JPS63151621A - Production of needle-like magnetic iron oxide particle powder - Google Patents
Production of needle-like magnetic iron oxide particle powderInfo
- Publication number
- JPS63151621A JPS63151621A JP61296168A JP29616886A JPS63151621A JP S63151621 A JPS63151621 A JP S63151621A JP 61296168 A JP61296168 A JP 61296168A JP 29616886 A JP29616886 A JP 29616886A JP S63151621 A JPS63151621 A JP S63151621A
- Authority
- JP
- Japan
- Prior art keywords
- iron oxide
- particles
- magnetic iron
- compound
- salt
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 101
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000000843 powder Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001868 water Inorganic materials 0.000 abstract description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 abstract description 5
- 229940044175 cobalt sulfate Drugs 0.000 abstract description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract description 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 2
- -1 ferric sulfate Chemical class 0.000 abstract 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 abstract 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000006247 magnetic powder Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 229910052598 goethite Inorganic materials 0.000 description 3
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000002123 temporal effect Effects 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、針状磁性酸化鉄粒子粉末の製造法に関するも
のであり、詳しくは、高密度記録用の磁性酸化鉄粒子粉
末として好適である高い保磁力を有し、且つ、消去特性
に優れている粒子表面がＣｏ化合物で被覆されている針
状磁性酸化鉄粒子粉末の製造法に関するものである
（従来の技術〕
近年、磁気記録再生用機器の小型軽量化が進むにつれて
磁気テープ、磁気ディスク等の磁気記録媒体に対する高
性能化の必要性が益々生じてきている。即ち、記録密度
特性の向上である。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing acicular magnetic iron oxide particles, and more specifically, it is suitable as magnetic iron oxide particles for high-density recording. This invention relates to a method for producing acicular magnetic iron oxide particles having high coercive force and excellent erasing properties, the particle surface of which is coated with a Co compound (prior art). As devices become smaller and lighter, there is an increasing need for improved performance in magnetic recording media such as magnetic tapes and magnetic disks. That is, improved recording density characteristics are required.
磁気記録媒体の記録密度特性を向上させる為には、用い
る磁性材料粒子粉末が出来るだけ高い保磁力を有するこ
とである。この事実は、例えば、社団法人電子通信学会
「電子通信学会技術研究報告」門Ｒ７７−３６（１９７
８年発行）、第３７頁の［磁気テープの記録密度を上げ
るためには、テープに用いる磁性粉の保磁力を大きくす
ることが必要である。」なる記載の通りである。In order to improve the recording density characteristics of a magnetic recording medium, it is important that the magnetic material particles used have as high a coercive force as possible. This fact can be seen, for example, in the Institute of Electronics and Communication Engineers, IEICE Technical Research Report, Section R77-36 (197
Published in 1998), page 37 [In order to increase the recording density of magnetic tape, it is necessary to increase the coercive force of the magnetic powder used in the tape. ” as stated.
現在、高い保磁力を有する磁性酸化鉄粒子粉末として所
謂、Ｃｏドープ型の針状磁性酸化鉄粒子と所謂、Ｃｏ被
着型の磁性酸化鉄粒子とが知られておリ、これら磁性酸
化鉄粒子の保磁力は、Ｃｏ量が多くなる程高くなる傾向
にある。前者は出発原料である針状ゲータイト粒子の生
成反応にあたり予めＣｏ塩を添加しておくことによりＣ
ｏ含有針状ゲータイト粒子を生成させ、次いで、還元し
てｃｏ含有針状マグネタイト粒子とするか、必要により
更に酸化してＣｏ含有針状マグヘマイト粒子とすること
により、後者は、出発原料である針状ゲータイト粒子を
還元、又は必要により更に酸化して得られた針状マグネ
タイト粒子又針状マグヘマイト粒子を前駆体粒子として
該前駆体粒子の粒子表面をＣｏ化合物で被覆することに
より得られる。Currently, so-called Co-doped acicular magnetic iron oxide particles and so-called Co-coated magnetic iron oxide particles are known as magnetic iron oxide particles having high coercive force. The coercive force tends to increase as the amount of Co increases. The former is achieved by adding Co salt in advance during the production reaction of acicular goethite particles, which are the starting materials.
