JP3129823B2 - Method for producing ferromagnetic iron oxide powder for magnetic recording - Google Patents
Method for producing ferromagnetic iron oxide powder for magnetic recordingInfo
- Publication number
- JP3129823B2 JP3129823B2 JP04065874A JP6587492A JP3129823B2 JP 3129823 B2 JP3129823 B2 JP 3129823B2 JP 04065874 A JP04065874 A JP 04065874A JP 6587492 A JP6587492 A JP 6587492A JP 3129823 B2 JP3129823 B2 JP 3129823B2
- Authority
- JP
- Japan
- Prior art keywords
- iron
- zinc
- manganese
- iron oxide
- atomic
- 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 - Fee Related
Links
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 223
- 230000005291 magnetic effect Effects 0.000 title claims description 82
- 239000000843 powder Substances 0.000 title claims description 79
- 230000005294 ferromagnetic effect Effects 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000002245 particle Substances 0.000 claims description 143
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 128
- 239000011701 zinc Substances 0.000 claims description 83
- 239000011572 manganese Substances 0.000 claims description 73
- 229910052725 zinc Inorganic materials 0.000 claims description 72
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 60
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 57
- 229910052748 manganese Inorganic materials 0.000 claims description 57
- 229910052742 iron Inorganic materials 0.000 claims description 55
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 44
- 229910052595 hematite Inorganic materials 0.000 claims description 34
- 239000011019 hematite Substances 0.000 claims description 34
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 30
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 230000001590 oxidative effect Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000007704 transition Effects 0.000 claims description 18
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000001869 cobalt compounds Chemical class 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 3
- 239000006249 magnetic particle Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000000543 intermediate Substances 0.000 description 68
- 239000007864 aqueous solution Substances 0.000 description 38
- 230000005415 magnetization Effects 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000001868 cobalt Chemical class 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000003513 alkali Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007900 aqueous suspension Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DILISPNYIVRDBP-UHFFFAOYSA-N 2-[3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]-2-naphthalen-2-ylimidazol-4-yl]acetonitrile Chemical compound OC(CNC1=NC=CC(=N1)N1C(=NC=C1CC#N)C1=CC2=CC=CC=C2C=C1)C DILISPNYIVRDBP-UHFFFAOYSA-N 0.000 description 2
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- MCRWZBYTLVCCJJ-DKALBXGISA-N [(1s,3r)-3-[[(3s,4s)-3-methoxyoxan-4-yl]amino]-1-propan-2-ylcyclopentyl]-[(1s,4s)-5-[6-(trifluoromethyl)pyrimidin-4-yl]-2,5-diazabicyclo[2.2.1]heptan-2-yl]methanone Chemical compound C([C@]1(N(C[C@]2([H])C1)C(=O)[C@@]1(C[C@@H](CC1)N[C@@H]1[C@@H](COCC1)OC)C(C)C)[H])N2C1=CC(C(F)(F)F)=NC=N1 MCRWZBYTLVCCJJ-DKALBXGISA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
- -1 phosphorus compound Chemical class 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- NYNZQNWKBKUAII-KBXCAEBGSA-N (3s)-n-[5-[(2r)-2-(2,5-difluorophenyl)pyrrolidin-1-yl]pyrazolo[1,5-a]pyrimidin-3-yl]-3-hydroxypyrrolidine-1-carboxamide Chemical compound C1[C@@H](O)CCN1C(=O)NC1=C2N=C(N3[C@H](CCC3)C=3C(=CC=C(F)C=3)F)C=CN2N=C1 NYNZQNWKBKUAII-KBXCAEBGSA-N 0.000 description 1
- SSORSZACHCNXSJ-UHFFFAOYSA-N 2-[2-(3,4-dichlorophenyl)-3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound ClC=1C=C(C=CC=1Cl)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NCC(C)O SSORSZACHCNXSJ-UHFFFAOYSA-N 0.000 description 1
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
- ONPGOSVDVDPBCY-CQSZACIVSA-N 6-amino-5-[(1r)-1-(2,6-dichloro-3-fluorophenyl)ethoxy]-n-[4-(4-methylpiperazine-1-carbonyl)phenyl]pyridazine-3-carboxamide Chemical compound O([C@H](C)C=1C(=C(F)C=CC=1Cl)Cl)C(C(=NN=1)N)=CC=1C(=O)NC(C=C1)=CC=C1C(=O)N1CCN(C)CC1 ONPGOSVDVDPBCY-CQSZACIVSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Hard Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
- Powder Metallurgy (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗布型高記録密度磁気
記録媒体に用いられる改良された磁性粉末に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved magnetic powder used for a coating type high recording density magnetic recording medium.
【０００２】[0002]
【発明が解決しようとする課題】磁気記録再生機器の小
型軽量化及び磁気記録における情報処理量の拡大化に伴
い、近年磁気記録媒体の高記録密度化、高出力化及び低
ノイズ化の指向が益々高まってきている。これとあいま
って、磁気記録媒体に使用される磁性酸化鉄粉末につい
ては、高保磁力化、高飽和磁化量化、微粒子化及び高配
向高充填化などの諸特性の要求が一段と強まっている。With the reduction in size and weight of magnetic recording / reproducing devices and the increase in the amount of information processing in magnetic recording, the trend toward higher recording density, higher output, and lower noise of magnetic recording media has recently been increasing. Increasingly. In conjunction with this, with respect to the magnetic iron oxide powder used for the magnetic recording medium, demands for various properties such as a high coercive force, a high saturation magnetization, a fine graining, and a high orientation and high filling are further increased.
【０００３】これら諸特性のうち、高飽和磁化量化につ
いても種々の試みが既に成されている。コバルト被着強
磁性酸化鉄粉末の出発原料をマグヘマイト粒子から中間
体粒子もしくはマグネタイト粒子に転換して高飽和磁化
量を実現させる方法がその一例である。しかし、その飽
和磁化量は未だ不十分である。[0003] Among these various properties, various attempts have already been made for increasing the saturation magnetization. One example is a method of converting the starting material of the cobalt-coated ferromagnetic iron oxide powder from maghemite particles to intermediate particles or magnetite particles to achieve a high saturation magnetization. However, the saturation magnetization is still insufficient.
【０００４】本発明の目的は、前記の問題点を解決すべ
く塗布型高記録密度磁気記録媒体に好適な高飽和磁化量
を有する強磁性酸化鉄粉末を提供することにある。[0004] An object of the present invention is to provide a ferromagnetic iron oxide powder having a high saturation magnetization suitable for a coating type high recording density magnetic recording medium in order to solve the above problems.
【０００５】[0005]
【課題を解決するための手段】本発明者は、高飽和磁化
である強磁性酸化鉄粉末の製造を実現させるため検討を
進めてきた結果、特願平３−１４０９において示した様
に、マグヘマイト粒子もしくはマグヘマイト化する前躯
体の水和酸化鉄粒子に、マンガン、亜鉛及び任意に鉄を
含む溶液で処理し、熱処理を施すことにより、それら金
属が粒子内部に固溶し、マンガンと亜鉛の複合効果によ
り飽和磁化量が向上したマグヘマイト粒子を得ることが
できた。Means for Solving the Problems The present inventor has conducted studies to realize the production of a ferromagnetic iron oxide powder having a high saturation magnetization. As a result, as shown in Japanese Patent Application No. 3-1409, maghemite is disclosed. The hydrated iron oxide particles, which are particles or maghemitized precursors, are treated with a solution containing manganese, zinc and optionally iron, and subjected to heat treatment, so that these metals form a solid solution inside the particles and form a composite of manganese and zinc. As a result, maghemite particles having an improved saturation magnetization can be obtained.
【０００６】引き続き検討を進めた結果、前記の飽和磁
化量が向上したマグヘマイト粒子を還元して中間体化
し、再度非酸化性雰囲気下で熱処理を施すことにより、
飽和磁化量がさらに向上することが明らかになった。こ
の原因については、第一鉄共存下において熱処理を施し
た場合、それら金属の拡散が容易になり固溶が促進され
るためと考えられる。また、この製法によれば、マンガ
ン及び亜鉛をさらに増量することが可能である。すなわ
ち、マンガンは単に亜鉛と共存して磁性体の飽和磁化量
を向上させるだけではなく、焼結防止剤としての効果も
有し、亜鉛単独の場合より熱処理温度を高くでき、飽和
磁化量を飛躍的に向上させることが可能となった。[0006] As a result of continued study, the above-mentioned maghemite particles having an improved saturation magnetization were reduced to an intermediate, and again subjected to a heat treatment in a non-oxidizing atmosphere.
It was found that the saturation magnetization was further improved. It is considered that the reason for this is that when heat treatment is performed in the coexistence of ferrous iron, diffusion of those metals is facilitated and solid solution is promoted. Further, according to this production method, it is possible to further increase the amounts of manganese and zinc. In other words, manganese not only improves the saturation magnetization of the magnetic material by coexisting with zinc, but also has an effect as a sintering inhibitor, so that the heat treatment temperature can be higher than in the case of zinc alone, and the saturation magnetization increases. It became possible to improve it.
【０００７】本発明は、鉄総量に対して０．１〜１９原
子重量％、好ましくは０．１〜１６原子重量％のマンガ
ン、及び鉄総量に対して３〜１９原子重量％、好ましく
は３〜１６原子重量％の亜鉛を含有する磁気記録用強磁
性酸化鉄粉末を提供するものであり、この磁気記録用強
磁性酸化鉄粉末は鉄総量に対して３１原子重量％以下の
第一鉄を含有することができる。さらに、該酸化鉄はコ
バルト塩、またはコバルト塩と第一鉄塩を含む溶液で処
理することができる。The present invention relates to manganese in an amount of 0.1 to 19 at.%, Preferably 0.1 to 16 at.%, Based on the total amount of iron, and 3 to 19 at.%, Preferably 3 to 19 at. The present invention provides a ferromagnetic iron oxide powder for magnetic recording containing about 16 atomic% by weight of zinc, wherein the ferromagnetic iron oxide powder for magnetic recording contains 31 atomic% by weight or less of ferrous iron based on the total amount of iron. Can be contained. Further, the iron oxide can be treated with a cobalt salt or a solution containing a cobalt salt and a ferrous salt.
【０００８】マンガン及び亜鉛が上記範囲の量よりも少
ない場合には本発明の効果を奏することができず、また
上記範囲の量よりも大きくしてももはや飽和磁化量は増
大しない。If the amount of manganese and zinc is less than the above range, the effect of the present invention cannot be obtained. If the amount is larger than the above range, the saturation magnetization no longer increases.
【０００９】また、第一鉄の含有量を鉄総量に対して３
１原子重量％以下としているのは、それより多くなると
マグネタイト（第一鉄の含有量が３３．３原子重量％）
近傍領域になるため、酸化安定性が著しく悪化し、室温
でも発火することがあるなど実際的でなくなるためであ
る。[0009] Further, the content of ferrous iron is 3 to the total amount of iron.
The reason why the content is set to 1 atomic weight% or less is that if the content is more than that, magnetite (the content of ferrous iron is 33.3 atomic weight%)
The reason for this is that, since it is in the vicinity, the oxidation stability is significantly deteriorated, and it becomes impractical, for example, it may ignite even at room temperature.
【００１０】本発明にかかる酸化鉄粉末を製造するため
の方法としては種々の方法が考えられるが、以下に好ま
しい方法について説明する。なお、本明細書において
「中間体粒子」とは、マグヘマイトとマグネタイトの中
間体粒子を意味する。又、「ｔＦｅ」を鉄総量を意味す
る記号として用いる。Various methods are conceivable as methods for producing the iron oxide powder according to the present invention. Preferred methods will be described below. In this specification, “intermediate particles” mean intermediate particles of maghemite and magnetite. "TFe" is used as a symbol indicating the total amount of iron.
