鉄粉末の製造方法。 ■、 前記両化合物のうち前段で破着するものについて
は、その被着時。 ２、 前記両化合物のうち前段で被着するものについて
は、その被着後で後段の化合物を被着する前。 ３、 前記両化合物のうち後段で被着するものについて
は、その被着時。[Scope of Claims] A magnetic iron oxide powder is first coated with a ferrous compound and then a cobalt compound is coated thereon, or alternatively, a cobalt compound is first coated and then a first iron compound is coated on the powder. In a method for producing cobalt-containing magnetic iron oxide powder by depositing an iron compound, Cs, Cu #Ag #Mg
#Ca, Sr, Ba# Zn a A7 #
Sc, Si * Ti t Zr e Sn jP
m V # Nb* Sb * Ta, Bi#
Cr, IVlo. W # Mn # Fe(II) m A method for producing a cobalt-containing magnetic iron oxide powder, which comprises incorporating at least one of the metal compounds of Ni and Ce into the magnetic iron oxide powder in any of the following steps. . (2) For those of the above-mentioned compounds that break in the first stage, at the time of adhesion. 2. For those of the above compounds to be deposited in the first stage, after that and before the second stage compound is deposited. 3. For those of the above-mentioned compounds that will be deposited later, at the time of deposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58012450A JPS59138312A (en) | 1983-01-28 | 1983-01-28 | Manufacture of magnetic ferrous oxide powder containing cobalt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58012450A JPS59138312A (en) | 1983-01-28 | 1983-01-28 | Manufacture of magnetic ferrous oxide powder containing cobalt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59138312A true JPS59138312A (en) | 1984-08-08 |
| JPH0425686B2 JPH0425686B2 (en) | 1992-05-01 |
Family
ID=11805670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58012450A Granted JPS59138312A (en) | 1983-01-28 | 1983-01-28 | Manufacture of magnetic ferrous oxide powder containing cobalt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59138312A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638223A (en) * | 1986-06-27 | 1988-01-14 | Showa Denko Kk | Production of ferromagnetic powder for magnetic recording |
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|---|---|---|---|---|
| JPS5085612A (en) * | 1973-11-30 | 1975-07-10 | ||
| JPS54106895A (en) * | 1978-02-08 | 1979-08-22 | Fuji Photo Film Co Ltd | Ferromagnetic powder |
| JPS55141712A (en) * | 1979-04-23 | 1980-11-05 | Basf Ag | Acicular magnetic iron oxide and method for producing same |
| JPS56104721A (en) * | 1980-01-22 | 1981-08-20 | Tdk Corp | Preparation of magnetic powder |
-
1983
- 1983-01-28 JP JP58012450A patent/JPS59138312A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5085612A (en) * | 1973-11-30 | 1975-07-10 | ||
| JPS54106895A (en) * | 1978-02-08 | 1979-08-22 | Fuji Photo Film Co Ltd | Ferromagnetic powder |
| JPS55141712A (en) * | 1979-04-23 | 1980-11-05 | Basf Ag | Acicular magnetic iron oxide and method for producing same |
| JPS56104721A (en) * | 1980-01-22 | 1981-08-20 | Tdk Corp | Preparation of magnetic powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638223A (en) * | 1986-06-27 | 1988-01-14 | Showa Denko Kk | Production of ferromagnetic powder for magnetic recording |
| JPH0351660B2 (en) * | 1986-06-27 | 1991-08-07 | Showa Denko Kk |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0425686B2 (en) | 1992-05-01 |
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