JPH0372014B2 - - Google Patents
Info
- Publication number
- JPH0372014B2 JPH0372014B2 JP61018834A JP1883486A JPH0372014B2 JP H0372014 B2 JPH0372014 B2 JP H0372014B2 JP 61018834 A JP61018834 A JP 61018834A JP 1883486 A JP1883486 A JP 1883486A JP H0372014 B2 JPH0372014 B2 JP H0372014B2
- Authority
- JP
- Japan
- Prior art keywords
- plate
- shaped
- zinc
- ferrite
- fine particles
- 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.)
- Expired - Lifetime
Links
- 229910000859 α-Fe Inorganic materials 0.000 claims description 70
- 239000002245 particle Substances 0.000 claims description 61
- 239000010419 fine particle Substances 0.000 claims description 52
- 239000011701 zinc Substances 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 20
- 229940007718 zinc hydroxide Drugs 0.000 claims description 20
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 230000005291 magnetic effect Effects 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000006104 solid solution Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 8
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000005415 magnetization Effects 0.000 description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、粒子表面に亜鉛が固溶している板状
Baフエライト微粒子からなる磁気記録用板状Ba
フエライト微粒子粉末及びその製造法である。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides plate-like particles in which zinc is solidly dissolved on the particle surface.
Platy Ba for magnetic recording made of fine Ba ferrite particles
A ferrite fine particle powder and a method for producing the same.
近年、例えば、特開昭55−86103号公報にも述
べられている通り、大きな磁化値と適当な抗磁力
とを有し、且つ、適当な平均粒度を有する強磁性
の非針状粒子が記録用磁性材料、特に垂直磁気記
録用磁性材料として要望されつつある。
In recent years, for example, as described in JP-A No. 55-86103, ferromagnetic non-acicular particles having a large magnetization value, an appropriate coercive force, and an appropriate average particle size have been recorded. It is increasingly being desired as a magnetic material for applications, especially for perpendicular magnetic recording.
一般に、強磁性の非針状粒子としてはBaフエ
ライト粒子がよく知られている。 Generally, Ba ferrite particles are well known as ferromagnetic non-acicular particles.
従来から板状Baフエライトの製造法の一つと
して、BaイオンとFe（）とが含まれたアルカリ
性懸濁液を反応装置としてオートクレーブを用い
て水熱処理する方法（以下、これを単に水熱合成
法という。）が知られている。 Conventionally, one of the methods for producing plate-shaped Ba ferrite is to hydrothermally treat an alkaline suspension containing Ba ions and Fe() using an autoclave as a reaction device (hereinafter referred to simply as hydrothermal synthesis). ) is known.
先ず、磁気特性について言えば、磁気記録用板
状Baフエライト粒子粉末の磁化値は、出来るだ
け大きいことが必要であり、この事実は、例えば
特開昭56−149328号公報の「……磁気記録媒体材
料に使われるマグネトプランバイトフエライトに
ついては可能な限り大きな飽和磁化……が要求さ
れる。」と記載されている通りである。 First, regarding magnetic properties, it is necessary that the magnetization value of plate-shaped Ba ferrite particles for magnetic recording be as large as possible. The magnetoplumbite ferrite used as a media material is required to have as large a saturation magnetization as possible.''
また、抗磁力は、一般に300〜1000Oe程度のも
のが要求されており、上記水熱合成法において生
成Baフエライト微粒子粉末の抗磁力を低減させ
適当な抗磁力とする為にフエライト中のFe（）
の一部をTi（）及びCo（）又はCo（）並び
にMn、Zn、Ni等の２価の金属イオンＭ（）で
置換することが提案されている。 In addition, a coercive force of about 300 to 1000 Oe is generally required, and Fe ()
It has been proposed to replace a part of the ions with Ti() and Co() or Co() and divalent metal ions M() such as Mn, Zn, Ni, etc.
次に、磁気記録用板状Baフエライト微粒子粉
末の粒度について言えば、出来るだけ微細な粒
子、殊に、0.3μｍ以下であることが要求されてい
る。 Next, regarding the particle size of the plate-shaped Ba ferrite fine particle powder for magnetic recording, it is required that the particles be as fine as possible, especially 0.3 μm or less.
この事実は、例えば、特開昭56−125219号公報
の「……垂直磁化記録が面内記録に対して、その
有為性が明らかとなるのは、記録波長が1μｍ以
下の領域である。しかしてこの波長領域で十分な
記録・再生を行うためには、上記フエライトの結
晶粒径は、略0.3μｍ以下が望ましい。しかし、
0.01μｍ程度となると、所望の強磁性を呈しない
ため、適切な結晶粒径としては0.01〜0.3μｍ程度
が要求される。」なる記載等の通りである。 This fact can be seen, for example, in Japanese Patent Application Laid-Open No. 125219/1983, "...The significance of perpendicular magnetization recording over longitudinal recording becomes clear in the region where the recording wavelength is 1 μm or less. However, in order to perform sufficient recording and reproduction in this wavelength range, the crystal grain size of the ferrite is preferably approximately 0.3 μm or less.