【００１１】（１） マグヘマイト粒子の水性懸濁液に
マンガン、亜鉛及び任意に鉄化合物を含む水溶液を添加
する。本発明に用いるマンガン、亜鉛及び鉄成分として
種々の化合物が使用できるが、例えばそれらの硫酸塩、
硝酸塩、塩化物などの水溶性のものが適当である。マン
ガン成分は第一マンガンを用いる必要があるが、鉄成分
については第一鉄もしくは第二鉄のいずれを用いても本
発明の効果は変わらない。マンガンは金属処理後のマグ
ヘマイト粒子中のＭｎ／ｔＦｅとして０．１〜１９原子
重量％、好ましくは０．１〜１６原子重量％を含有し、
一方亜鉛はＺｎ／ｔＦｅとして３〜１９原子重量％、好
ましくは３〜１６原子重量％を含有する様に添加する。
鉄は無添加にするかもくしはモル基準でマンガン及び亜
鉛の総添加量の２倍量までを添加できる。さらにアルカ
リを添加してｐＨを１０〜１１に調整し、添加金属を基
体粒子表面上に水酸化物として被着させてから、濾過、
水洗し懸濁液中に残存する余剰のアルカリなどを除去す
る。そして空気中５０〜１１０°Ｃの乾燥を行なう。引
き続いて公知の方法を適用することにより還元し、第一
鉄の含有量がＦｅ（ＩＩ）／ｔＦｅとして３１原子重量
％以下の中間体にする。その方法は、例えば水素ガス流
通下２３０°Ｃの還元をする方法であるが、第一鉄の含
有量は還元時間を調整することで所望のレベルにするこ
とができる。さらに非酸化性雰囲気下で熱処理する。雰
囲気を非酸化性にする理由は、第一鉄と第一マンガンの
酸化を防止するためであり、窒素、二酸化炭素及びヘリ
ウム、アルゴンなどの希ガスを用いることができる。熱
処理の温度は４００°Ｃ〜ヘマタイトへの転移が生じな
い上限温度までとする。好ましくは４００〜７５０°Ｃ
である。熱処理の時間は０．５〜２４時間、好ましくは
１〜６時間とする。前記の金属被着処理直後の段階にお
いては、添加金属は基体粒子表面上に非磁性の水酸化物
もしくは酸化物として存在するだけであるが、還元及び
熱処理することで結晶内部に固溶し、マンガン及び亜鉛
の複合効果で飽和磁化量が向上するものと考えられる。(1) An aqueous solution containing manganese, zinc and optionally an iron compound is added to the aqueous suspension of maghemite particles. Various compounds can be used as the manganese, zinc and iron components used in the present invention, for example, their sulfates,
Water-soluble substances such as nitrates and chlorides are suitable. It is necessary to use ferrous manganese for the manganese component, but the effect of the present invention does not change even if ferrous or ferric iron is used for the iron component. Manganese contains 0.1 to 19 atomic weight%, preferably 0.1 to 16 atomic weight% as Mn / tFe in the maghemite particles after the metal treatment,
On the other hand, zinc is added so as to contain 3 to 19 atomic weight%, preferably 3 to 16 atomic weight% as Zn / tFe.
Iron may be added without addition or up to twice the total amount of manganese and zinc added on a molar basis. Further, the pH is adjusted to 10 to 11 by adding an alkali, and the added metal is deposited as a hydroxide on the surface of the base particles.
Washing with water removes excess alkali and the like remaining in the suspension. Then, drying at 50 to 110 ° C. in air is performed. It is subsequently reduced by applying known methods to intermediates having a ferrous iron content of less than 31 at.% By weight as Fe (II) / tFe. The method is, for example, a method of reducing the temperature at 230 ° C. under a flow of hydrogen gas. The content of ferrous iron can be adjusted to a desired level by adjusting the reduction time. Further, heat treatment is performed in a non-oxidizing atmosphere. The reason why the atmosphere is made non-oxidizing is to prevent oxidation of ferrous iron and manganese, and nitrogen, carbon dioxide, and a rare gas such as helium or argon can be used. The temperature of the heat treatment is from 400 ° C. to the upper limit temperature at which the transition to hematite does not occur. Preferably 400-750 ° C
It is. The time of the heat treatment is 0.5 to 24 hours, preferably 1 to 6 hours. At the stage immediately after the metal deposition treatment, the added metal is present only as a non-magnetic hydroxide or oxide on the surface of the base particles, but is solid-solved inside the crystal by reduction and heat treatment, It is considered that the saturation magnetization is improved by the combined effect of manganese and zinc.
【００１２】（２） 第１鉄の含有量がＦｅ（ＩＩ）／
ｔＦｅとして３１原子重量％以下である中間体粒子の水
性懸濁液にマンガン、亜鉛及び任意に鉄化合物を含む水
溶液を添加する。マンガンは金属処理後の中間体粒子中
のＭｎ／ｔＦｅとして０．１〜１９原子重量％、好まし
くは０．１〜１６原子重量％を含有し、一方亜鉛はＺｎ
／ｔＦｅとして３〜１９原子重量％、好ましくは３〜１
６原子重量％を含有する様に添加する。鉄は無添加にす
るかもしくはモル基準でマンガン及び亜鉛の総添加量の
２倍量までを添加できる。さらにアルカリを添加してｐ
Ｈを１０〜１１に調整し、添加金属を基体粒子表面上に
水酸化物として被着させてから、濾過、水洗し懸濁液中
に残存する余剰のアルカリなどを除去する。そして非酸
化性雰囲気下で５０〜１１０°Ｃの乾燥を行ない、引き
続いて同じく非酸化性雰囲気下で熱処理する。熱処理の
温度は４００°Ｃ〜ヘマタイトへの転移が生じない上限
温度までとする。好ましくは４００〜７５０°Ｃであ
る。熱処理の時間は０．５〜２４時間、好ましくは１〜
６時間とする。(2) The ferrous iron content is Fe (II) /
An aqueous solution containing manganese, zinc and optionally an iron compound is added to an aqueous suspension of intermediate particles having a tFe of 31 atomic weight% or less. Manganese contains 0.1 to 19 atomic weight%, preferably 0.1 to 16 atomic weight% as Mn / tFe in the intermediate particles after metal treatment, while zinc contains Zn
3 to 19 atomic weight%, preferably 3 to 1
It is added so as to contain 6 atomic weight%. Iron can be left unadded or added up to twice the total amount of manganese and zinc on a molar basis. Add alkali and add p
After adjusting the H to 10 to 11 and attaching the added metal as a hydroxide on the surface of the base particles, filtration and washing with water are performed to remove excess alkali and the like remaining in the suspension. Then, drying is performed at 50 to 110 ° C. in a non-oxidizing atmosphere, followed by heat treatment in the same non-oxidizing atmosphere. The temperature of the heat treatment is from 400 ° C. to the upper limit temperature at which the transition to hematite does not occur. Preferably it is 400-750 degreeC. The heat treatment time is 0.5 to 24 hours, preferably 1 to 24 hours.
6 hours.
【００１３】（３） 水和酸化鉄粒子の水性懸濁液にマ
ンガン及び亜鉛化合物を含む水溶液を添加する。マンガ
ンは加熱脱水してヘマタイト化した段階でＭｎ／ｔＦｅ
として０．１〜１９原子重量％、好ましくは０．１〜１
６原子重量％を含有し、一方亜鉛はＺｎ／ｔＦｅとして
３〜１９原子重量％、好ましくは３〜１６原子重量％を
含有する様に添加する。さらにアルカリを添加してｐＨ
を１０〜１１に調整し、添加金属を基体粒子表面上に水
酸化物として被着させてから、濾過、水洗して懸濁液中
に残存する余剰のアルカリなどを除去し、空気中５０〜
１１０°Ｃの乾燥を行なう。引き続き５００〜６５０°
Ｃ−０．５時間の加熱脱水を行ない、水素ガス流通下３
００〜３５０°Ｃ−３時間の還元、さらに非酸化性雰囲
気下で熱処理をする。熱処理の温度は４００°Ｃ〜ヘマ
タイトへの転移が生じない上限温度までとする。好まし
くは４００〜７５０°Ｃである。熱処理の時間は、０．
５〜２４時間、好ましくは１〜６時間とする。後工程は
公知の方法で中間体粒子もしくはマグヘマイト粒子に仕
上げる。例えば中間体粒子に仕上げる場合は、空気流通
下で５０°Ｃ−２時間の酸化をして酸化が完結する前に
取り出す。一方マグヘマイト粒子に仕上げる場合は、空
気流通下２５０°Ｃ−３時間の酸化をしてマグヘマイト
化する。(3) An aqueous solution containing manganese and zinc compounds is added to the aqueous suspension of hydrated iron oxide particles. Manganese is Mn / tFe when heated and dehydrated to form hematite.
0.1 to 19 atomic weight%, preferably 0.1 to 1
Zinc is added to contain 3 to 19 atomic weight%, preferably 3 to 16 atomic weight% as Zn / tFe. Further add alkali to pH
Is adjusted to 10 to 11 and the added metal is applied as a hydroxide on the surface of the base particles, and then filtered and washed with water to remove excess alkali and the like remaining in the suspension.
Dry at 110 ° C. Continue 500-650 °
C-Perform heat dehydration for 0.5 hour,
Reduction is performed at 00 to 350 ° C. for 3 hours, and heat treatment is performed in a non-oxidizing atmosphere. The temperature of the heat treatment is from 400 ° C. to the upper limit temperature at which the transition to hematite does not occur. Preferably it is 400-750 degreeC. The heat treatment time is 0.
5 to 24 hours, preferably 1 to 6 hours. In the subsequent step, intermediate particles or maghemite particles are finished by a known method. For example, in the case of finishing to intermediate particles, the particles are oxidized at 50 ° C. for 2 hours under a flow of air and taken out before the oxidation is completed. On the other hand, when finishing to maghemite particles, the particles are oxidized at 250 ° C. for 3 hours under air flow to form maghemite.
【００１４】（４） 金属の被着処理から還元によるマ
グネタイト化までは（３）と同じである。以降の工程
は、次の通りである。空気流通下５０°Ｃで酸化して中
間体化する。中間体の第一鉄含有量は、酸化時間を調整
することで所望のレベルにすることができる。引き続き
熱処理して、中間体として仕上げる。熱処理の温度は４
００°Ｃ〜ヘマタイトの転移が生じない上限温度までと
する。好ましくは４００〜７５０°Ｃである。熱処理の
時間は０．５〜２４時間、好ましくは１〜６時間とす
る。マグヘマイト粒子に仕上げる場合は、さらに空気流
通下２５０°Ｃ−３時間の酸化をする。(4) The process from the deposition of the metal to the formation of magnetite by reduction is the same as (3). The subsequent steps are as follows. It is oxidized at 50 ° C under air flow to form an intermediate. The ferrous content of the intermediate can be brought to a desired level by adjusting the oxidation time. Subsequently, it is heat-treated and finished as an intermediate. Heat treatment temperature is 4
The temperature is from 00 ° C. to an upper limit temperature at which the transformation of hematite does not occur. Preferably it is 400-750 degreeC. The time of the heat treatment is 0.5 to 24 hours, preferably 1 to 6 hours. When finishing to maghemite particles, oxidation is further performed at 250 ° C. for 3 hours under air flow.
【００１５】（５） 前記（３）と（４）で得られた飽
和磁化量が向上したマグヘマイト粒子または中間体粒子
を希薄な酸性溶液で洗浄し、粒子表面に残存する非磁性
のマンガン及び亜鉛の酸化物等を除去する。引き続き、
マグヘマイト粒子は（１）、中間体粒子は（２）と同様
の金属被着処理及び熱処理をすることにより、飽和磁化
量をさらに高めることができる。（１）及び（２）と異
なる点としては、マンガン及び亜鉛と同時に鉄を必ず添
加する必要がある。鉄は、モル基準でマンガン及び亜鉛
の総添加量の１〜２倍量を添加する必要がある。マンガ
ン及び亜鉛の適正含有量は、Ｍｎ／ｔＦｅとして０．１
〜１９原子重量％、好ましくは０．１〜１６原子重量
％、一方亜鉛はＺｎ／ｔＦｅとして３〜１９原子重量
％、好ましくは３〜１６原子重量％である。(5) The maghemite particles or intermediate particles having improved saturation magnetization obtained in (3) and (4) are washed with a dilute acidic solution, and non-magnetic manganese and zinc remaining on the particle surfaces Oxides and the like are removed. Continued
The saturation magnetization can be further increased by subjecting the maghemite particles to (1) and the intermediate particles to the same metal deposition treatment and heat treatment as in (2). The difference from (1) and (2) is that iron must be added simultaneously with manganese and zinc. Iron must be added in an amount of 1 to 2 times the total amount of manganese and zinc on a molar basis. The proper content of manganese and zinc is 0.1 as Mn / tFe.