By producing o-containing acicular goethite particles and then reducing them to produce co-containing acicular magnetite particles, or optionally further oxidizing them to produce cobalt-containing acicular maghemite particles, the latter can be obtained from the starting material needles. Acicular magnetite particles or acicular maghemite particles obtained by reducing or, if necessary, further oxidizing goethite particles are used as precursor particles, and the particle surfaces of the precursor particles are coated with a Co compound.
一方、磁気記録媒体は、繰り返して長期に亘り使用する
ものであるから磁気特性が熱的、経時的に安定であり、
且つ、消去特性にすぐれていることが強く要望されてい
る。On the other hand, since magnetic recording media are used repeatedly over long periods of time, their magnetic properties are stable thermally and over time.
In addition, it is strongly desired that the material has excellent erasing characteristics.
磁気記録媒体に対する上記のような要求を満足させる為
には、用いられる磁性酸化鉄粒子の磁気特性が熱的、経
時的に安定であり、且つ、消去特性に優れていることが
必要である。In order to satisfy the above requirements for magnetic recording media, it is necessary that the magnetic properties of the magnetic iron oxide particles used be stable both thermally and over time, and that the erasing properties are excellent.
高い保磁力を有し、且つ、熱的、経時的に安定であり、
しかも消去特性に優れた磁性酸化鉄粒子は、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Ｃｏド
ープ型の磁性酸化鉄粒子は、高い保磁力を有するもので
あるが、一方、Ｃｏが結晶内に拡散す６等に起因して保
磁力分布の拡がりが大きくなり、その結果、熱的、経時
的に不安定であり、消去特性が悪いという欠点を有する
ものである。It has high coercive force and is stable thermally and over time.
Moreover, magnetic iron oxide particles with excellent erasing properties are currently in the greatest demand. Co-doped magnetic iron oxide particles as described above have a high coercive force; Due to 6 etc. diffusing into the crystal, the coercive force distribution widens, resulting in thermal and temporal instability and poor erasing characteristics.
この現象は、前出「電子通信学会技術研究報告」のｒＣ
ｏ固溶型（ドープ型）酸化鉄磁性粉は、保磁力が熱的、
経時的に変化しやすいため、テープにしたとき、転写及
び消去特性が劣るという大きな欠点を有している。これ
らの欠点は、室温でもＣ。This phenomenon is explained in the rC
o Solid solution type (doped type) iron oxide magnetic powder has a coercive force of thermal
Since it easily changes over time, it has a major drawback in that when it is made into a tape, its transfer and erasing properties are poor. These drawbacks are C even at room temperature.
イオンが結晶内を動くことに起因する、と考えられてい
る。」なる記載の通りである。It is believed that this is caused by the movement of ions within the crystal. ” as stated.
また、上述した通りのＣｏ被着型の磁性酸化鉄粒子は、
高い保磁力を有すると同時に、Ｃｏドープ型の磁性酸化
鉄に比べ、熱的、経時的にも安定であり、消去特性が優
れているという特徴を有するものである。この現象は、
前出「電子通信学会技術研究報告」の「・・・・Ｇｏエ
ピタキシャル（Ｃｏ被着型）酸化鉄磁性粉においては、
二重構造になっているため、これらの欠点は解消され、
熱的経時的にも安定で、この磁性粉を使用したテープは
、すぐれた転写特性、消去特性を有する。・・・・」な
る記載の通りである。In addition, the Co-coated magnetic iron oxide particles as described above are
In addition to having a high coercive force, it is also thermally and temporally stable compared to Co-doped magnetic iron oxide, and has excellent erasing properties. This phenomenon is
Regarding Go epitaxial (Co-adhered type) iron oxide magnetic powder in the aforementioned "IEICE Technical Research Report",
Because it has a double structure, these drawbacks are eliminated,
It is stable both thermally and over time, and tapes using this magnetic powder have excellent transfer and erasing properties. It is as stated in ``...''.
しかしながら、近時、消去特性の改良に対する要請はと
どまるところがな（、上記Ｃｏ被着型の磁性酸化鉄粒子
においても未だ、保磁力分布の拡がりが太き（、消去特
性が優れたものとは言い難いことが指摘されている。However, in recent years, there has been an unrelenting demand for improved erasing properties (and even the above-mentioned Co-coated magnetic iron oxide particles still have a wide spread of coercive force distribution (although it cannot be said that they have excellent erasing properties). It has been pointed out that this is difficult.