If it is about 0.01 μm, the desired ferromagnetism will not be exhibited, so a suitable crystal grain size is required to be about 0.01 to 0.3 μm. ” is as stated.
大きな磁化値と適当な抗磁力とを有し、且つ、
適当な平均粒度を有する板状Baフエライト粒子
粉末は、現在最も要求されているところである
が、上述した通りの水熱合成法においては、反応
条件を選ぶことによつて各種のBaフエライト粒
子が沈澱してくる。この沈澱粒子は通常六角板状
を呈しており、生成条件によつてその粒度分布や
平均径が相違することによつて磁気的性質が異な
る。
It has a large magnetization value and an appropriate coercive force, and
Plate-shaped Ba ferrite particles having an appropriate average particle size are currently most in demand, but in the hydrothermal synthesis method described above, various Ba ferrite particles can be precipitated by selecting reaction conditions. I'll come. These precipitated particles usually have a hexagonal plate shape, and their particle size distribution and average diameter vary depending on the production conditions, so their magnetic properties vary.
本発明者は、永年に亘り、水熱合成法による板
状Baフエライト粒子の研究及び開発に携わつて
いるものであるが、その過程において反応条件に
よつて平均径0.05〜0.3μｍを有する板状Baフエラ
イト微粒子が得られるという知見を得ている。 The present inventor has been involved in the research and development of plate-shaped Ba ferrite particles using a hydrothermal synthesis method for many years. We have obtained knowledge that Ba ferrite fine particles can be obtained.
しかしながら、上記平均径0.05〜0.3μｍを有す
る板状Baフエライト粒子は、抗磁力を1000Oe以
下に制御しようとする場合には、磁化値を
50emu／ｇ以上に維持することが困難なものであ
る。 However, when trying to control the coercive force to 1000 Oe or less, the plate-shaped Ba ferrite particles having an average diameter of 0.05 to 0.3 μm have a lower magnetization value.
It is difficult to maintain the concentration above 50 emu/g.
また、従来、水熱合成法により水溶液中から生
成した板状Baフエライト微粒子を800℃以上の温
度で加熱焼成して磁化値を向上させる方法が知ら
れている（特公昭60−12973号公報）。 Furthermore, a method is known in which the magnetization value is improved by heating and firing plate-shaped Ba ferrite fine particles produced from an aqueous solution using a hydrothermal synthesis method at a temperature of 800°C or higher (Japanese Patent Publication No. 12973/1983). .
しかしながら、この方法による場合、磁化値
は、加熱焼成温度が高くなる程大きくなる傾向が
あり、大きな磁化値、殊に57〜60emu／ｇ程度以
上を得ようとすれば900℃以上の高温が必要であ
り、この場合には、粒子及び粒子相互間における
焼結が顕著となつて塊状粒子となつてしまい、磁
気記録用磁性粒子粉末として好ましくない。 However, when using this method, the magnetization value tends to increase as the heating and firing temperature increases, and in order to obtain a large magnetization value, especially about 57 to 60 emu/g or more, a high temperature of 900°C or higher is required. In this case, sintering between particles and particles becomes significant, resulting in lumpy particles, which is not preferable as a magnetic particle powder for magnetic recording.
また、加熱焼成して得られた板状Baフエライ
ト微粒子の抗磁力を1000Oe以下に制御する為に
は、前述した抗磁力低減剤を多量に添加しなけれ
ばならず、このことは磁化値を低下させる原因と
なり、大きな磁化値、殊に、57〜60emu／ｇ以上
を維持しながら抗磁力を300〜1000Oeの範囲に制
御することは困難であつた。 In addition, in order to control the coercive force of the plate-shaped Ba ferrite fine particles obtained by heating and firing to 1000 Oe or less, it is necessary to add a large amount of the above-mentioned coercive force reducing agent, which reduces the magnetization value. Therefore, it was difficult to control the coercive force within the range of 300 to 1000 Oe while maintaining a large magnetization value, especially 57 to 60 emu/g or more.
そこで、大きな磁化値と適当な抗磁力とを有
し、且つ、適当な平均粒度を有する板状Baフエ
ライト粒子を得る方法の確立が強く要望されてい
る。 Therefore, it is strongly desired to establish a method for obtaining plate-shaped Ba ferrite particles having a large magnetization value, an appropriate coercive force, and an appropriate average particle size.