-19 at%, preferably 0.1-16 at%, while zinc is 3-19 at%, preferably 3-16 at% as Zn / tFe.
【００１６】（６） 前記（１）〜（５）で得られた飽
和磁化量が向上したマグヘマイト粒子もしくは中間体粒
子は、公知の方法により粒子表面にコバルト塩もしくは
コバルト塩と第一鉄塩を含む溶液で被着処理することに
より、保磁力を高めて磁気特性をより一層向上させるこ
とができる。被着処理の方法は、例えば以下の通りであ
る。マグヘマイト粒子もしくは中間体粒子の水性懸濁液
に、アルカリ及びコバルト塩もしくはアルカリ，コバル
ト塩及び第一鉄塩を添加して反応させる。コバルトの被
着量は基体粒子基準で１〜９ｗｔ％、好ましくは２〜８
ｗｔ％、第一鉄塩を併用する場合、第一鉄塩の被着量は
Ｆｅ（ＩＩ）として１０ｗｔ％以下、好ましくは３〜８
ｗｔ％とする。さらに８０〜９５°Ｃまで加熱して２〜
７時間の熟成を行う。被着反応後、濾過、水洗、乾燥し
てコバルト被着強磁性酸化鉄粉末にする。(6) The maghemite particles or intermediate particles having improved saturation magnetization obtained in the above (1) to (5) are prepared by adding a cobalt salt or a cobalt salt and a ferrous salt to the particle surface by a known method. By performing the deposition treatment with the solution containing the magnetic material, the coercive force can be increased and the magnetic characteristics can be further improved. The method of the deposition process is, for example, as follows. Alkali and cobalt salts or alkali, cobalt salts and ferrous salts are added to an aqueous suspension of maghemite particles or intermediate particles and reacted. The coating amount of cobalt is 1 to 9 wt%, preferably 2 to 8 wt%, based on the base particles.
When the ferrous salt is used in combination with the ferrous salt, the amount of the ferrous salt to be applied is 10 wt% or less as Fe (II), preferably 3 to 8%.
wt%. And then heat to 80-95 ° C
Aging for 7 hours. After the deposition reaction, it is filtered, washed with water, and dried to obtain a cobalt-deposited ferromagnetic iron oxide powder.
【００１７】以上をまとめると、本発明にかかる酸化鉄
粉末の製造方法の態様としては以下のものが挙げられ
る。To summarize the above, embodiments of the method for producing iron oxide powder according to the present invention include the following.
【００１８】１． マグヘマイト粒子をマンガン、亜鉛
及び任意に鉄を含む溶液で処理し、鉄総量に対して０．
１〜１９原子重量％のマンガン、及び鉄総量に対して３
〜１９原子重量％の亜鉛を含有させたマグヘマイト粒子
を、還元して鉄総量に対して３１原子重量％以下の第一
鉄を含有する中間体粒子とし、さらに非酸化性雰囲気下
にて４００°Ｃ〜ヘマタイトへの転移が生じない上限温
度で熱処理することを特徴とする磁気記録用強磁性酸化
鉄粉末の製造方法。1. The maghemite particles are treated with a solution containing manganese, zinc and optionally iron, with a concentration of 0.1% based on the total iron.
1 to 19 atomic% by weight of manganese and 3 based on the total amount of iron
The maghemite particles containing １９19 at.% By weight of zinc are reduced to intermediate particles containing less than 31 at.% By weight of ferrous iron based on the total amount of iron, and further 400 ° C. in a non-oxidizing atmosphere. A method for producing a ferromagnetic iron oxide powder for magnetic recording, comprising performing heat treatment at an upper limit temperature at which a transition from C to hematite does not occur.
【００１９】２． 鉄総量に対して３１原子重量％以下
の第一鉄を含有する中間体粒子をマンガン、亜鉛及び任
意に鉄を含む溶液で処理し、鉄総量に対して０．１〜１
９原子重量％のマンガン、及び鉄総量に対して３〜１９
原子重量％の亜鉛を含有させた中間体粒子とし、さらに
非酸化性雰囲気下にて４００°Ｃ〜ヘマタイトへの転移
が生じない上限温度で熱処理することを特徴とする磁気
記録用強磁性酸化鉄粉末の製造方法。2. Intermediate particles containing less than 31 atomic weight percent ferrous iron, based on total iron, are treated with a solution containing manganese, zinc, and optionally iron, with 0.1 to 1 relative to total iron.
9 atomic weight% of manganese and 3 to 19 based on the total amount of iron
A ferromagnetic iron oxide for magnetic recording, comprising: an intermediate particle containing atomic weight% of zinc; and a heat treatment in a non-oxidizing atmosphere at 400 ° C. to an upper limit temperature at which a transition to hematite does not occur. Powder manufacturing method.
【００２０】３． 水和酸化鉄粒子をマンガン及び亜鉛
を含む溶液で処理し、加熱脱水、還元し、鉄総量に対し
て０．１〜１９原子重量％のマンガン、及び鉄総量に対
して３〜１９原子重量％の亜鉛を含有させたマグネタイ
ト粒子とし、その後非酸化性雰囲気下にて４００℃〜ヘ
マタイトへの転移が生じない上限温度で熱処理し、さら
に酸化してマグヘマイトとすることを特徴とする磁気記
録用強磁性酸化鉄粉末の製造方法。3. The hydrated iron oxide particles are treated with a solution containing manganese and zinc, heat dehydrated and reduced, and 0.1 to 19 atomic weight% manganese based on the total iron, and 3 to 19 atomic weight% based on the total iron. A magnetite particle containing zinc, and then heat-treated in a non-oxidizing atmosphere at 400 ° C. to an upper limit temperature at which the transition to hematite does not occur, and further oxidized to maghemite. Manufacturing method of magnetic iron oxide powder.
【００２１】４． 前記の酸化が微酸化である、上記３
記載の製造方法。4. 3. The above-mentioned item 3, wherein the oxidation is slight oxidation.
The manufacturing method as described.
【００２２】５． 水和酸化鉄粒子をマンガン及び亜鉛
を含む溶液で処理し、加熱脱水、還元し、微酸化し、鉄
総量に対して０．１〜１９原子重量％のマンガン、及び
鉄総量に対して３〜１９原子重量％の亜鉛を含有させた
中間体粒子とし、その後非酸化性雰囲気下にて４００°
Ｃ〜ヘマタイトへの転移が生じない上限温度で熱処理す
ることを特徴とする磁気記録用強磁性酸化鉄粉末の製造
方法。5. The hydrated iron oxide particles are treated with a solution containing manganese and zinc, thermally dehydrated, reduced, slightly oxidized, and 0.1 to 19 atomic weight% manganese based on the total iron, and 3 to 3 atomic% based on the total iron. Intermediate particles containing 19 atomic% by weight of zinc and then 400 ° C. in a non-oxidizing atmosphere
A method for producing a ferromagnetic iron oxide powder for magnetic recording, comprising performing heat treatment at an upper limit temperature at which a transition from C to hematite does not occur.
【００２３】６． 前記熱処理後、さらに酸化してマグ
ヘマイトとすることを特徴とする前記５記載の磁気記録
用強磁性酸化鉄粉末の製造方法。6. 6. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to the item 5, wherein the heat treatment is further oxidized to maghemite.
【００２４】７． 前記マグヘマイトを希薄酸性溶液で
洗浄し、さらにマンガン、亜鉛及び鉄を含む溶液で処理
し、鉄総量に対して０．１〜１９原子重量％のマンガ
ン、及び鉄総量に対して３〜１９原子重量％の亜鉛を含
有させたマグヘマイト粒子とし、その後還元して中間体
粒子とし、さらに非酸化性雰囲気下にて４００℃〜ヘマ
タイトへの転移が生じない上限温度で熱処理する工程を
さらに含むことを特徴とする前記３又は６記載の磁気記
録用強磁性酸化鉄粉末の製造方法。[7] The maghemite is washed with a dilute acidic solution, further treated with a solution containing manganese, zinc and iron, 0.1 to 19 atomic weight% manganese based on the total iron, and 3 to 19 atomic weight based on the total iron. % Of zinc-containing maghemite particles, and then reduced to intermediate particles, and further subjected to a heat treatment in a non-oxidizing atmosphere at a temperature from 400 ° C. to an upper limit temperature at which transformation to hematite does not occur. 7. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to the above item 3 or 6.
【００２５】８． 前記中間体を希薄酸性溶液で洗浄
し、さらにマンガン、亜鉛及び鉄を含む溶液で処理し、
鉄総量に対して０．１〜１９原子重量％のマンガン、及
び鉄総量に対して３〜１９原子重量％の亜鉛を含有させ
た中間体粒子とし、さらに非酸化性雰囲気下にて４００
℃〜ヘマタイトへの転移が生じない上限温度で熱処理す
る工程をさらに含むことを特徴とする前記４又は５記載
の磁気記録用強磁性酸化鉄粉末の製造方法。8. Washing the intermediate with a dilute acidic solution and further treating with a solution containing manganese, zinc and iron;
Intermediate particles containing 0.1 to 19 atomic% by weight of manganese with respect to the total amount of iron, and 3 to 19 atomic% by weight of zinc with respect to the total amount of iron.
6. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to the above item 4 or 5, further comprising a step of performing a heat treatment at a maximum temperature at which the transition to ℃ to hematite does not occur.
【００２６】９． コバルト化合物またはコバルトと第
一鉄塩の化合物を含む溶液で処理する工程をさらに含む
前記１から８のいずれか１項記載の製造方法。9. The method according to any one of claims 1 to 8, further comprising a step of treating with a solution containing a cobalt compound or a compound of cobalt and a ferrous salt.
【００２７】尚上記において「酸化」するとはマグネタ
イトをマグヘマイトまで酸化することを意味し、「微酸
化」するとはマグネタイトとマグヘマイトの中間体まで
酸化することを意味する。In the above description, "oxidation" means that magnetite is oxidized to maghemite, and "slight oxidation" means that it is oxidized to an intermediate between magnetite and maghemite.
【００２８】本発明者らはさらに、鉄総量に対して０．
１〜５原子重量％のマンガン、０．４〜２０原子重量％
の亜鉛、０．１〜２．５原子重量％のリンまたはケイ
素、及び３１原子重量％以下の第一鉄を含有する磁気記
録用強磁性酸化鉄粉末、及びこれをさらにコバルト塩、
またはコバルト塩と第一鉄塩を含む溶液で処理した酸化
鉄粉末によっても優れた結果がえられることを見いだ
し、請求項２および３に記載された発明を完成した。The present inventors have further determined that the total iron content is not more than 0.1%.
1-5 atomic weight% manganese, 0.4-20 atomic weight%
A ferromagnetic iron oxide powder for magnetic recording, comprising zinc, 0.1 to 2.5 at.% Phosphorus or silicon, and 31 at.% Or less ferrous iron, and further comprising a cobalt salt;
Alternatively, it has been found that excellent results can be obtained by using iron oxide powder treated with a solution containing a cobalt salt and a ferrous salt, and the inventions described in claims 2 and 3 have been completed.
【００２９】かかる磁気記録用強磁性酸化鉄粉末は、水
和酸化鉄生成時にマンガンと亜鉛とを添加した原料を用
いた場合中間体粒子を非酸化性雰囲気で熱処理を施すこ
とにより得られるが、同一金属含有量における飽和磁化
量がさらに向上することが見いだされた。この原因は前
記の方法はマグヘマイト、中間体もしくは水和酸化鉄の
粒子表面にマンガン、亜鉛を被着するのでマンガン及び
亜鉛の分布が不均一になるが、水和酸化鉄生成段階でマ
ンガン及び亜鉛を均一に沈澱させておけば第一鉄存在下
の熱処理においてマンガン及び亜鉛の固溶が容易かつ均
一になる為と考えられる。又、マンガンと亜鉛を共存さ
せると亜鉛単独よりも飽和磁化量の高い中間体粒子を得
ることができ、マンガン、亜鉛の複合効果によるものと
考えられる。Such a ferromagnetic iron oxide powder for magnetic recording can be obtained by subjecting intermediate particles to a heat treatment in a non-oxidizing atmosphere when using a raw material to which manganese and zinc are added during the formation of hydrated iron oxide. It has been found that the saturation magnetization at the same metal content is further improved. The reason for this is that the above-mentioned method deposits manganese and zinc on the surface of maghemite, intermediate or hydrated iron oxide particles, so that the distribution of manganese and zinc becomes uneven. It is considered that the uniform precipitation of manganese and manganese and zinc in the heat treatment in the presence of ferrous iron becomes easy and uniform if the precipitates are uniformly precipitated. Further, when manganese and zinc coexist, intermediate particles having a higher saturation magnetization than zinc alone can be obtained, which is considered to be due to the combined effect of manganese and zinc.