この事実は、例えば、特開昭６１−１７４２６号公報の
「・・・・上記γ−Ｆ＋４０３粒子を使用した磁性粉に
あっては、このγ−Ｆｅ、Ｏ，粒子が微粒子になるにつ
れ抗磁力分布が広がり、さらにコバルト被着を行うとこ
の抗磁力分布はより一層広がる傾向にあることがわかっ
た。・・・・高密度記録を図るために上記コバルト被着
型γ−ＦｅｚＯｚ粒子の微細化を進めると、所定の抗磁
力Ｈｃは得られても、抗磁力分布の悪い消去特性に劣る
磁性粉しか得られない、・・・・」なる記載の通りであ
る。This fact is explained, for example, in JP-A No. 17426/1983, "...In the magnetic powder using the above γ-F+403 particles, as the γ-Fe, O, particles become finer, the coercive force increases. It was found that the coercive force distribution tends to widen, and when cobalt is further deposited, the coercive force distribution tends to become even wider. In order to achieve high-density recording, the above-mentioned cobalt-coated γ-FezOz particles are made finer. As described above, even if a predetermined coercive force Hc is obtained, only magnetic powder with poor coercive force distribution and poor erasing properties is obtained.
そして、Ｃｏ被着型の磁性酸化鉄粒子の保磁力分布の拡
がりはＣｏ被覆量が多くなる程大きくなり、その結果、
消去特性は劣化する傾向にあり、保磁力の向上とは逆の
相関関係にある。The spread of the coercive force distribution of Co-coated magnetic iron oxide particles increases as the amount of Co coating increases, and as a result,
Erasing characteristics tend to deteriorate, which is inversely correlated with improvement in coercive force.
そこで、Ｃｏ被着型磁性酸化鉄粒子の保磁力をより少な
いＣｏ被覆量で効果的に向上させる為の技術手段の確立
が強く要望されている。Therefore, there is a strong demand for the establishment of technical means for effectively improving the coercive force of Co-coated magnetic iron oxide particles with a smaller amount of Co coating.
本発明者は、Ｃｏ被着型磁性酸化鉄粒子の保磁力を少な
いＣｏ被覆量で効果的に向上させる方法について、種々
検討を重ねた結果、本発明に到達したのである。The present inventor has arrived at the present invention as a result of various studies on a method for effectively improving the coercive force of Co-coated magnetic iron oxide particles with a small amount of Co coating.
即ち、本発明は、針状磁性酸化鉄粒子の水分散液と少な
くともＣＯ塩水溶液及びアルカリ水溶液とを混合して得
られたｐｏ１１以上の混合液を、５０〜１００℃の温度
範囲で加熱処理して、前記針状磁性酸化鉄粒子の粒子表
面にＣｏ化合物を生成させることにより、粒子表面がＣ
ｏ化合物で被覆されている針状磁性酸化鉄粒子粉末を製
造する方法において、前記ｐｔｌ１１以上の混合液に、
Ｃｏ化合物の生成反応開始後から終了までの間に、混合
液中の針状磁性酸化鉄粒子に対しＣｕ換算で０．２〜２
．０重量％の銅塩を添加することからなる針状磁性酸化
鉄粒子粉末の製造法である。That is, the present invention heat-treats a mixed solution of po 11 or higher obtained by mixing an aqueous dispersion of acicular magnetic iron oxide particles and at least an aqueous CO salt solution and an aqueous alkaline solution in a temperature range of 50 to 100 °C. By generating a Co compound on the particle surface of the acicular magnetic iron oxide particles, the particle surface becomes carbon.
In the method for producing acicular magnetic iron oxide particle powder coated with an o compound, in the mixed solution of ptl11 or more,
Between the start and end of the Co compound production reaction, 0.2 to 2
．． This is a method for producing acicular magnetic iron oxide particles by adding 0% by weight of copper salt.
先ず、本発明において最も重要な点は、前駆体粒子であ
る針状磁性酸化鉄粒子の粒子表面をＣｏ化合物で被覆す
るにあたり、Ｃｏ化合物の生成反応開始後から終了まで
の間に銅塩を添加した場合には、少ないＣｏ被覆量で効
果的に保磁力を向上させることができる点である。First, the most important point in the present invention is that when coating the particle surface of the acicular magnetic iron oxide particles, which are precursor particles, with a Co compound, a copper salt is added between the start and end of the Co compound production reaction. In this case, the coercive force can be effectively improved with a small amount of Co coating.
今、本発明者が行った数多くの実験例から、その一部を
抽出して説明すれば次の通りである。The following is an explanation of some of the many experimental examples conducted by the present inventor.