本発明者は、上述したところに鑑み、水熱処理
法において平均径0.05〜0.3μｍを有する板状Baフ
エライト粒子の抗磁力を300〜1000Oeとし、且
つ、磁化値を更に高めるべく種々研究を重ねた結
果、本発明に到達したものである。
In view of the above, the present inventor conducted various studies in order to increase the coercive force of plate-shaped Ba ferrite particles having an average diameter of 0.05 to 0.3 μm to 300 to 1000 Oe and further increase the magnetization value using a hydrothermal treatment method. As a result, we have arrived at the present invention.
即ち、本発明は、粒子表面に亜鉛が固溶してい
る板状Baフエライト微粒子からなる磁気記録溶
板状Baフエライト微粒子粉末及び板状Baフエラ
イト微粒子をPH4.0〜12.0の亜鉛を含む水溶液中
に懸濁され、粒子表面に亜鉛の水酸化物が沈着し
ている板状Baフエライト微粒子を得、該粒子を
別、乾燥し、次いで、600〜900℃の温度範囲で
加熱焼成することにより、前記板状Baフエライ
ト微粒子の粒子表面に亜鉛を固溶させることから
なる磁気記録用板状Baフエライト微粒子粉末の
製造法である。 That is, the present invention provides magnetic recording solution consisting of plate-shaped Ba ferrite fine particles in which zinc is dissolved solidly on the particle surface, and plate-shaped Ba ferrite fine particles in an aqueous solution containing zinc with a pH of 4.0 to 12.0. By obtaining plate-shaped Ba ferrite fine particles suspended in the powder and having zinc hydroxide deposited on the particle surface, the particles are separately dried, and then heated and calcined in a temperature range of 600 to 900 ° C. This is a method for producing plate-shaped Ba ferrite fine particles for magnetic recording, which comprises dissolving zinc as a solid solution on the surface of the plate-shaped Ba ferrite fine particles.
先ず、本発明において最も重要な点は、板状
Baフエライト粒子をPH4.0〜12.0の亜鉛を含む水
溶液中に懸濁させ、粒子表面に亜鉛の水酸化物が
沈着している板状Baフエライト微粒子を得、該
粒子を別、乾燥し、次いで、600〜900℃の温度
範囲で加熱焼成した場合には、前記板状Baフエ
ライト微粒子表面に亜鉛を固溶させることがで
き、その結果、板状Baフエライト粒子の磁化値
を900℃以下の加熱焼成温度で効果的に大きくす
ることがてき、しかも、抗磁力を低下させる効果
を有することに起因して、磁化値を低下させる原
因となる抗磁力低減剤の添加量を少なくすること
ができる為、大きな磁化値を維持しながら効果的
に抗磁力を300〜1000Oeの範囲に制御することが
できるという点である。
First, the most important point in the present invention is that the plate-shaped
Ba ferrite particles are suspended in an aqueous solution containing zinc with a pH of 4.0 to 12.0 to obtain plate-shaped Ba ferrite fine particles with zinc hydroxide deposited on the particle surface.The particles are separated, dried, and then , when heating and firing in a temperature range of 600 to 900°C, zinc can be solid-dissolved on the surface of the plate-shaped Ba ferrite particles, and as a result, the magnetization value of the plate-shaped Ba ferrite particles can be heated to 900°C or less. It can be effectively increased at the firing temperature, and the amount of coercive force reducer, which causes a decrease in magnetization value, can be reduced because it has the effect of reducing coercive force. The point is that the coercive force can be effectively controlled within the range of 300 to 1000 Oe while maintaining a large magnetization value.
本発明において、板状Baフエライト微粒子の
磁化値を効果的に大きくすることができ、しか
も、大きな磁化値を維持しながら抗磁力を制御す
ることができる理由について、本発明者は、後述
する比較例に示される通り、水熱処理法において
板状Baフエライト微粒子の生成反応にあたり亜
鉛を添加する（例えば、特公昭46−3545号公報、
前出特公昭60−12973号公報）場合及び板状Baフ
エライト微粒子の粒子表面を亜鉛の酸化物及び／
又は水酸化物で被覆する（特開昭58−56232号公
報）場合のいずれの場合も本件発明の効果が得ら
れないことから、板状Baフエライト微粒子の粒
子表面に亜鉛が固溶していることによるものと考
えている。 In the present invention, the reason why the magnetization value of the plate-shaped Ba ferrite fine particles can be effectively increased and the coercive force can be controlled while maintaining the large magnetization value is explained by the following comparison. As shown in the example, zinc is added during the formation reaction of plate-shaped Ba ferrite fine particles in the hydrothermal treatment method (for example, Japanese Patent Publication No. 46-3545,
In the case of the above-mentioned Japanese Patent Publication No. 12973/1983), the surface of the plate-shaped Ba ferrite fine particles is coated with zinc oxide and/or
or coating with hydroxide (Japanese Patent Laid-Open No. 58-56232), the effect of the present invention cannot be obtained, so zinc is solidly dissolved on the surface of the plate-shaped Ba ferrite fine particles. I think this is due to this.