【００３０】本発明は水和酸化鉄中にマンガン並びに亜
鉛を均一に沈澱させた後、マグネタイト化もしくは中間
体化した粒子を熱処理することにより飽和磁化量が向上
した中間体粒子を得ることに特徴をもち、水和酸化鉄の
製造と中間体粒子の製造とに大別される。The present invention is characterized in that manganese and zinc are uniformly precipitated in hydrated iron oxide, and then the magnetized or intermediate particles are heat-treated to obtain intermediate particles having an improved saturation magnetization. It is roughly divided into production of hydrated iron oxide and production of intermediate particles.
【００３１】水和酸化鉄にはいくつかの製造方法がある
が、水和酸化鉄中にマンガン並びに亜鉛を均一に沈澱さ
せようとする場合、添加したマンガンや亜鉛が１００％
沈澱しないｐＨ領域で水和酸化鉄の製造を行う方法で
は、マンガンや亜鉛の沈澱量が不安定になりやすく好ま
しくない。これに対し、本発明では水酸化鉄（ＩＩＩ）
を主成分とするアルカリ性懸濁液から水和酸化鉄を製造
する方法を用い、水和酸化鉄生成時のｐＨが酸性側や１
４以上にもなる高アルカリ側に片寄ることがない為、添
加したマンガン並びに亜鉛を１００％沈澱させることが
可能であり、特性安定性、製造安定性を得ることができ
る。There are several production methods for hydrated iron oxide. When it is desired to uniformly precipitate manganese and zinc in hydrated iron oxide, 100% of the added manganese and zinc are added.
In the method of producing hydrated iron oxide in a pH range in which precipitation does not occur, the amount of manganese and zinc precipitated becomes unstable, which is not preferable. On the other hand, in the present invention, iron (III) hydroxide
Using a method for producing hydrated iron oxide from an alkaline suspension containing as a main component the pH of the hydrated iron oxide when the
Since there is no bias toward the high alkali side of 4 or more, it is possible to precipitate 100% of the added manganese and zinc, and it is possible to obtain characteristic stability and production stability.
【００３２】水和酸化鉄の製造方法としては水酸化鉄
（ＩＩＩ）を主成分とするｐＨ１０以上のアルカリ性懸
濁液を室温熟成した後水熱処理する方法（安藤：粉体及
び粉末治金、Ｖｏ１．１３．Ｎｏ．１．１９６６）が知
られている。しかし、多量のマンガン並びに亜鉛を含有
する系では熟成速度が小さくなる為、室温熟成から加熱
熟成に変更する必要を生じた。更に、前記の系では加熱
により熟成を行っても水熱処理後にヘマタイトと水和酸
化鉄の２相が生成すると云う欠点があった。水和酸化鉄
の単一相を生成させる条件を種々検討した結果、熟成後
に水溶性ケイ酸塩もしくは水溶性リン酸塩を添加するこ
とによりヘマタイトの生成を抑制できることを見い出し
た。As a method for producing hydrated iron oxide, a method in which an alkaline suspension containing iron (III) hydroxide as a main component and having a pH of 10 or more is aged at room temperature and then subjected to hydrothermal treatment (Ando: Powder and powder metallurgy, Vo1) .13.No.1.1966) is known. However, in a system containing a large amount of manganese and zinc, the ripening rate becomes low, so that it is necessary to change from room temperature aging to heating aging. Further, the above-mentioned system has a drawback that two phases of hematite and hydrated iron oxide are formed after hydrothermal treatment even when aging is performed by heating. As a result of various studies on the conditions for forming a single phase of hydrated iron oxide, it was found that the formation of hematite can be suppressed by adding a water-soluble silicate or a water-soluble phosphate after aging.
【００３３】アルカリ性懸濁液の作製は、水溶性マンガ
ン塩並びに水溶性亜鉛塩を第二鉄塩中に添加、溶解し、
該第二鉄塩溶液とアルカリ性溶液とをｐＨ１０〜１３の
範囲に保ちながら同時添加し、第二鉄、マンガン並びに
亜鉛を均一かつ同時に沈澱させる。マンガン塩並びに亜
鉛塩を溶解させた第二鉄塩溶液中にアルカリ溶液を添加
する方法、あるいはアルカリ溶液中にマンガン塩並びに
亜鉛塩を溶解させた第二鉄塩溶液を添加する方法では、
各金属の沈澱ｐＨがそれぞれ異なることから不均一な沈
澱となる為好ましくない。又、水溶性マンガン塩並びに
水溶性亜鉛塩の添加量は次工程で得られる飽和磁化量が
向上した中間体粒子において、Ｍｎ／ｔＦｅとして０．
１〜５原子重量％、好ましくは０．１〜４原子重量％並
びにＺｎ／ｔＦｅとして０．４〜２０原子重量％、好ま
しくは１〜１５原子重量％になる様に添加する。To prepare an alkaline suspension, a water-soluble manganese salt and a water-soluble zinc salt are added and dissolved in a ferric salt.
The ferric salt solution and the alkaline solution are simultaneously added while maintaining the pH in the range of 10 to 13, to uniformly and simultaneously precipitate ferric iron, manganese and zinc. In a method of adding an alkaline solution to a ferric salt solution in which a manganese salt and a zinc salt are dissolved, or a method of adding a ferric salt solution in which a manganese salt and a zinc salt are dissolved in an alkaline solution,
Since the precipitation pH of each metal is different from each other, the precipitation becomes uneven, which is not preferable. Further, the amount of the water-soluble manganese salt and the water-soluble zinc salt to be added is set to 0.1 as Mn / tFe in the intermediate particles having an improved saturation magnetization obtained in the next step.
It is added in an amount of 1 to 5 atomic weight%, preferably 0.1 to 4 atomic weight%, and 0.4 to 20 atomic weight%, preferably 1 to 15 atomic weight% as Zn / tFe.
【００３４】次に５０〜１００°Ｃにおいてアルカリ性
懸濁液の熟成を行う。マンガンや亜鉛の割合が多くなる
に従い熟成条件を強化する、即ち熟成温度を高くした
り、熟成時間を長くする等の条件が必要になる。例えば
熟成時におけるマンガン並びに亜鉛の含有量がＭｎ／Ｆ
ｅとして０．５原子重量％、Ｚｎ／Ｆｅとして５原子重
量％の場合８５°Ｃ×５Ｈ程度の熟成で良いが、Ｍｎ／
Ｆｅとして３原子重量％、Ｚｎ／Ｆｅとして１５原子重
量％の場合９５°Ｃ×２４Ｈ以上の熟成が必要である。
熟成が不充分なときは水熱処理の後に水酸化物のコロイ
ドが残存する。Next, the alkaline suspension is aged at 50 to 100 ° C. As the proportions of manganese and zinc increase, aging conditions must be strengthened, that is, conditions such as increasing the aging temperature and lengthening the aging time are required. For example, when the content of manganese and zinc during aging is Mn / F
When e is 0.5 atomic weight% and Zn / Fe is 5 atomic weight%, aging at about 85 ° C. × 5H is sufficient, but Mn /
When Fe is 3 atomic weight% and Zn / Fe is 15 atomic weight%, aging at 95 ° C. × 24H or more is required.
When the aging is insufficient, the hydroxide colloid remains after the hydrothermal treatment.
【００３５】水熱処理は事前に水溶性ケイ酸塩もしくは
水溶性リン酸塩を添加する。ケイ酸塩もしくはリン酸塩
の添加量は、Ｓｉ／ＦｅもしくはＰ／Ｆｅとして０．１
〜２．５原子重量％、好ましくは０．２〜２．０原子重
量％である。尚、ケイ酸塩並びにリン酸塩添加の本来の
目的は水熱処理時のヘマタイト生成抑制であるが焼結防
止剤としても作用し好都合である。In the hydrothermal treatment, a water-soluble silicate or a water-soluble phosphate is added in advance. The amount of silicate or phosphate added is 0.1 / 0.1 as Si / Fe or P / Fe.
To 2.5 at.%, Preferably 0.2 to 2.0 at.%. The original purpose of the addition of the silicate and the phosphate is to suppress the formation of hematite during the hydrothermal treatment, but it advantageously acts as a sintering inhibitor.
【００３６】以上の様にして得られた水和酸化鉄は、濾
過、水洗し懸濁液中に残存する余剰のアルカリなどを除
去した後、必要に応じてケイ素化合物、リン化合物など
の焼結防止剤の後処理を施し、再び濾過、水洗した後、
空気中５０〜１１０°Ｃで乾燥し、飽和磁化量が向上し
た中間体粒子の原料とする。The hydrated iron oxide thus obtained is filtered and washed with water to remove excess alkali and the like remaining in the suspension, and then, if necessary, sintered with a silicon compound, a phosphorus compound or the like. After the post treatment of the inhibitor, after filtering and washing again,
It is dried at 50 to 110 ° C. in the air, and is used as a raw material for intermediate particles having an improved saturation magnetization.
【００３７】飽和磁化量が向上した中間体粒子は、
（ｉ）マグネタイト粒子、（ｉｉ）マグネタイト粒子を
微酸化した中間体粒子、（ｉｉｉ）マグネタイト粒子を
酸化して一旦マグヘマイト粒子とした後、再還元した中
間体粒子、のいずれの粒子でも非酸化性雰囲気下で熱処
理をすれば同程度の飽和磁化量を示す。原料の水和酸化
鉄を５００〜７５０°Ｃ×０．５時間の加熱脱水を行っ
た後、公知の範囲内で作製した熱処理前のマグネタイト
粒子もしくは中間体粒子、即ち（ｉ）水素ガス流通下３
００〜４００°Ｃ×２〜６時間の還元をすることにより
得られるマグネタイト粒子、（ｉｉ）水素ガス流通下３
００〜４００°Ｃ×２〜６時間の還元の後、２５０°Ｃ
以下において空気酸化により所望の第一鉄含有率になる
まで微酸化することにより得られる中間体粒子、（ｉｉ
ｉ）水素ガス流通下３００〜４００°Ｃ×２〜６時間の
還元後、２５０°Ｃ以下において空気酸化してマグヘマ
イト粒子とし、再び３００〜４００°Ｃにおいて所望の
第一鉄含有率になるまで還元することにより得られる中
間体粒子、を非酸化性雰囲気下にて４００°Ｃ〜ヘマタ
イトへの転移が生じない上限温度、好ましくは４００〜
７５０°Ｃにおいて０．５〜２４時間、好ましくは１〜
６時間の熱処理を施す。その後、前記（ｉ）のマグネタ
イトの状態で熱処理を施した粒子は２５０°Ｃ以下にお
いて空気酸化により所望の第一鉄含有率になるまで微酸
化して、又、中間体の状態で熱処理を施した粒子はその
ままの状態で飽和磁化量が向上した中間体粒子に仕上げ
る。このとき中間体粒子中の第一鉄含有率はＦｅ（Ｉ
Ｉ）／ｔＦｅとして３１原子重量％以下に調整する。The intermediate particles having the improved saturation magnetization are as follows:
Any of (i) magnetite particles, (ii) intermediate particles obtained by slightly oxidizing magnetite particles, and (iii) oxidized magnetite particles into maghemite particles and then re-reduced intermediate particles are non-oxidizing. When heat treatment is performed in an atmosphere, the same saturation magnetization is exhibited. The raw material hydrated iron oxide is heated and dehydrated at 500 to 750 ° C. for 0.5 hour, and then magnetite particles or intermediate particles before heat treatment prepared within a known range, that is, (i) under hydrogen gas flow. 3
Magnetite particles obtained by reduction at 00 to 400 ° C. for 2 to 6 hours, (ii) 3 under hydrogen gas flow
After reduction of 00 to 400 ° C x 2 to 6 hours, 250 ° C
Intermediate particles obtained by micro-oxidation to a desired ferrous content by air oxidation below, (ii)
i) After reducing at 300 to 400 ° C for 2 to 6 hours under flowing hydrogen gas, air oxidation is performed at 250 ° C or lower to form maghemite particles, and the desired ferrous iron content is again obtained at 300 to 400 ° C. The intermediate particles obtained by reduction, under a non-oxidizing atmosphere, at a temperature of 400 ° C. to a maximum temperature at which the transition to hematite does not occur, preferably 400 to 400 ° C.