図１は、Ｃｏ化合物で被覆されている針状磁性酸化鉄粒
子粉末の保磁力とＣｕ塩の添加量との関係図である。FIG. 1 is a diagram showing the relationship between the coercive force of acicular magnetic iron oxide particles coated with a Co compound and the amount of Cu salt added.
即ち、針状γ−Ｆｅ、Ｏ，粒子（平均長軸径０．３μ鴎
、軸比（長軸：短軸）８：ｌ、保磁力３７００ｅ）１０
０ｇを含む２．０１の水分散液とＣｏ１．Ｏｍｏｌ／
１を含む水溶液５１ｍ１及び１８−ＮのＮａ０ＩＩ ２
５ｍ１とを混合して得られたｐＨ１３の混合液を９０℃
に昇温した後、空気の混入を防止して攪拌しながら混合
液中の針状γ−Ｆｅ、Ｏ。That is, acicular γ-Fe, O, particles (average major axis diameter 0.3μ, axial ratio (major axis: minor axis) 8:l, coercive force 3700e) 10
An aqueous dispersion of 2.01 containing 0g and Co1. Omol/
51 ml of an aqueous solution containing 1 and 18-N Na0II 2
5ml of the mixture with a pH of 13 obtained at 90°C.
After raising the temperature to , the acicular γ-Fe and O in the mixed solution are stirred while preventing air from entering.
粒子に対しＣｕ換算で０〜２．０重量％のＣｕ５Ｑ４を
添加し、次いで３００分間保持することにより得られた
粒子表面がＣｏ化合物で被覆されている針状γ−Ｆｅｚ
Ｏ。Acicular γ-Fez whose particle surface is coated with a Co compound obtained by adding 0 to 2.0% by weight of Cu5Q4 in terms of Cu to the particles and then holding for 300 minutes
O.
粒子の保磁力とＣｕ塩の添加量との関係を示したもので
ある。This figure shows the relationship between the coercive force of particles and the amount of Cu salt added.
図１から明らかな通り、１．０重量％付近を最高値とし
てＣｕ塩の増加に伴って保磁力は向上する傾向を示す。As is clear from FIG. 1, the coercive force tends to increase as the Cu salt content increases, with the maximum value around 1.0% by weight.
次に、本発明実施にあたっての諸条件について述べる。Next, various conditions for implementing the present invention will be described.
本発明における針状磁性酸化鉄粒子としては、針状マグ
ヘマイト粒子、針状マグネタイト粒子（Ｅｄｘ−Ｆｅｔ
ｕｓ Ｏ＜ ｘ ≦１）及びこれらにＣｏ、 Ｎｉ。The acicular magnetic iron oxide particles in the present invention include acicular maghemite particles and acicular magnetite particles (Edx-Fet
us O<x≦1) and Co, Ni to these.
５１１Ａ１％ Ｚｎ％Ｐ等の一種又は二種以上を含む粒
子を用いることができる。Particles containing one or more of 511A1%Zn%P and the like can be used.
本発明における磁性酸化鉄粒子のＣｏ化合物による被覆
は、針状磁性酸化鉄粒子の水分散液と少なくともＣｏ塩
水溶液及びアルカリ水溶液とを混合することにより得ら
れたｐＨ１１以上の混合液を５０〜１００℃の温度範囲
で加熱処理すればよい。Ｃｏ塩水溶液は必要により硫酸
鉄、塩化鉄等のＦｅ０Ｄ塩水溶液を含んでいてもよい。In the present invention, magnetic iron oxide particles are coated with a Co compound by mixing a mixed solution with a pH of 11 or more obtained by mixing an aqueous dispersion of acicular magnetic iron oxide particles with at least an aqueous Co salt solution and an aqueous alkali solution. The heat treatment may be carried out in the temperature range of °C. The Co salt aqueous solution may contain an Fe0D salt aqueous solution such as iron sulfate or iron chloride, if necessary.
Ｃｏ塩水溶液としては、硫酸コバルト、塩化コバルト、
硝酸コバルト等の水溶液を使用することができる。加熱
処理の雰囲気は、Ｎ２等の不活性ガス流下における非酸
化性雰囲気、空気等の酸素含有ガス流下における酸化性
雰囲気のいずれであってもよい。Cobalt sulfate, cobalt chloride,
Aqueous solutions such as cobalt nitrate can be used. The atmosphere for the heat treatment may be either a non-oxidizing atmosphere under a flow of an inert gas such as N2 or an oxidizing atmosphere under a flow of an oxygen-containing gas such as air.