本件発明においては、Baフエライト微粒子の
粒子表面に固溶している亜鉛の量が増加する程、
効果的に磁化値を大きくすることができ、且つ、
抗磁力を制御することができる。 In the present invention, as the amount of zinc dissolved in solid solution on the particle surface of Ba ferrite fine particles increases,
The magnetization value can be effectively increased, and
Coercive force can be controlled.
本発明において、粒子表面に固溶している亜鉛
量の制御は、粒子表面に亜鉛の水酸化物を沈着さ
せる際のPHと亜鉛添加量とを調整することによつ
て行われる。 In the present invention, the amount of zinc dissolved on the particle surface is controlled by adjusting the pH and the amount of zinc added when depositing zinc hydroxide on the particle surface.
粒子表面への亜鉛の水酸化物の沈着量は、PH８
〜10付近を最高値としてPHが高くなる程増加する
傾向にある。 The amount of zinc hydroxide deposited on the particle surface is PH8
The maximum value is around ~10, and it tends to increase as the pH increases.
次に、本発明実施にあたつての諸条件について
述べる。 Next, various conditions for implementing the present invention will be described.
本発明における出発原料としての板状Baフエ
ライト微粒子とは、板状BaO・nFe2O3（４≦ｎ≦
８）微粒子及びこれらに前述した周知の抗磁力低
減剤を添加したものをいい、水熱合成法により水
溶液中から生成した板状Baフエライト微粒子は
もちろん、これを加熱焼成したもの、水溶液中か
らBaイオンとFeイオンとを沈澱させ、該沈澱物
を加熱焼成する所謂共沈法により得られた板状
Baフエライト微粒子及びBaフエライトの成分原
料とガラス形成物質とを混合、溶融した後、該溶
融物を急速冷却する所謂ガラス溶融法により得ら
れた板状Baフエライト微粒子のいずれをも用い
ることができる。 The plate-shaped Ba ferrite fine particles as the starting material in the present invention are plate-shaped BaO・nFe 2 O 3 (4≦n≦
8) Refers to fine particles and those to which the well-known coercive force reducing agent mentioned above is added, including plate-shaped Ba ferrite fine particles produced from an aqueous solution by hydrothermal synthesis, Ba ferrite particles produced by heating and firing these, and Ba ferrite particles from an aqueous solution. A plate-shaped plate obtained by a so-called coprecipitation method in which ions and Fe ions are precipitated and the precipitate is heated and fired.
Any of Ba ferrite fine particles and plate-shaped Ba ferrite fine particles obtained by a so-called glass melting method in which a component raw material of Ba ferrite and a glass-forming substance are mixed and melted and then the melt is rapidly cooled can be used.
本発明における亜鉛の水酸化物の沈着は、板状
Baフエライト微粒子をPH4.0〜12.0の亜鉛を含む
水溶液中に懸濁させればよい。 The deposition of zinc hydroxide in the present invention is plate-like.
Ba ferrite fine particles may be suspended in an aqueous solution containing zinc with a pH of 4.0 to 12.0.
亜鉛を含む水溶液としては、塩化亜鉛、臭化亜
鉛、ヨウ化亜鉛等のハロゲン化物、硝酸亜鉛、硫
酸亜鉛、酢酸亜鉛等を使用することができる。 As the aqueous solution containing zinc, halides such as zinc chloride, zinc bromide, and zinc iodide, zinc nitrate, zinc sulfate, zinc acetate, and the like can be used.
PHが４未満又は12を越えるである場合には、亜
鉛の沈着が困難となる。 If the pH is less than 4 or more than 12, zinc deposition becomes difficult.
本発明における加熱焼成温度は、600〜900℃で
ある。 The heating and firing temperature in the present invention is 600 to 900°C.
600℃未満である場合には、板状Baフエライト
粒子の粒子表面への亜鉛の固溶が十分ではない。 If the temperature is lower than 600°C, solid solution of zinc on the surface of the plate-shaped Ba ferrite particles is not sufficient.
900℃を越える場合には、粒子及び粒子相互間
の焼結が顕著となる。 When the temperature exceeds 900°C, sintering of particles and particles becomes noticeable.
本発明における加熱焼成にあたつては、板状
Baフエライト微粒子の粒子表面を、あらかじめ、
焼結防止効果を有するSi化合物、Al化合物、Ｐ
化合物等により被覆しておいてもよい。 In heating and firing in the present invention, plate-shaped
The particle surface of Ba ferrite fine particles is prepared in advance.
Si compounds, Al compounds, P that have sintering prevention effect
It may be coated with a compound or the like.