0.5 to 24 hours at 750 ° C, preferably 1 to
A heat treatment is performed for 6 hours. Thereafter, the particles heat-treated in the state of magnetite (i) are slightly oxidized by air oxidation at 250 ° C. or lower until the desired ferrous iron content is reached, and heat-treated in the state of an intermediate. The finished particles are finished as they are as intermediate particles having an improved saturation magnetization. At this time, the ferrous content in the intermediate particles is Fe (I
I) / tFe is adjusted to 31 atomic weight% or less.
【００３８】飽和磁化量が向上した中間体粒子は、公知
の方法により粒子表面にコバルト塩もしくはコバルト塩
と第一鉄塩を含む溶液で被着処理することにより、保磁
力を高めて磁気特性を一層向上させることができる。被
着処理の方法は、例えば以下の通りである。中間体粒子
の水性懸濁液に、アルカリ及びコバルト塩もしくはアル
カリ、コバルト塩及び第一鉄塩を添加して反応させる。
コバルトの被着量は基体粒子基準で１〜９ｗｔ％、好ま
しくは２〜８ｗｔ％、第一鉄塩を併用する場合、第一鉄
塩の被着量はＦｅ（ＩＩ）として１０ｗｔ％以下、好ま
しくは３〜８ｗｔ％である。更に８０〜９５°Ｃまで加
熱して２〜７時間の熟成を行う。被着反応後、濾過、水
洗、乾燥して、コバルト被着強磁性酸化鉄粉末に仕上げ
る。The intermediate particles having an improved saturation magnetization are coated on the particle surface with a solution containing a cobalt salt or a cobalt salt and a ferrous salt by a known method to increase the coercive force and improve the magnetic properties. It can be further improved. The method of the deposition process is, for example, as follows. An alkali and a cobalt salt or an alkali, a cobalt salt and a ferrous salt are added to an aqueous suspension of the intermediate particles and reacted.
The deposition amount of cobalt is 1 to 9 wt%, preferably 2 to 8 wt%, based on the base particles. When a ferrous salt is used in combination, the deposition amount of the ferrous salt is preferably 10 wt% or less as Fe (II). Is 3 to 8% by weight. Further, the mixture is heated to 80 to 95 ° C. and aged for 2 to 7 hours. After the deposition reaction, the resultant is filtered, washed with water, and dried to obtain a cobalt-deposited ferromagnetic iron oxide powder.
【００３９】本発明によれば、マグヘマイト粒子、中間
体粒子もしくは水和酸化鉄粒子の表面を金属で被着処理
し熱処理して固溶させることにより、飽和磁化量が向上
したマグヘマイト粒子もしくは中間体粒子を得ることが
できる。According to the present invention, the surface of maghemite particles, intermediate particles or hydrated iron oxide particles is coated with a metal, heat-treated to form a solid solution, and thereby the maghemite particles or intermediate particles having an improved saturation magnetization are obtained. Particles can be obtained.
【００４０】又、本発明によれば、金属を均一に沈澱さ
せた水和酸化鉄を原料としたマグネタイト粒子もしくは
中間体粒子を熱処理することにより、飽和磁化が向上し
た中間体粒子を得ることができる。According to the present invention, intermediate particles having improved saturation magnetization can be obtained by heat-treating magnetite particles or intermediate particles made from hydrated iron oxide in which a metal is uniformly precipitated. it can.
【００４１】更にコバルト塩もしくはコバルト塩と第一
鉄塩を被着処理することで磁気特性をより一層好ましい
ものにして高記録密度磁気テープに極めて好適な高飽和
磁化量を有する強磁性酸化鉄粉末を製造することができ
る。本発明の効果については、以下に実施例と比較例を
挙げて具体的に説明する。Further, a ferromagnetic iron oxide powder having a high saturation magnetization which is further preferable by applying a cobalt salt or a cobalt salt and a ferrous salt so that the magnetic properties are further improved and which is very suitable for a high recording density magnetic tape. Can be manufactured. The effects of the present invention will be specifically described below with reference to examples and comparative examples.
【００４２】[0042]
実施例−１ 保磁力Ｈｃ＝２５００ｅ、飽和磁化量σｓ＝６８．５ｅ
ｍｕ／ｇ、比表面積＝６２．０ｍ2 ／ｇのマグヘマイト
（γ−Ｆｅ2 Ｏ3 ）粒子１００ｇを、純水１．５リット
ル中に分散させた後、攪拌下でＭｎとして５０ｇ／ｌの
ＭｎＳＯ4 水溶液１０６．３ｍｌ、Ｚｎとして５０ｇ／
ｌのＺｎＳＯ4 水溶液１２６．６ｍｌ、Ｆｅとして５０
ｇ／ｌのＦｅ2 （ＳＯ4 ）3 水溶液８４．０ｍｌの混合
溶液を添加した。次いで１２０ｇ／ｌのＮａＯＨ水溶液
を徐添加しｐＨ＝１０．０に調整後３０分保持し濾過、
水洗そして１１０°Ｃで２時間乾燥した。次いで水素ガ
ス流通下２３０°Ｃで３時間還元を行い、窒素ガス流通
下６５０°Ｃで３時間熱処理して目的の磁性酸化鉄粉末
を得た。（試料Ａ−１） 比較例−１ 実施例−１において５０ｇ／ｌのＺｎＳＯ4 水溶液１２
６．６ｍｌを３５．６ｍｌに変更したほかは同様に処理
し、比較試料の磁性酸化鉄粉末を得た。（試料Ａ−２） 実施例−２ 実施例−１において５０ｇ／ｌのＺｎＳＯ4 水溶液１２
６．６ｍｌを２０２．４ｍｌに変更したほかは同様に処
理し、目的の磁性酸化鉄粉末を得た。（試料Ａ−３） 比較例−２ 実施例−１において５０ｇ／ｌのＺｎＳＯ4 水溶液１２
６．６ｍｌを３３７．３ｍｌに変更したほかは同様に処
理し、比較試料の磁性酸化鉄粉末を得た。（試料Ａ−
４） 比較例−３ 実施例−１においてＭｎＳＯ4 水溶液を無添加としＺｎ
ＳＯ4 水溶液１２６．６ｍｌを５９．１ｍｌに変更した
ほかは同様に処理し、比較試料の磁性酸化鉄粉末を得
た。（試料Ａ−５） 実施例−３ 実施例−１において５０ｇ／ｌのＭｎＳＯ4 水溶液１０
６．３ｍｌを１７０．１ｍｌに変更したほかは同様に処
理し、目的の磁性酸化鉄粉末を得た。（試料Ａ−６） 実施例−４ 実施例−１において５０ｇ／ｌのＭｎＳＯ4 水溶液１０
６．３ｍｌを１７０．１ｍｌに変更したほかは同様に処
理し、目的の磁性酸化鉄粉末を得た。（試料Ａ−７） 比較例−４ 実施例−１においてＭｎＳＯ4 水溶液、ＺｎＳＯ4 水溶
液、及びＦｅ2 （ＳＯ4 ）3 水溶液を無添加としたほか
は同様に処理し、比較試料の磁性酸化鉄粉末を得た。
（試料Ａ−８） 比較例−５ 実施例−１において６５０°Ｃで３時間の熱処理を３５
０°Ｃで３時間の熱処理に変更したほかは同様に処理
し、比較試料の磁性酸化鉄粉末を得た。（試料Ａ−９） 実施例−５ 実施例−１において６５０°Ｃで３時間の熱処理を５０
０°Ｃで３時間の熱処理に変更したほかは同様に処理
し、目的の磁性酸化鉄粉末を得た。（試料Ａ−１０） 実施例−６ 実施例−１において６５０°Ｃで３時間の熱処理を７５
０°Ｃで３時間の熱処理に変更したほかは同様に処理
し、目的の磁性酸化鉄粉末を得た。（試料Ａ−１１） 比較例−６ 実施例−１において６５０°Ｃで３時間の熱処理を８５
０°Ｃで３時間の熱処理に変更したほかは同様に処理
し、比較試料の磁性酸化鉄粉末を得た。（試料Ａ−１
２） 実施例−７ 実施例−１において６５０°Ｃで３時間の熱処理を６５
０°Ｃで１時間の熱処理に変更したほかは同様に処理
し、目的の磁性酸化鉄粉末を得た。（試料Ａ−１３） 実施例−８ 実施例−１において６５０°Ｃで３時間の熱処理を６５
０°Ｃで１２時間の熱処理に変更したほかは同様に処理
し、目的の磁性酸化鉄粉末を得た。（試料Ａ−１４） 実施例−９ 実施例−１において６５０°Ｃで３時間の熱処理を６５
０°Ｃで２４時間の熱処理に変更したほかは同様に処理
し、目的の磁性酸化鉄粉末を得た。（試料Ａ−１５） 実施例−１０ 保磁力Ｈｃ＝２５００ｅ、飽和磁化量σｓ＝６８．５ｅ
ｍｕ／ｇ、比表面積＝６２．０ｍ2 ／ｇのマグヘマイト
（γ−Ｆｅ2 Ｏ3 ）粒子を水素ガス流通下２３０°Ｃで
３時間還元し中間体化した後１００ｇを純水１．５リッ
トル中に分散させ攪拌下でＭｎとして５０ｇ／ｌのＭｎ
ＳＯ4 水溶液１０６．３ｍｌ，Ｚｎとして５０ｇ／ｌの
ＺｎＳＯ4 水溶液１２６．６ｍｌ，Ｆｅとして５０ｇ／
ｌＦｅ2（ＳＯ4 ）3 水溶液８４．０ｍｌの混合溶液を
添加した。次いで１２０ｇ／ｌのＮａＯＨ水溶液を徐添
加し、ｐＨ＝１０．０に調整後３０分保持し、濾過、水
洗そして窒素ガス流通下５０°Ｃで３時間乾燥した。次
いで窒素ガス流通下６５０°Ｃで３時間熱処理して目的
の磁性酸化鉄粉末を得た。Example 1 Coercive force Hc = 2500 e, saturation magnetization σs = 68.5 e
After dispersing 100 g of maghemite (γ-Fe 2 O 3 ) particles having a specific surface area of 62.0 m 2 / g in 1.5 L of pure water, 50 g / l of MnSO as Mn was stirred under stirring. 4 106.3 ml of aqueous solution, 50 g /
126.6 ml of an aqueous solution of ZnSO 4 , 50 as Fe
A mixed solution of 84.0 ml of a g / l aqueous solution of Fe 2 (SO 4 ) 3 was added. Then, a 120 g / l NaOH aqueous solution was gradually added to adjust the pH to 10.0, and the mixture was held for 30 minutes and filtered.
Washed and dried at 110 ° C for 2 hours. Next, reduction was carried out at 230 ° C. for 3 hours under a flow of hydrogen gas, and heat treatment was carried out at 650 ° C. for 3 hours under a flow of nitrogen gas to obtain a target magnetic iron oxide powder. ZnSO 4 aqueous solution 12 of 50 g / l in (Sample A-1) Comparative Example 1 Example -1
The same treatment was carried out except that 6.6 ml was changed to 35.6 ml, to obtain a magnetic iron oxide powder of a comparative sample. ZnSO 4 aqueous solution 12 of 50 g / l in (Sample A-2) Example -2 Example -1
The same treatment was carried out except that 6.6 ml was changed to 202.4 ml to obtain a target magnetic iron oxide powder. ZnSO 4 aqueous solution 12 of 50 g / l in (Sample A-3) Comparative Example -2 Example -1
The same treatment was carried out except that 6.6 ml was changed to 337.3 ml to obtain a magnetic iron oxide powder of a comparative sample. (Sample A-
4) In Comparative Example -3 Example -1 and no addition of MnSO 4 aqueous Zn
In addition to changing the SO 4 aqueous solution 126.6ml to 59.1ml The same treatment was to obtain a magnetic iron oxide powder of Comparative Sample. MnSO 4 aqueous solution 10 of 50 g / l in (Sample A-5) Example -3 Example -1
The same treatment was carried out except that 6.3 ml was changed to 170.1 ml to obtain a target magnetic iron oxide powder. MnSO 4 aqueous solution 10 of 50 g / l in (Sample A-6) Example -4 Example -1
The same treatment was carried out except that 6.3 ml was changed to 170.1 ml to obtain a target magnetic iron oxide powder. MnSO 4 aqueous solution in (Sample A-7) Comparative Example -4 Example -1, ZnSO 4 solution, and Fe 2 (SO 4) 3 except that the aqueous solution was not added was treated in the same manner, the magnetic iron oxide of Comparative Sample A powder was obtained.