本件発明におけるＣｕ塩としては、硫酸銅、塩化銅及び
硝酸銅等を使用することができる。As the Cu salt in the present invention, copper sulfate, copper chloride, copper nitrate, etc. can be used.
Ｃｕ塩の添加時期は、Ｃｏ化合物の生成反応開始後から
終了までの間であり、Ｃｏ化合物の生成反応開始前、即
ち、針状磁性酸化鉄の水分散液と少なくともＣｏ塩水溶
液及びアルカリ水溶液との混合液を５０℃以上に昇温す
る前にＣｕ塩を添加しても本発明の効果は得られない。The Cu salt is added between the start and end of the Co compound production reaction, that is, before the Co compound production reaction starts, when the aqueous dispersion of acicular magnetic iron oxide and at least the Co salt aqueous solution and the alkaline aqueous solution are added. Even if the Cu salt is added before the temperature of the mixed solution is raised to 50° C. or higher, the effect of the present invention cannot be obtained.
Ｃｕ塩の添加量は、針状磁性酸化鉄粒子に対し、Ｃｕ換
算で０．２〜２．０重量％である。０．２重量％以下で
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。２．０重量％以上である場合には、Ｃｏ化合物で
被覆されている針状磁性酸化鉄粒子の純度の低下により
飽和磁束密度が減少し好ましくない。The amount of Cu salt added is 0.2 to 2.0% by weight in terms of Cu, based on the acicular magnetic iron oxide particles. If it is less than 0.2% by weight, the object of the present invention cannot be fully achieved. If it is 2.0% by weight or more, the saturation magnetic flux density decreases due to a decrease in the purity of the acicular magnetic iron oxide particles coated with the Co compound, which is not preferable.
Ｃｏ化合物で被覆されている針状ｉｆｆ性酸化鉄粒子の
保磁力及び飽和磁束密度を考慮した場合、０．５〜１．
５重量％が好ましい。When considering the coercive force and saturation magnetic flux density of the acicular IF-like iron oxide particles coated with a Co compound, it is 0.5 to 1.
5% by weight is preferred.
（実 施 例〕 次に、実施例及び比較例により本発明を説明する。(Example〕 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粒子
径及び軸比は電子顕微鏡写真から測定した数値の平均値
で示し、保磁力は「振動試料型磁力計ＶＳＭ−３Ｓ−１
５Ｊ （東英工業■製）を用いて外部磁場を１０ｋＯ
ｅまでかけて測定した０粒子中のＣｏ量及びＣｕ量は、
「螢光Ｘ線分析装置３０６３Ｍ型」 （理学電機工業■
製）を使用し、ＪＩＳＫＯ１１９の螢光Ｘ線分析通則に
従って、螢光Ｘ線分析を行うことにより測定した。In addition, the average particle diameter and axial ratio of the particles in the following examples and comparative examples are shown as the average values of values measured from electron micrographs, and the coercive force is determined by "vibrating sample magnetometer VSM-3S-1".
5J (manufactured by Toei Kogyo) with an external magnetic field of 10 kO.
The amounts of Co and Cu in the 0 particles measured up to e are:
"Fluorescent X-ray analyzer model 3063M" (Rigaku Denki Kogyo ■
(manufactured by JIS KO119) and in accordance with the general rules for fluorescent X-ray analysis of JISKO119.
実施例１
前駆体として針状γ−Ｆｅｚｅｓ粒子（平均長軸径０．
３μ糟、軸比（長軸：短軸）８：１、保磁力３７００ｅ
）を用い、該前駆体粒子粉末１００ｇを２１の水に分散
させて得られた分散液と、硫酸第一鉄と硫酸コバルトと
を用いて第一鉄０．２ ａ＋ｏｌ及びコバルト０．１ｍ
ｏｌを溶存させた水溶液５００＋ｗ １とを混合した後
６−ＮのＮａＯＨ水溶液５００ｍ ｌを加え、ＰＨ１４
の混合液とした。得られた混合液を９５℃に昇温した後
、空気の混入を防止して攪拌しながら６０分間保持した
後、ＣｌｌＳＯ４２，５ｇ （混合液中の針状ｒ−Ｆｅ
ｚ０２粒子に対し１．０重量％に該当する。）を添加し
、引き続き１８０分間保持して黒褐色沈澱粒子を生成さ
せた。Example 1 Acicular γ-Fezes particles as a precursor (average long axis diameter 0.