本発明における板状Baフエライト微粒子への
亜鉛の固溶量は0.2〜5.0重量％である。 The solid solution amount of zinc in the plate-shaped Ba ferrite fine particles in the present invention is 0.2 to 5.0% by weight.
0.2重量％未満である場合には、本発明の目的
を十分達成することができない。 If it is less than 0.2% by weight, the object of the present invention cannot be fully achieved.
5.0重量％を越える場合にも本発明の目的を達
成することはできるが必要以上に添加することは
意味がない。 Although the purpose of the present invention can be achieved even if the amount exceeds 5.0% by weight, there is no point in adding more than necessary.
次に、実施例及び比較例により本発明を説明す
る。
Next, the present invention will be explained with reference to Examples and Comparative Examples.
尚、以下の実施例並びに比較例における粒子の
平均径は、電子顕微鏡写真により測定した値であ
る。 In addition, the average diameter of particles in the following Examples and Comparative Examples is a value measured using an electron micrograph.
また、磁化値及び抗磁力は粉末状態で10KOe
の磁場において測定したものである。 In addition, the magnetization value and coercive force are 10KOe in powder form.
This was measured in a magnetic field of
実施例 １
水熱合成法により、Feに対し9.52モル％のBa、
8.57モル％のCo及び2.86モル％のTiを含有する板
状Baフエライト微粒子を得た。Example 1 By hydrothermal synthesis, 9.52 mol% Ba and
Platy Ba ferrite fine particles containing 8.57 mol% Co and 2.86 mol% Ti were obtained.
得られた微粒子100ｇを0.07molの塩化亜鉛水
溶液中に分散混合し、PH6.0において粒子表面に
亜鉛の水酸化物を沈着させた後、別、乾燥し、
次いで、800℃において1.5時間加熱焼成した。 100 g of the obtained fine particles were dispersed and mixed in a 0.07 mol zinc chloride aqueous solution to deposit zinc hydroxide on the particle surface at pH 6.0, and then dried separately.
Next, it was heated and baked at 800°C for 1.5 hours.
加熱焼成して得られた微粒子は、平均径0.08μ
ｍであり、磁性は抗磁力Hcが680Oe、磁化値が
61.2emu／ｇであつた。 The fine particles obtained by heating and firing have an average diameter of 0.08μ.
m, and the magnetism has a coercive force Hc of 680 Oe and a magnetization value of
It was 61.2 emu/g.
また、この微粒子は、図１のＸ線回析付から明
らかな通り、マグネトプランバイト型構造を示す
ピークのみが認められ、且つ、化学分析の結果、
アルカル溶液中で加熱抽出される亜鉛酸化物、亜
鉛水酸化物が検出されないことから亜鉛が固溶し
たものと認められ、亜鉛の固溶量は、螢光Ｘ線分
析の結果、2.5重量％であつた。 In addition, as is clear from the X-ray diffraction analysis in Figure 1, only a peak indicating a magnetoplumbite structure was observed in this fine particle, and as a result of chemical analysis,
Zinc oxide and zinc hydroxide extracted by heating in the alkaline solution were not detected, so it was recognized that zinc was dissolved in solid solution.The amount of solid solution of zinc was determined to be 2.5% by weight as a result of fluorescent X-ray analysis. It was hot.
尚、亜鉛の水酸化物を沈着させなかつた以外
は、上記と同様にして得られたCo及びTiを含有
した板状Baフエライト微粒子は、平均径0.08μ
ｍ、磁性は、抗磁力が1210Oe、磁化値が
54.4emu／ｇであつた。 Incidentally, the plate-shaped Ba ferrite fine particles containing Co and Ti obtained in the same manner as above except that zinc hydroxide was not deposited had an average diameter of 0.08μ.
m, magnetism: coercive force is 1210Oe, magnetization value is
It was 54.4 emu/g.
実施例 ２
水熱合成法により、Feに対し10.0モル％のBa
を含有する板状Baフエライト微粒子を得た。Example 2 By hydrothermal synthesis, 10.0 mol% Ba was added to Fe.
Platy Ba ferrite fine particles containing .
得られた微粒子100ｇを0.1molの硝酸亜鉛水溶
液中に分散混合し、PH6.0において粒子表面に亜
鉛の水酸化物を沈着させた後、別、乾燥し、次
いで750℃において1.5時間加熱焼成した。 100 g of the obtained fine particles were dispersed and mixed in a 0.1 mol zinc nitrate aqueous solution, and after depositing zinc hydroxide on the particle surface at pH 6.0, it was separately dried, and then heated and calcined at 750°C for 1.5 hours. .
加熱焼成して得られた微粒子は、平均径0.2μｍ
であり、磁性は抗磁力Hcが980Oe、磁化値が
64.5emu／ｇであつた。 The fine particles obtained by heating and firing have an average diameter of 0.2 μm.
The coercive force Hc is 980 Oe, and the magnetization value is
It was 64.5 emu/g.