(Sample A-8) Comparative Example-5 The heat treatment at 650 ° C. for 3 hours in Example 1 was performed for 35 hours.
The same treatment was performed except that the heat treatment was performed at 0 ° C. for 3 hours to obtain a magnetic iron oxide powder of a comparative sample. (Sample A-9) Example-5 The heat treatment at 650 ° C. for 3 hours in Example-1 was performed 50 times.
The same treatment was carried out except that the heat treatment was performed at 0 ° C. for 3 hours to obtain a target magnetic iron oxide powder. (Sample A-10) Example-6 The heat treatment at 650 ° C. for 3 hours in Example-1 was carried out for 75 hours.
The same treatment was carried out except that the heat treatment was performed at 0 ° C. for 3 hours to obtain a target magnetic iron oxide powder. (Sample A-11) Comparative Example-6 The heat treatment at 650 ° C. for 3 hours in Example-1 was performed for 85 hours.
The same treatment was performed except that the heat treatment was performed at 0 ° C. for 3 hours to obtain a magnetic iron oxide powder of a comparative sample. (Sample A-1
2) Example-7 In Example-1, the heat treatment at 650 ° C for 3 hours was performed for 65 hours.
The same treatment was carried out except that the heat treatment was performed at 0 ° C. for 1 hour to obtain a target magnetic iron oxide powder. (Sample A-13) Example-8 The heat treatment at 650 ° C. for 3 hours in Example-1 was performed for 65 hours.
The same treatment was carried out except that the heat treatment was performed at 0 ° C. for 12 hours to obtain a target magnetic iron oxide powder. (Sample A-14) Example -9 In Example 1, heat treatment was performed at 650 ° C. for 3 hours for 65 hours.
The same treatment was carried out except that the heat treatment was performed at 0 ° C. for 24 hours to obtain a target magnetic iron oxide powder. (Sample A-15) Example-10 Coercive force Hc = 2500 e, saturation magnetization σs = 68.5 e
maghemite (γ-Fe 2 O 3 ) particles having a specific surface area of 62.0 m 2 / g were reduced at 230 ° C. for 3 hours under a hydrogen gas flow to form an intermediate. Dispersed therein and stirred with Mn of 50 g / l as Mn.
106.3 ml of an aqueous solution of SO 4, 126.6 ml of a 50 g / l aqueous solution of ZnSO 4 as Zn, and 50 g /
mixed solution of lFe 2 (SO 4) 3 aqueous solution 84.0ml was added. Then, a 120 g / l NaOH aqueous solution was gradually added, the pH was adjusted to 10.0, the mixture was kept for 30 minutes, filtered, washed with water, and dried at 50 ° C. for 3 hours under a flow of nitrogen gas. Then, heat treatment was performed at 650 ° C. for 3 hours under a nitrogen gas flow to obtain a target magnetic iron oxide powder.
【００４３】（試料Ｂ−１） 実施例−１１ 比表面積１０９．０ｍ2 ／ｇのゲーサイト（α−ＦｅＯ
ＯＨ）粒子１００ｇを純水３リットル中に分散させた
後、攪拌下でＭｎとして５０ｇ／ｌのＭｎＳＯ4水溶液
９２．７ｍｌ，Ｚｎとして５０ｇ／ｌのＺｎＳＯ4 水溶
液１１０．４ｍｌの混合溶液を添加した。次いで１２０
ｇ／ｌのＮａＯＨ水溶液を徐添加しｐＨ＝１０．０に調
整後リン化合物を処理して、濾過、水洗しアルカリを除
去した後１１０°Ｃで２時間乾燥した。このゲーサイト
粒子を６２０°Ｃで０．５時間加熱脱水を行い、マンガ
ン及び亜鉛含有ヘマタイト粒子を得た。このヘマタイト
粒子を炭酸ガスを含む水素ガス流通下３５０°Ｃで３時
間還元した後、窒素ガス流通下６５０°Ｃで３時間熱処
理を行い空気流通下５０°Ｃで２時間酸化を行い中間体
化して目的の磁性酸化鉄粉末を得た。（試料Ｃ−１） 比較例−７ 実施例１１においてＭｎＳＯ4 水溶液及びＺｎＳＯ4 水
溶液を無添加としたほかは同様に処理し、比較試料の磁
性酸化鉄粉末を得た。（試料Ｃ−２） 実施例−１２ 実施例−１１において５０°Ｃで２時間の酸化を、２５
０°Ｃで３時間の酸化に変更してマグヘマイト化したほ
かは同様に処理を行い、目的の磁性酸化鉄粉末を得た。
（試料Ｄ−１） 実施例−１３ 実施例−１１の炭酸ガスを含む水素ガス流通下３５０°
Ｃで３時間還元した後、空気流通下５０°Ｃで２時間酸
化を行い中間体化し、さらに窒素ガス流通下６５０°Ｃ
で３時間の熱処理を行って目的の磁性酸化鉄粉末を得
た。（試料Ｅ−１） 実施例−１４ 実施例−１３を行った後、空気流通下で２５０°Ｃで３
時間酸化して目的の磁性酸化鉄粉末を得た。（試料Ｆ−
１） 実施例−１５ 実施例−１２で得られたマグヘマイト粒子（試料Ｄ−
１）２００ｇを２０ｇ／ｌのＨ2 ＳＯ4 ２リットルに分
散させ、４５°Ｃに昇温し、５時間保持した。次いで濾
過、水洗そして１１０°Ｃで２時間乾燥して、酸洗浄品
を得た。(Sample B-1) Example-11 Goethite (α-FeO) having a specific surface area of 109.0 m 2 / g
After the OH) particles 100g were dispersed in pure water 3 liters, MnSO 4 aqueous solution 92.7ml as Mn under stirring 50 g / l, was added a mixed solution of ZnSO 4 aqueous solution 110.4ml of 50 g / l as Zn . Then 120
After adjusting the pH to 10.0 by gradually adding a g / l NaOH aqueous solution, the phosphorus compound was treated, filtered, washed with water to remove alkali, and dried at 110 ° C for 2 hours. The goethite particles were dehydrated by heating at 620 ° C. for 0.5 hours to obtain manganese and zinc-containing hematite particles. The hematite particles are reduced at 350 ° C. for 3 hours under a flow of hydrogen gas containing carbon dioxide gas, heat-treated at 650 ° C. for 3 hours under a flow of nitrogen gas, and oxidized at 50 ° C. for 2 hours under a flow of air to form an intermediate. Thus, the desired magnetic iron oxide powder was obtained. (Sample C-1) Comparative Example-7 A magnetic iron oxide powder of a comparative sample was obtained in the same manner as in Example 11, except that the aqueous solution of MnSO 4 and the aqueous solution of ZnSO 4 were not added. (Sample C-2) Example-12 Oxidation at 50 ° C. for 2 hours in Example-11 was carried out for 25 hours.
The same treatment was carried out except that the maghemite was formed by changing the oxidation to 0 ° C. for 3 hours to obtain the desired magnetic iron oxide powder.
(Sample D-1) Example-13 350 ° in flowing hydrogen gas containing carbon dioxide gas of Example-11
C. for 3 hours, oxidize at 50 ° C. for 2 hours under an air stream to form an intermediate, and further 650 ° C. under a nitrogen stream.
For 3 hours to obtain the desired magnetic iron oxide powder. (Sample E-1) Example-14 After performing Example-13, 3 was performed at 250 ° C. under an air flow.
Oxidation was performed for a time to obtain the desired magnetic iron oxide powder. (Sample F-
1) Example-15 Maghemite particles obtained in Example-12 (sample D-
1) 200 g was dispersed in 2 liters of 20 g / l H 2 SO 4 , the temperature was raised to 45 ° C., and kept for 5 hours. Then, it was filtered, washed with water and dried at 110 ° C. for 2 hours to obtain an acid-washed product.
【００４４】酸洗浄したマグヘマイト粒子１００ｇを純
水１．５リットル中に分散させた後、攪拌下でＭｎとし
て５０ｇ／ｌのＭｎＳＯ4 水溶液３５．５ｍｌ，Ｚｎと
して５０ｇ／ｌのＺｎＳＯ4 水溶液４２．２ｍｌ，Ｆｅ
として５０ｇ／ｌのＦｅ2 （ＳＯ4 ）3 水溶液８４．０
ｍｌの混合溶液を添加した。次いで１２０ｇ／ｌのＮａ
ＯＨ水溶液を徐添加し、ｐＨ＝１０．０に調整後３０分
保持し濾過、水洗そして１１０°Ｃで２時間乾燥した。
次いで水素ガス流通下２３０°Ｃで３時間還元を行い、
窒素ガス流通下６５０°Ｃで３時間熱処理して目的の磁
性酸化鉄粉末を得た。（試料Ｇ−１） 実施例−１６ 実施例−１１で得られた中間体粒子（試料Ｃ−１）２０
０ｇを２０ｇ／ｌのＨ2 ＳＯ4 ２リットルに分散させ、
窒素ガスを吹き込みながら４５°Ｃに昇温し、５時間保
持した。次いで濾過、水洗そして窒素ガス流通下５０°
Ｃで３時間乾燥して、酸洗浄品を得た。[0044] After dispersing the maghemite particles 100g of acid washed in pure water 1.5 l, MnSO 4 aqueous solution 35.5ml as Mn under stirring 50g / l, ZnSO 4 solution of 50 g / l as Zn 42. 2ml, Fe
50 g / l Fe 2 (SO 4 ) 3 aqueous solution 84.0
ml of the mixed solution was added. Then 120 g / l Na
An OH aqueous solution was gradually added, and after adjusting the pH to 10.0, the mixture was maintained for 30 minutes, filtered, washed with water, and dried at 110 ° C for 2 hours.
Next, reduction was carried out at 230 ° C. for 3 hours under flowing hydrogen gas.
Heat treatment was performed at 650 ° C. for 3 hours under a nitrogen gas flow to obtain a target magnetic iron oxide powder. (Sample G-1) Example-16 Intermediate particle (sample C-1) 20 obtained in Example-11
0 g are dispersed in 2 liters of 20 g / l H 2 SO 4 ,
The temperature was raised to 45 ° C. while blowing nitrogen gas, and maintained for 5 hours. Then, filtration, washing and 50 ° under nitrogen gas flow
After drying at C for 3 hours, an acid-washed product was obtained.