3μ wire, axial ratio (long axis: short axis) 8:1, coercive force 3700e
), and using a dispersion obtained by dispersing 100 g of the precursor particles in 21 water, ferrous sulfate and cobalt sulfate, ferrous 0.2 a + ol and cobalt 0.1 m
After mixing 500 ml of an aqueous solution containing ol dissolved in w1, 500 ml of a 6-N NaOH aqueous solution was added, and the pH was adjusted to 14.
A mixed solution of After heating the obtained mixed solution to 95°C and holding it for 60 minutes while stirring to prevent air from entering, 2.5 g of CllSO4 (acicular r-Fe in the mixed solution) was heated to 95°C.
This corresponds to 1.0% by weight based on the z02 particles. ) was added and then held for 180 minutes to form dark brown precipitated particles.
上記黒褐色沈澱を含む反応溶液は、常法により濾過、水
洗、乾燥した。The reaction solution containing the blackish brown precipitate was filtered, washed with water, and dried by a conventional method.
得られた黒褐色粒子粉末は、螢光Ｘ線分析及びＸ線回折
の結果、粒子表面がＣｏ化合物で被覆されている針状γ
−Ｆｅ＠０２粒子粉末（Ｃｏ量は、Ｃｏ被覆γ−Ｆｅｚ
Ｏ３粒子粉末に対し２．５重量％に該当する。）であり
、該粒子は、０．８５重量％のＣｕを含有していた。As a result of fluorescent X-ray analysis and X-ray diffraction, the obtained dark brown particles were found to be acicular γ particles whose surfaces were coated with a Co compound.
-Fe@02 particle powder (Co amount is Co-coated γ-Fez
This corresponds to 2.5% by weight based on the O3 particle powder. ), and the particles contained 0.85% by weight of Cu.
このＣｕを含有するＣｏ化合物で被覆されている針状γ
−Ｆｅｚ０３粒子粉末の保磁力は７８４０ｅであった。Acicular γ coated with this Cu-containing Co compound
-The coercive force of the Fez03 particles was 7840e.
実施例２
前駆体として針状γ−Ｆｅｔｕｓ粒子（平均長軸径０．
３μｍ、軸比（長軸：短軸）８１、保磁力３７００ｅ）
を用い、該前駆体粒子粉末１００ｇを２１の水に分散さ
せて得られた分散液と、硫酸第一鉄と硫酸コバルトとを
用いて第一鉄０．２ ｍｏｌ及びコバルト０．１ｍｏｌ
を溶存させた水溶液５０ｈ＋ １とを混合した後６−Ｎ
のＮａＯＨ水溶液５００ｍ Ａを加え、ｐＨ１４の混合
液とした。得られた混合液を９５℃に昇温した後、空気
の混入を防止して撹拌しながら２４０分間保持した後、
ＣｕＳＯ４２，５ｇ （混合液中の針状ｒ−Ｆｅｚ０３
粒子に対し１．０重量％に該当する。）を添加し、引き
続き６０分間保持して黒褐色沈澱粒子を生成させた。Example 2 Acicular γ-Fetus particles (average major axis diameter 0.
3μm, axial ratio (long axis: short axis) 81, coercive force 3700e)
0.2 mol of ferrous iron and 0.1 mol of cobalt using a dispersion obtained by dispersing 100 g of the precursor particle powder in 21 water, and ferrous sulfate and cobalt sulfate.
After mixing with 50 hours of an aqueous solution containing dissolved
500 mA of NaOH aqueous solution was added to obtain a mixed solution having a pH of 14. After raising the temperature of the obtained mixture to 95 ° C., and holding it for 240 minutes while stirring while preventing air from entering,
CuSO42.5g (acicular r-Fez03 in the mixture
This corresponds to 1.0% by weight based on the particles. ) was added and then held for 60 minutes to form dark brown precipitated particles.
上記黒褐色沈澱を含む反応溶液は、常法により濾過、水
洗、乾燥した。The reaction solution containing the blackish brown precipitate was filtered, washed with water, and dried by a conventional method.