また、この微粒子は、Ｘ線回折の結果、マグネ
トプラントバイト型構造を示すピークのみが認め
られ、且つ、化学分析の結果、アルカリ溶液中で
加熱、抽出される亜鉛酸化物、亜鉛水酸化物が検
出されないことから亜鉛が固溶したものと認めら
れ、亜鉛の固溶量は、螢光Ｘ線分析の結果、3.1
重量％であつた。 In addition, as a result of X-ray diffraction, only a peak indicating a magnetoplantite structure was observed in this fine particle, and as a result of chemical analysis, zinc oxide and zinc hydroxide were extracted by heating in an alkaline solution. Since it was not detected, it was recognized that zinc was dissolved in solid solution, and as a result of fluorescent X-ray analysis, the amount of zinc dissolved in solid solution was 3.1
It was in weight%.
尚、亜鉛の水酸化物を沈着させなかつた以外
は、上記と同様にして得られた板状Baフエライ
ト微粒子は、平均径0.2μｍ、磁性は、抗磁力が
2200Oe、磁化値が57.0emu／ｇであつた。 The plate-shaped Ba ferrite fine particles obtained in the same manner as above except that zinc hydroxide was not deposited had an average diameter of 0.2 μm and a coercive force.
The magnetization value was 2200 Oe and 57.0 emu/g.
実施例 ３
実施例１と同様にして水熱合成法により得られ
たFeに対し9.52モル％のBa、8.57モル％のCo及
び2.86モル％のTiを含有する板状Baフエライト
微粒子100ｇを３号水ガラス10ｇを含水溶液中に
分散させSiで被覆した後、0.07molの硝酸亜鉛水
溶液中に分散混合し、PH9.0において粒子表面に
亜鉛の水酸化物を沈着させた後、別、乾燥し、
次いで、800℃において1.5時間加熱焼成した。Example 3 100 g of plate-shaped Ba ferrite fine particles containing 9.52 mol% Ba, 8.57 mol% Co, and 2.86 mol% Ti based on Fe obtained by the hydrothermal synthesis method in the same manner as in Example 1 were added to No. 3. After dispersing 10 g of water glass in an aqueous solution and coating it with Si, it was dispersed and mixed in a 0.07 mol zinc nitrate aqueous solution, and after depositing zinc hydroxide on the particle surface at pH 9.0, it was separately dried. ,
Next, it was heated and baked at 800°C for 1.5 hours.
加熱焼成して得られた微粒子は、平均径0.05μ
ｍであり、磁性は抗磁力Hcが595Oe、磁化値が
62.2emu／ｇであつた。 The fine particles obtained by heating and firing have an average diameter of 0.05μ.
m, and the magnetism has a coercive force Hc of 595 Oe and a magnetization value of
It was 62.2 emu/g.
また、この微粒子は、Ｘ線回折の結果、マグネ
トプラントバイト型構造を示すピークのみが認め
られ、且つ、化学分析の結果、アルカリ溶液中で
加熱、抽出される亜鉛酸化物、亜鉛水酸化物が検
出されないことから亜鉛が固溶したものと認めら
れ、亜鉛の固溶量は、螢光Ｘ線分析の結果、2.9
重量％であつた。 In addition, as a result of X-ray diffraction, only a peak indicating a magnetoplantite structure was observed in this fine particle, and as a result of chemical analysis, zinc oxide and zinc hydroxide were extracted by heating in an alkaline solution. Since it was not detected, it was recognized that zinc was dissolved in solid solution, and as a result of fluorescent X-ray analysis, the amount of zinc dissolved in solid solution was 2.9
It was in weight%.
比較例 １
Co及びTiを含有する板状Baフエライト微粒子
に亜鉛の水酸化物を沈着させず、且つ、加熱焼成
温度を920℃とした以外は実施例１と同様にして
板状Baフエライト微粒子を得た。Comparative Example 1 Platy Ba ferrite particles were prepared in the same manner as in Example 1, except that zinc hydroxide was not deposited on the plate-shaped Ba ferrite particles containing Co and Ti, and the firing temperature was 920°C. Obtained.
得られた板状Baフエライト微粒子のBET比表
面積は18m2／ｇであり、加熱焼成前の板状Baフ
エライト微粒子のBET比表面積75m2／ｇに比べ
大幅に低下しており、粒子及び粒子相互間で焼結
が生起したものであつた。 The BET specific surface area of the obtained plate-shaped Ba ferrite particles was 18 m 2 /g, which is significantly lower than the BET specific surface area of the plate-shaped Ba ferrite particles before heating and firing, which was 75 m 2 /g. Sintering occurred between the two.
また、磁性は、抗磁力Hcが1086Oe、磁化値が
57.0emu／ｇであつた。 In addition, regarding magnetism, the coercive force Hc is 1086 Oe, and the magnetization value is
It was 57.0 emu/g.