【００４５】酸洗浄した中間体粒子１００ｇを純水１．
５リットル中に分散させた後、攪拌下でＭｎとして５０
ｇ／ｌのＭｎＳＯ4 水溶液３５．５ｍｌ、Ｚｎとして５
０ｇ／ｌのＺｎＳＯ4 水溶液４２．２ｍｌ、Ｆｅとして
５０ｇ／ｌのＦｅ2 （ＳＯ4）3 水溶液８４．０ｍｌの
混合溶液を添加した。次いで１２０ｇ／ｌのＮａＯＨ水
溶液を徐添加し、ｐＨ１０．０に調整後、３０分保持し
濾過、水洗そして窒素ガス流通下５０°Ｃで３時間乾燥
した。次いで窒素ガス流通下６５０°Ｃで３時間熱処理
して目的の磁性酸化鉄粉末を得た。（試料Ｈ−１） 実施例−１７ 実施例−１６において、Ｍｎとして５０ｇ／ｌのＭｎＳ
Ｏ4 水溶液３５．５ｍｌを１５７．１ｍｌ、Ｚｎとして
５０ｇ／ｌのＺｎＳＯ4 水溶液４２．２ｍｌを１８４．
０ｍｌ、Ｆｅとして５０ｇ／ｌのＦｅ2 （ＳＯ4 ）3 水
溶液８４．０ｍｌを３１９．５ｍｌに変更したほかは同
様に処理し、目的の磁性酸化鉄粉末を得た。（試料Ｈ−
２） 実施例−１８ 実施例−１において得られたマンガン、亜鉛含有中間体
粒子（試料Ａ−１）１００ｇを純水５００ｍｌに分散さ
せた後、窒素ガスを吹き込みながら攪拌下３５°Ｃで２
０４．１ｇのＮａＯＨ（純度９８％）を溶解し５００ｍ
ｌに調整した溶液を添加した。次いで３４．０７ｇのＣ
ｏＳＯ4 ・７Ｈ2 Ｏ（純度９８％）を溶解し１２５ｍｌ
に調整した溶液と、３５．５４ｇのＦｅＳＯ4 ・７Ｈ2
Ｏ（純度９８％）を溶解し１２５ｍｌに調整した溶液を
添加した後、９５°Ｃで５時間熟成した。得られた沈澱
物を濾過、水洗した後、大気中５５°Ｃで３時間乾燥し
て目的のコバルト被着磁性酸化鉄粉末を得た。（試料Ｉ
−１） 比較例−８ 実施例−１において得られた中間体粒子を比較例−４で
得られた中間体粒子（試料Ａ−８）に変更したことほか
は実施例−２１と同様に処理を行い、比較試料のコバル
ト被着磁性酸化鉄粒子を得た。（試料Ｉ−２） 前記実施例−１〜１８及び比較例−１〜８で作製した磁
性酸化鉄試料（Ａ−１）〜（Ｉ−２）について、通常の
方法にて第一鉄含有量（Ｆｅ（ＩＩ）／ｔＦｅ），及び
飽和磁化量（σｓ）などを測定した。これらの結果を第
１表と第２表に示す。100 g of the acid-washed intermediate particles were added to pure water 1.
After dispersing in 5 liters, Mn is 50
g / l MnSO 4 aqueous solution 35.5 ml, Zn 5
A mixed solution of 42.2 ml of a 0 g / l aqueous solution of ZnSO 4 and 84.0 ml of a 50 g / l aqueous solution of Fe 2 (SO 4 ) 3 as Fe was added. Next, a 120 g / l NaOH aqueous solution was gradually added to adjust the pH to 10.0, and the mixture was held for 30 minutes, filtered, washed with water, and dried at 50 ° C. for 3 hours under flowing nitrogen gas. Then, heat treatment was performed at 650 ° C. for 3 hours under a nitrogen gas flow to obtain a target magnetic iron oxide powder. (Sample H-1) Example-17 In Example-16, MnS of 50 g / l as Mn was used.
157.1 ml of an O 4 aqueous solution, and 184.2 ml of a 50 g / l ZnSO 4 aqueous solution of 50 g / l as Zn.
The same treatment was carried out except that 84.0 ml of an aqueous Fe 2 (SO 4 ) 3 solution of 0 ml and 50 g / l Fe was changed to 319.5 ml to obtain the desired magnetic iron oxide powder. (Sample H-
2) Example-18 After dispersing 100 g of the manganese and zinc-containing intermediate particles (sample A-1) obtained in Example 1 in 500 ml of pure water, the dispersion was stirred at 35 ° C while blowing nitrogen gas.
Dissolve 44.1 g of NaOH (98% purity) and 500m
The solution adjusted to 1 was added. Then 34.07 g of C
It was dissolved oSO 4 · 7H 2 O (purity 98%) 125 ml
A solution adjusted to, FeSO of 35.54g 4 · 7H 2
After adding a solution adjusted to 125 ml by dissolving O (purity 98%), the mixture was aged at 95 ° C. for 5 hours. The obtained precipitate was filtered, washed with water, and dried in the air at 55 ° C. for 3 hours to obtain the desired cobalt-coated magnetic iron oxide powder. (Sample I
-1) Comparative Example-8 The same treatment as in Example-21 except that the intermediate particles obtained in Example-1 were changed to the intermediate particles (sample A-8) obtained in Comparative Example-4 Was performed to obtain a cobalt-coated magnetic iron oxide particle of a comparative sample. (Sample I-2) Ferrous iron content of the magnetic iron oxide samples (A-1) to (I-2) prepared in Examples 1-1 to 18 and Comparative Examples -1 to 8 by a usual method. (Fe (II) / tFe), saturation magnetization (σs) and the like were measured. The results are shown in Tables 1 and 2.
【００４６】以上の結果において本発明による実施例の
磁性酸化鉄試料は、飽和磁化量が高く優れた磁気特性を
示すことは明かである。From the above results, it is apparent that the magnetic iron oxide sample of the example according to the present invention has a high saturation magnetization and exhibits excellent magnetic properties.
【００４７】 実施例１９ Ｆｅ（ＩＩＩ）として１３．９６ｇを含むＦｅ2 （ＳＯ
4 ） 3溶液中に０．４４０ｇのＭｎＳＯ4 ・ｎＨ2 Ｏ
（Ｍｎ純度３１．２％）及び７．３４ｇのＺｎＳＯ4 ・
７Ｈ2 Ｏ（純度９８％）とを添加、溶解させた後液量を
５００ｍｌに調整した溶液と、６１．２２ｇのＮａＯＨ
（純度９８％）を溶解し７５０ｍｌに調整した溶液と
を、攪拌下の１２５０ｍｌ水溶液中にｐＨ１２．５±
０．５を保ちながら同時に添加することにより赤褐色の
懸濁液を調整した。この懸濁液を９５°Ｃ×２４Ｈの熟
成を行った後、Ｓｉとして１７．５ｇ／ｌのＳｉＯ2 ・
Ｎａ2 Ｏ水溶液１．０ｍｌを添加し、１５０°Ｃ×３Ｈ
の水熱処理を行い黄色懸濁液を得た。その後、濾過、水
洗、乾燥により黄色の粉末を回収した。（試料Ｊ−１）
この黄色粉末は第１図に示す様にＸ線回折により水和酸
化鉄の単一相であることが確認された。又、Ｘ線回折に
よる格子定数測定結果は第３表の通りであり、前記黄色
粉末の格子定数は水和酸化鉄のそれより大きくなってい
ることから、この合成相は水和酸化鉄の結晶格子中にＦ
ｅ（ＩＩＩ）より大きいイオン半径を有するＭｎ（Ｉ
Ｉ）、Ｚｎ（ＩＩ）が固溶していると解釈され、Ｍｎ
（ＩＩ）並びにＺｎ（ＩＩ）が均一に沈澱していること
が判る。[0047] Example 19 Fe 2 (SO 2 ) containing 13.96 g as Fe (III)
4 ) 0.440 g of MnSO 4 .nH 2 O in 3 solutions
(Mn purity 31.2%) and 7.34 g of ZnSO 4.
After adding and dissolving 7H 2 O (purity 98%), the solution was adjusted to 500 ml in volume, and 61.22 g of NaOH
(Purity 98%) was dissolved and adjusted to 750 ml in a 1250 ml aqueous solution with stirring at pH 12.5 ±
A reddish-brown suspension was prepared by simultaneous addition while maintaining 0.5. The suspension was aged at 95 ° C. × 24 H, and then 17.5 g / l of SiO 2.
Na 2 O aqueous solution (1.0 ml) was added, and 150 ° C. × 3H
Was subjected to hydrothermal treatment to obtain a yellow suspension. Thereafter, a yellow powder was recovered by filtration, washing with water and drying. (Sample J-1)
As shown in FIG. 1, the yellow powder was confirmed to be a single phase of hydrated iron oxide by X-ray diffraction. The measurement results of lattice constants by X-ray diffraction are as shown in Table 3. Since the lattice constant of the yellow powder is larger than that of the hydrated iron oxide, this synthetic phase is composed of crystals of the hydrated iron oxide. F in the grid
Mn (I) having an ionic radius larger than e (III)
I) and Zn (II) are interpreted as a solid solution,
It can be seen that (II) and Zn (II) are uniformly precipitated.
【００４８】 比較例９ 実施例１９において、熟成後にＳｉＯ2 ・Ｎａ2 Ｏ水溶
液を添加しなかったほかは実施例１９と同様にした。得
られた粉末は黄褐色を呈し、Ｘ線回折の結果、第２図に
示す様に水和酸化鉄とヘマタイトの二相が生成していた
（試料Ｊ−２）。第２図においては↓印はヘマタイトの
ピークを示す。[0048] Comparative Example 9 The procedure of Example 19 was repeated, except that the aqueous solution of SiO 2 and Na 2 O was not added after aging. The obtained powder was yellow-brown, and as a result of X-ray diffraction, two phases of hydrated iron oxide and hematite were formed as shown in FIG. 2 (sample J-2). In FIG. 2, the arrow mark indicates the peak of hematite.