得られた黒褐色粒子粉末は、螢光Ｘ線分析及びＸ線回折
の結果、粒子表面がＣｏ化合物で被覆されている針状ｒ
−Ｆｅ、Ｏ，粒子粉末（Ｃｏ量は、Ｃｏ被覆γ−Ｆｅｚ
Ｏｘ粒子粉末に対し２．５重量％に該当する。）であり
、該粒子は、０．８ ＠量％のＣｕを含有していた。As a result of fluorescent X-ray analysis and X-ray diffraction, the obtained black-brown particle powder was found to have an acicular shape whose particle surface was coated with a Co compound.
-Fe, O, particle powder (Co amount is Co-coated γ-Fez
This corresponds to 2.5% by weight based on the Ox particle powder. ), and the particles contained 0.8% Cu.
このＣｕを含有するＣｏ化合物で被覆されている針状γ
−Ｆｅ２０３粒子粉末の保磁力は８０４０ｅであった。Acicular γ coated with this Cu-containing Co compound
-The coercive force of the Fe203 particles was 8040e.
実施例３
前駆体として針状γ−Ｆｅｚ’：ｈ粒子（平均長軸径０
．３μｍ、軸比（長軸：短軸）８：１、保磁力３７００
ｅ）を用い、該前駆体粒子粉末１００ｇを２１の水に分
散させて得られた分散液と、硫酸第一鉄と硫酸コバルト
とを用いて第一鉄０．２ ｍｏｌ及びコバルト０．１ｍ
ｏｌを溶存させた水溶液５００ｍ ｌとを混合した後６
−ＮのＮａＯＨ水溶液５００ｍ ｌを加え、ρ旧４の混
合液とした。得られた混合液を９５℃に昇温した後、空
気の混入を防止して攪拌しながら２４０分間保持した後
、ＣｕＳＯ４１，２６ｇ（混合液中の針状７−Ｆｅ２Ｏ
３粒子に対し０．５重量％に該当する。）を添加し、引
き続き１８０分間保持して黒褐色沈澱粒子を生成させた
。Example 3 Acicular γ-Fez':h particles (average major axis diameter 0) as a precursor
．． 3μm, axial ratio (long axis: short axis) 8:1, coercive force 3700
Using e), 0.2 mol of ferrous iron and 0.1 m of cobalt were prepared using a dispersion obtained by dispersing 100 g of the precursor particles in 21 water, and ferrous sulfate and cobalt sulfate.
After mixing with 500 ml of an aqueous solution containing 6
-N NaOH aqueous solution (500 ml) was added to prepare a mixed solution of ρ-old 4. After heating the obtained mixed solution to 95°C and holding it for 240 minutes while stirring to prevent air from entering, 1.26 g of CuSO4 (acicular 7-Fe2O in the mixed solution) was heated.
This corresponds to 0.5% by weight for 3 particles. ) was added and then held for 180 minutes to form dark brown precipitated particles.
上記黒褐色沈澱を含む反応溶液は、常法により濾過、水
洗、乾燥した。The reaction solution containing the blackish brown precipitate was filtered, washed with water, and dried by a conventional method.
得られた黒褐色粒子粉末は、螢光Ｘ線分析及びＸ線回折
の結果、粒子表面がＣｏ化合物で被覆されている針状γ
−Ｆｅｔｕｓ粒子粉末（Ｃｏ量は、Ｃｏ被覆Ｔ−Ｆｅ２
０３粒子粉末に対し２．５重量％に該当する。）であり
、該粒子は、０．４０重量％のＣｕを含有していた。As a result of fluorescent X-ray analysis and X-ray diffraction, the obtained dark brown particles were found to be acicular γ particles whose surfaces were coated with a Co compound.
-Fetus particle powder (Co amount is Co-coated T-Fe2
This corresponds to 2.5% by weight based on the 03 particle powder. ), and the particles contained 0.40% by weight of Cu.
このＣｕを含有するＣｏ化合物で被覆されている針状γ
−Ｐｅ１０．粒子粉末の保磁力は７９００ｅであった。Acicular γ coated with this Cu-containing Co compound
-Pe10. The coercive force of the particle powder was 7900e.
比較例ｌ
Ｃｕ５Ｏｎを添加しなかった以外は、実施例１と同様に
してＣｏ化合物で被覆されている針状ｒ −ＦｅｚＯｉ
粒子粉末を得た。Comparative Example 1 Acicular r -FezOi coated with a Co compound in the same manner as in Example 1 except that Cu5On was not added.
A particulate powder was obtained.