比較例 ２
実施例１の水熱合成反応において塩化亜鉛
0.98molを添加することにより得られたFeに対し
9.52モル％のBa、7.0モル％のZn、8.57モル％の
Co及び2.86モル％のTiの粒子内部に均一に含有
する板状Baフエライト粒子を出発原料として用
い、且つ亜鉛の水酸化物を沈着させなかつた以外
は実施例１と同様にして板状Baフエライト微粒
子を得た。Comparative Example 2 Zinc chloride in the hydrothermal synthesis reaction of Example 1
For Fe obtained by adding 0.98mol
9.52 mol% Ba, 7.0 mol% Zn, 8.57 mol%
Platy Ba ferrite particles were prepared in the same manner as in Example 1, except that plate-shaped Ba ferrite particles containing Co and 2.86 mol% Ti uniformly inside the particles were used as the starting material, and no zinc hydroxide was deposited. Fine particles were obtained.
得られた板状Baフエライト粒子は、Ｘ線回折
の結果、マグネトプランバイト型構造を示すピー
クのみが認められた。 As a result of X-ray diffraction, only a peak indicating a magnetoplumbite structure was observed in the obtained plate-shaped Ba ferrite particles.
また、この板状Baフエライト微粒子は、平均
径0.1μｍであり、磁性は抗磁力Hcが1180Oe、磁
化値が53.2emu／ｇであつた。 The plate-shaped Ba ferrite fine particles had an average diameter of 0.1 μm, a coercive force Hc of 1180 Oe, and a magnetization value of 53.2 emu/g.
比較例 ３
亜鉛の水酸化物を沈着させなかつた以外は、実
施例１と同様にして得られたCo及びTiを含有す
る板状Baフエライト微粒子100ｇを0.07molの塩
化亜鉛水溶液中に分散混合し、PH6.0において粒
子表面に亜鉛の水酸化物を沈着させた後、別
し、150℃で乾燥した。Comparative Example 3 100 g of plate-shaped Ba ferrite fine particles containing Co and Ti obtained in the same manner as in Example 1 except that zinc hydroxide was not deposited were dispersed and mixed in a 0.07 mol zinc chloride aqueous solution. After depositing zinc hydroxide on the particle surface at pH 6.0, the particles were separated and dried at 150°C.
得られた板状Baフエライト微粒子は、平均径
0.08μｍであり、磁性は、抗磁力Hcが1200Oe、磁
化値が52.4emu／ｇであつた。 The obtained plate-shaped Ba ferrite fine particles have an average diameter of
The magnetic field had a coercive force Hc of 1200 Oe and a magnetization value of 52.4 emu/g.
上記板状Baフエライト微粒子は、化学分析の
結果、アルアリ水溶液中で加熱、抽出される亜鉛
酸化物、亜鉛水酸化物が検出されたことから、亜
鉛が粒子表面に亜鉛酸化物、亜鉛水酸化物として
存在しており、固溶していないものであることが
確認された。 As a result of chemical analysis, zinc oxide and zinc hydroxide were detected in the above plate-shaped Ba ferrite fine particles by heating and extraction in the Al-Ali aqueous solution. It was confirmed that there was no solid solution.
比較例 ４
150℃で乾燥する代わりに500℃で焼成した以外
は、比較例３と同様にして板状Baフエライトを
得た。Comparative Example 4 A plate-shaped Ba ferrite was obtained in the same manner as Comparative Example 3, except that it was fired at 500°C instead of drying at 150°C.
得られた板状Baフエライト微粒子は、平均径
0.08μｍであり、磁性は、抗磁力Hcが1190Oe、磁
化値が53.0emu／ｇであつた。 The obtained plate-shaped Ba ferrite fine particles have an average diameter of
The magnetic field had a coercive force Hc of 1190 Oe and a magnetization value of 53.0 emu/g.
上記板状Baフエライト微粒子は、化学分析の
結果、アルカリ水溶液中で加熱、抽出される亜鉛
酸化物、亜鉛水酸化物が検出されたことから、亜
鉛が粒子表面に亜鉛酸化物、亜鉛水酸化物として
存在しており、固溶していないものであることが
確認された。 As a result of chemical analysis, zinc oxide and zinc hydroxide were detected in the above plate-shaped Ba ferrite fine particles by heating and extraction in an alkaline aqueous solution. It was confirmed that there was no solid solution.