得られたＣｏ化合物で被覆されている針状γ−Ｆｅ２０
３粒子粉末の保磁力は７３４０ｅであった。Acicular γ-Fe20 coated with the obtained Co compound
The coercive force of the 3-grain powder was 7340e.
本発明における針状磁性酸化鉄粒子粉末の製造法によれ
ば、前出実施例に示した通り、少ないＣ。According to the method for producing acicular magnetic iron oxide particles of the present invention, as shown in the previous example, the amount of C is reduced.
被覆量で保磁力を効果的に向上させることができること
に起因して、高い保磁力を有し、且つ、消去特性に優れ
ているＣｏ化合物で被覆されている針状磁性酸化鉄粒子
粉末を得ることができるので、高密度記録用磁性酸化鉄
粒子粉末として好適である。Obtaining acicular magnetic iron oxide particle powder coated with a Co compound that has a high coercive force and excellent erasing properties due to the fact that the coercive force can be effectively improved by changing the coating amount. Therefore, it is suitable as a magnetic iron oxide particle powder for high-density recording.
図１は、Ｃｏ化合物で被覆されている針状磁性酸化鉄粒
子粉末の保磁力とＣｕ塩の添加量との関係図である。FIG. 1 is a diagram showing the relationship between the coercive force of acicular magnetic iron oxide particles coated with a Co compound and the amount of Cu salt added.
Claims (1)
塩水溶液及びアルカリ水溶液とを混合して得られたｐＨ
１１以上の混合液を、５０〜１００℃の温度範囲で加熱
処理して、前記針状磁性酸化鉄粒子の粒子表面にＣｏ化
合物を生成させることにより、粒子表面がＣｏ化合物で
被覆されている針状磁性酸化鉄粒子粉末を製造する方法
において、前記ｐＨ１１以上の混合液に、Ｃｏ化合物の
生成反応開始後から終了までの間に、混合液中の針状磁
性酸化鉄粒子に対しＣｕ換算で０．２〜２．０重量％の
銅塩を添加することを特徴とする針状磁性酸化鉄粒子粉
末の製造法。(1) An aqueous dispersion of acicular magnetic iron oxide particles and at least Co
pH obtained by mixing salt aqueous solution and alkaline aqueous solution
Needles whose particle surfaces are coated with a Co compound by heating a mixture of 11 or more at a temperature range of 50 to 100° C. to generate a Co compound on the particle surface of the acicular magnetic iron oxide particles. In the method for producing acicular magnetic iron oxide particles powder, in the mixed liquid having a pH of 11 or more, from the start to the end of the reaction for producing a Co compound, 0 is added in terms of Cu to the acicular magnetic iron oxide particles in the mixed liquid. . A method for producing acicular magnetic iron oxide particles, characterized by adding 2 to 2.0% by weight of copper salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61296168A JPH0822745B2 (en) | 1986-12-12 | 1986-12-12 | Method for producing acicular magnetic iron oxide particle powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61296168A JPH0822745B2 (en) | 1986-12-12 | 1986-12-12 | Method for producing acicular magnetic iron oxide particle powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63151621A true JPS63151621A (en) | 1988-06-24 |
| JPH0822745B2 JPH0822745B2 (en) | 1996-03-06 |
Family
ID=17830040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61296168A Expired - Fee Related JPH0822745B2 (en) | 1986-12-12 | 1986-12-12 | Method for producing acicular magnetic iron oxide particle powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0822745B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03161904A (en) * | 1989-11-21 | 1991-07-11 | Shiseido Co Ltd | Manufacture of needlelike crystal magnetic iron oxide powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106895A (en) * | 1978-02-08 | 1979-08-22 | Fuji Photo Film Co Ltd | Ferromagnetic powder |
| JPS5635614A (en) * | 1979-08-30 | 1981-04-08 | Amp Inc | Tool for separating conductor from flexible insulating flat cable with multicore conductors |
-
1986
- 1986-12-12 JP JP61296168A patent/JPH0822745B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106895A (en) * | 1978-02-08 | 1979-08-22 | Fuji Photo Film Co Ltd | Ferromagnetic powder |
| JPS5635614A (en) * | 1979-08-30 | 1981-04-08 | Amp Inc | Tool for separating conductor from flexible insulating flat cable with multicore conductors |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03161904A (en) * | 1989-11-21 | 1991-07-11 | Shiseido Co Ltd | Manufacture of needlelike crystal magnetic iron oxide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0822745B2 (en) | 1996-03-06 |
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