本発明に係る板状Baフエライト粒子粉末は、
前出実施例に示した通り、10KOeの磁場におけ
る磁化値が大きく、抗磁力Hcが300〜1000Oeで
あつて、粒子表面に亜鉛が固溶している平均径
0.05〜0.3μｍを有する板状BaBaフエライト微粒
子を得ることができるので、磁気記録用磁性材
料、特に、垂直磁気記録用材料として最適であ
る。
The plate-shaped Ba ferrite particle powder according to the present invention is
As shown in the previous example, the average diameter has a large magnetization value in a magnetic field of 10 KOe, a coercive force Hc of 300 to 1000 Oe, and a solid solution of zinc on the particle surface.
Since plate-like BaBa ferrite fine particles having a diameter of 0.05 to 0.3 μm can be obtained, it is optimal as a magnetic material for magnetic recording, particularly as a material for perpendicular magnetic recording.
図１は、実施例１で得られた亜鉛が固溶してい
る板状Baフエライト微粒子のＸ線回折図である。
FIG. 1 is an X-ray diffraction diagram of plate-shaped Ba ferrite fine particles obtained in Example 1 in which zinc is dissolved in solid solution.
Claims (1)
ライト微粒子からなる磁気記録用板状Baフエラ
イト微粒子粉末。 ２ 板状Baフエライト微粒子をPH4.0〜12.0の亜
鉛を含む水溶液中に懸濁させ、粒子表面に亜鉛の
水酸化物が沈着している板状Baフエライト微粒
子を得、該粒子を別、乾燥し、次いで、600〜
900℃の温度範囲で加熱焼成することにより、前
記板状Baフエライト微粒子の粒子表面に亜鉛を
固溶させることを特徴とする磁気記録用板状Ba
フエライト微粒子粉末の製造法。[Claims] 1. A plate-shaped Ba ferrite fine particle powder for magnetic recording comprising plate-shaped Ba ferrite fine particles in which zinc is solidly dissolved on the particle surface. 2 Platy Ba ferrite fine particles are suspended in an aqueous solution containing zinc with a pH of 4.0 to 12.0 to obtain plate-like Ba ferrite fine particles with zinc hydroxide deposited on the particle surface, and the particles are separated and dried. and then 600~
A plate-shaped Ba for magnetic recording, characterized in that zinc is dissolved in solid solution on the particle surface of the plate-shaped Ba ferrite fine particles by heating and firing in a temperature range of 900°C.
Method for producing ferrite fine particle powder.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61018834A JPS62176918A (en) | 1986-01-29 | 1986-01-29 | Fine platy barium ferrite powder for magnetic recording and its preparation |
| US07/008,466 US4806429A (en) | 1986-01-29 | 1987-01-29 | Plate-like barium ferrite particles suitable for use in magnetic recording and process for producing the same |
| US07/008,439 US4851292A (en) | 1986-01-29 | 1987-01-29 | Plate-like barium ferrite particles suitable for use in magnetic recording and process for producing the same |
| DE8787300779T DE3773008D1 (en) | 1986-01-29 | 1987-01-29 | PLATE-SHAPED BARIUM FERRIDE PARTICLES FOR MAGNETIC RECORDING AND METHOD FOR THEIR PRODUCTION. |
| EP87300779A EP0232131B1 (en) | 1986-01-29 | 1987-01-29 | Plate-like barium ferrite particles suitable for use in magnetic recording and process for producing the same |
| EP87300780A EP0232132B1 (en) | 1986-01-29 | 1987-01-29 | Plate-like barium ferrite particles suitable for use in magnetic recording and process for producing the same |
| DE8787300780T DE3773403D1 (en) | 1986-01-29 | 1987-01-29 | PLATE-SHAPED BARIUM FERRIDE PARTICLES FOR MAGNETIC RECORDING AND METHOD FOR THEIR PRODUCTION. |
| KR870000794A KR870007538A (en) | 1986-01-29 | 1987-01-30 | Plate-shaped barium ferrite particles for magnetic recording and manufacturing method thereof |
| KR870000795A KR870007539A (en) | 1986-01-29 | 1987-01-30 | Plate-shaped barium ferrite particles for magnetic recording and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61018834A JPS62176918A (en) | 1986-01-29 | 1986-01-29 | Fine platy barium ferrite powder for magnetic recording and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62176918A JPS62176918A (en) | 1987-08-03 |
| JPH0372014B2 true JPH0372014B2 (en) | 1991-11-15 |
Family
ID=11982592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61018834A Granted JPS62176918A (en) | 1986-01-29 | 1986-01-29 | Fine platy barium ferrite powder for magnetic recording and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62176918A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62265121A (en) * | 1986-05-09 | 1987-11-18 | Toda Kogyo Corp | Particulate powder of lamellate ba ferrite and its production |
| JP2741198B2 (en) * | 1987-11-06 | 1998-04-15 | 戸田工業 株式会社 | Plate-like magnetoplumbite-type ferrite fine particle powder for magnetic recording |
-
1986
- 1986-01-29 JP JP61018834A patent/JPS62176918A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62176918A (en) | 1987-08-03 |
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