【００４９】実施例２０ 実施例１９で得られた水和酸化鉄粒子を６２０°Ｃで
０．５時間加熱脱水を行い、マンガン、亜鉛及びケイ素
を含有するヘマタイト粒子を得た。このヘマタイト粒子
を炭酸ガスを含む水素ガス流通下３５０°Ｃで６時間還
元した後、窒素ガス流通下４７５°Ｃで６時間熱処理を
行い、空気流通下７０°Ｃで１時間酸化を行い中間体化
して目的の磁性酸化鉄粉末を得た。（試料Ｋ−１） 実施例２１ 実施例１９で得られた水和酸化鉄粒子を６２０°Ｃで
０．５時間加熱脱水を行い、マンガン、亜鉛及びケイ素
を含有するヘマタイト粒子を得た。このヘマタイト粒子
を炭酸ガスを含む水素ガス流通下３５０°Ｃで６時間還
元した後、空気流通下７０°Ｃで１時間酸化を行い中間
体化し、窒素ガス流通下４７５°Ｃで６時間熱処理を行
って目的の磁性酸化鉄粉末を得た。（試料Ｋ−２） 実施例２２ 実施例１９で得られた水和酸化鉄粒子を６２０°Ｃで
０．５時間加熱脱水を行い、マンガン、亜鉛及びケイ素
を含有するヘマタイト粒子を得た。このヘマタイト粒子
を炭酸ガスを含む水素ガス流通下３５０°Ｃで３時間還
元した後、空気流通下２５０°Ｃで２時間酸化してマグ
ヘマイト粒子にした。次いで水素ガス流通下３００°Ｃ
で１．５時間還元した後、窒素ガス流通下４７５°Ｃで
６時間熱処理を行って目的の磁性酸化鉄粉末を得た。
（試料Ｋ−３） 実施例２３ 実施例１９において、ＳｉＯ2 −Ｎａ2 Ｏ水溶液添加の
代りに、Ｐとして１９．３ｇ／ｌのＮａ 3ＰＯ4 水溶液
１．０ｍｌを添加したほかは同様にして水和酸化鉄の単
一相を得た。つづいて実施例２０の条件で中間体粒子に
仕上げて目的の磁性酸化鉄粉末を得た。（試料Ｋ−４） 実施例２４ 実施例１９において添加したＺｎＳＯ4 ・７Ｈ2 Ｏの量
を変えて実験を行った。得られた各水和酸化鉄粒子を実
施例２０の条件で中間体粒子に仕上げて目的の磁性酸化
鉄粉末を得た。（試料Ｋ−５〜Ｋ−８） 実施例２５ 実施例１９において添加したＭｎＳＯ4 ・ｎＨ2 Ｏの量
を変えた実験を行った。得られた各水和酸化鉄粒子を実
施例２０の条件で中間体粒子に仕上げて目的の磁性酸化
鉄粉末を得た。（試料Ｋ−９，Ｋ−１０） 比較例１０ 実施例１９においてＭｎＳＯ4 ・ｎＨ2 Ｏを添加しなか
ったほかは実施例１９と同様にした後、実施例２０の条
件で中間体粒子に仕上げて比較試料の磁性酸化鉄粉末を
得た。（試料Ｋ−１１） 比較例１１ 実施例１９においてＺｎＳＯ4 ・７Ｈ2 Ｏの添加量を１
１．０１ｇとしたこととＭｎＳＯ4 ・ｎＨ2 Ｏを添加し
なかったほかは実施例１９と同様にした後、実施例２０
の条件で中間体粒子に仕上げて比較試料の磁性酸化鉄粉
末を得た。（試料Ｋ−１２） 比較例１２ 実施例１９でＭｎＳＯ4 ・ｎＨ2 Ｏ及びＺｎＳＯ4 ・７
Ｈ2 Ｏを添加しなかったほかは実施例１９と同様にした
後、実施例２０の条件で中間体粒子に仕上げて比較試料
の磁性酸化鉄粉末を得た。（試料Ｋ−１３） 実施例２６ 実施例２０及び実施例２３において還元温度を４００°
Ｃにしたほかは実施例２０の条件で中間体粒子に仕上げ
て目的の磁性酸化鉄粉末を得た。（試料Ｋ−１４〜Ｋ−
１８） 実施例２７ 実施例２５の試料Ｋ−１０で熱処理温度を６２５°Ｃに
したほかは同様にして中間体粒子に仕上げて目的の磁性
酸化鉄粉末を得た。（試料Ｋ−１９） 実施例２８ 実施例２０において得られた中間体粒子（試料Ｋ−１）
１００ｇを純水５００ｍｌに分散させた後、窒素ガスを
吹き込みながら攪拌下３５°Ｃで２０４．１ｇのＮａＯ
Ｈ（純度９８％）を溶解し５００ｍｌに調整した溶液を
添加した。次いで３４．０７ｇのＣｏＳＯ4 ・７Ｈ2 Ｏ
（純度９８％）を溶解し１２５ｍｌに調整した溶液と、
３５．５４ｇのＦｅＳＯ4 ・７Ｈ2 Ｏ（純度９８％）を
溶解し１２５ｍｌに調整した溶液を添加した後、９５°
Ｃで５時間熟成した。得られた沈澱物を濾過、水洗した
後、大気中５５°Ｃで３時間乾燥して目的のコバルト被
着磁性酸化鉄粉末を得た。（試料Ｌ−１） 比較例１３ 実施例２０において得られた中間体粒子を比較例１２で
得られた中間体粒子に変更したほかは実施例２６と同様
に処理し、比較試料のコバルト被着磁性酸化鉄粒子を得
た。（試料Ｌ−２） 前記実施例２０〜２８及び比較例１０〜１３で得られた
磁性酸化鉄試料（Ｋ−１）〜（Ｌ−２）について、通常
の方法により、飽和磁化量（σｓ）、第一鉄含有量（Ｆ
ｅ（ＩＩ）／ｔＦｅ）等を測定した。これらの結果を第
４表と第５表に示す。Example 20 The hydrated iron oxide particles obtained in Example 19 were heated and dehydrated at 620 ° C. for 0.5 hours to obtain hematite particles containing manganese, zinc and silicon. The hematite particles are reduced at 350 ° C. for 6 hours under a flow of hydrogen gas containing carbon dioxide, heat-treated at 475 ° C. for 6 hours under a flow of nitrogen gas, and oxidized at 70 ° C. for 1 hour under a flow of air to produce an intermediate. To obtain the desired magnetic iron oxide powder. (Sample K-1) Example 21 The hydrated iron oxide particles obtained in Example 19 were dehydrated by heating at 620 ° C. for 0.5 hour to obtain hematite particles containing manganese, zinc and silicon. The hematite particles are reduced at 350 ° C. for 6 hours under a flow of hydrogen gas containing carbon dioxide gas, oxidized at 70 ° C. for 1 hour under a flow of air to be an intermediate, and heat-treated at 475 ° C. for 6 hours under a flow of nitrogen gas. Then, the desired magnetic iron oxide powder was obtained. (Sample K-2) Example 22 The hydrated iron oxide particles obtained in Example 19 were heated and dehydrated at 620 ° C for 0.5 hours to obtain hematite particles containing manganese, zinc and silicon. The hematite particles were reduced at 350 ° C. for 3 hours under a flow of hydrogen gas containing carbon dioxide gas, and then oxidized at 250 ° C. for 2 hours under a flow of air to form maghemite particles. Then 300 ° C under hydrogen gas flow
And then heat-treated at 475 ° C. for 6 hours under nitrogen gas flow to obtain the desired magnetic iron oxide powder.
(Sample K-3) Example 23 The procedure of Example 19 was repeated, except that 1.0 ml of a 19.3 g / l Na 3 PO 4 aqueous solution was added as P instead of adding the SiO 2 —Na 2 O aqueous solution. A single phase of hydrated iron oxide was obtained. Subsequently, intermediate particles were finished under the conditions of Example 20 to obtain a target magnetic iron oxide powder. Experiments were conducted by changing the amount of ZnSO 4 · 7H 2 O were added in (Sample K-4) Example 24 Example 19. Each of the obtained hydrated iron oxide particles was finished into an intermediate particle under the conditions of Example 20 to obtain a target magnetic iron oxide powder. (Samples K-5 to K-8) Example 25 An experiment was performed in which the amount of MnSO 4 .nH 2 O added in Example 19 was changed. Each of the obtained hydrated iron oxide particles was finished into an intermediate particle under the conditions of Example 20 to obtain a target magnetic iron oxide powder. (Samples K-9 and K-10) Comparative Example 10 The same procedure as in Example 19 was carried out except that MnSO 4 .nH 2 O was not added, and then finished as intermediate particles under the conditions of Example 20. Thus, a magnetic iron oxide powder of a comparative sample was obtained. 1 the amount of ZnSO 4 · 7H 2 O in (Sample K-11) Comparative Example 11 Example 19
Example 20 was carried out in the same manner as in Example 19 except that the amount was 1.01 g and MnSO 4 .nH 2 O was not added.
Under the conditions described above, intermediate particles were finished to obtain a magnetic iron oxide powder of a comparative sample. (Sample K-12) in Comparative Example 12 Example 19 MnSO 4 · nH 2 O and ZnSO 4 · 7
After following the same procedures as in Example 19 except that H 2 O was not added, intermediate particles were finished under the conditions of Example 20 to obtain a magnetic iron oxide powder of a comparative sample. (Sample K-13) Example 26 The reduction temperature was set to 400 ° in Examples 20 and 23.
Except for using C, intermediate particles were finished under the same conditions as in Example 20 to obtain the desired magnetic iron oxide powder. (Samples K-14 to K-
18) Example 27 Intermediate particles were prepared in the same manner as in Example 25 except that the heat treatment temperature was changed to 625 ° C in Sample K-10 to obtain a target magnetic iron oxide powder. (Sample K-19) Example 28 Intermediate particles obtained in Example 20 (Sample K-1)
After dispersing 100 g in 500 ml of pure water, 204.1 g of NaO was added at 35 ° C. with stirring while blowing nitrogen gas.
A solution prepared by dissolving H (purity 98%) to 500 ml was added. Then the 34.07g CoSO 4 · 7H 2 O
(Purity 98%), and adjusted to 125 ml.
After adding the adjusted solution and dissolved 35.54g of FeSO 4 · 7H 2 O (purity 98%) 125ml, 95 °
Aged for 5 hours at C. The obtained precipitate was filtered, washed with water, and dried in the air at 55 ° C. for 3 hours to obtain the desired cobalt-coated magnetic iron oxide powder. (Sample L-1) Comparative Example 13 The same procedure as in Example 26 was carried out except that the intermediate particles obtained in Example 20 were changed to the intermediate particles obtained in Comparative Example 12, to deposit cobalt on the comparative sample. Magnetic iron oxide particles were obtained. (Sample L-2) With respect to the magnetic iron oxide samples (K-1) to (L-2) obtained in Examples 20 to 28 and Comparative Examples 10 to 13, the saturation magnetization (σs) was obtained by an ordinary method. , Ferrous content (F
e (II) / tFe) and the like were measured. The results are shown in Tables 4 and 5.
【００５０】以上の結果において本発明による実施例の
磁性酸化鉄試料は、飽和磁化量が高く優れた磁気特性を
示すことは明らかである。From the above results, it is apparent that the magnetic iron oxide sample of the example according to the present invention has a high saturation magnetization and exhibits excellent magnetic properties.
【００５１】 [0051]
【図１】図１は実施例１９で得られた粒子粉末のＸ線回
析図である。FIG. 1 is an X-ray diffraction diagram of the particle powder obtained in Example 19.
【図２】図２は比較例９で得られた粒子粉末のＸ線回析
図である。FIG. 2 is an X-ray diffraction diagram of the particle powder obtained in Comparative Example 9.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中原 清 山口県宇部市大字小串1978番地の25 チ タン工業株式会社内 (72)発明者 黒崎 浩二 山口県宇部市大字小串1978番地の25 チ タン工業株式会社内 (72)発明者 渡辺 一 山口県宇部市大字小串1978番地の25 チ タン工業株式会社内 (56)参考文献 特開 昭55−141712（ＪＰ，Ａ) 特開 平２−149428（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01F 1/06 C01G 49/06 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kiyoshi Nakahara Inside of 1925 Kogushi, Ogushi, Ube City, Yamaguchi Prefecture Inside (72) Inventor Koji Kurosaki 25 Titan Industry, 1978 Kogushi, Ube City, Yamaguchi Prefecture Incorporated (72) Inventor Kazu Watanabe 1978 Kogushi, Ube City, Yamaguchi Prefecture Inside 25 Titan Kogyo Co., Ltd. (56) References JP-A-55-141712 (JP, A) JP-A-2-149428 (JP) , A) (58) Field surveyed (Int. Cl. 7 , DB name) H01F 1/06 C01G 49/06
Claims (13)
含む溶液で処理し、鉄総量に対して０．１〜１９原子重
量％のマンガン、及び鉄総量に対して３〜１９原子重量
％の亜鉛を含有させたマグヘマイト粒子を、還元して鉄
総量に対して、３１原子重量％以下の第一鉄を含有する
中間体粒子とし、さらに非酸化性雰囲気下にて４００℃
〜ヘマタイトへの転移が生じない上限温度で熱処理する
ことを特徴とする磁気記録用強磁性酸化鉄粉末の製造方
法。The maghemite particles are treated with a solution containing manganese and zinc, and contain manganese in an amount of 0.1 to 19 atomic weight% based on the total amount of iron and 3 to 19 atomic% by weight of zinc based on the total amount of iron. The maghemite particles thus reduced are reduced to intermediate particles containing ferrous iron of 31 atomic weight% or less based on the total amount of iron, and further heated to 400 ° C. in a non-oxidizing atmosphere.
A method for producing a ferromagnetic iron oxide powder for magnetic recording, comprising performing heat treatment at an upper limit temperature at which no transition to hematite occurs.
一鉄を含有する中間体粒子をマンガン及び亜鉛を含む溶
液で処理し、鉄総量に対して０．１〜１９原子重量％の
マンガン、及び鉄総量に対して３〜１９原子重量％の亜
鉛を含有させた中間体粒子とし、さらに非酸化性雰囲気
下にて４００℃〜ヘマタイトへの転移が生じない上限温
度で熱処理することを特徴とする磁気記録用強磁性酸化
鉄粉末の製造方法。2. Intermediate particles containing less than 31 at.% Ferrous iron, based on the total amount of iron, are treated with a solution containing manganese and zinc. Intermediate particles containing zinc in an amount of 3 to 19 atomic weight% with respect to the total amount of manganese and iron, and further heat-treating in a non-oxidizing atmosphere at 400 ° C. to an upper limit temperature at which the transition to hematite does not occur. A method for producing a ferromagnetic iron oxide powder for magnetic recording.
む溶液で処理し、加熱脱水、還元し、鉄総量に対して
０．１〜１９原子重量％のマンガン、及び鉄総量に対し
て３〜１９原子重量％の亜鉛を含有させたマグネタイト
粒子とし、その後非酸化性雰囲気下にて４００℃〜ヘマ
タイトへの転移が生じない上限温度で熱処理し、さらに
酸化してマグヘマイトとすることを特徴とする磁気記録
用強磁性酸化鉄粉末の製造方法。3. The hydrated iron oxide particles are treated with a solution containing manganese and zinc, dehydrated by heating and reduced, and are manganese in an amount of 0.1 to 19 atomic weight% based on the total amount of iron and 3% based on the total amount of iron. A magnetite particle containing up to 19 atomic% by weight of zinc, followed by heat treatment in a non-oxidizing atmosphere at 400 ° C. to an upper limit temperature at which no transition to hematite occurs, and further oxidized to maghemite. Of producing ferromagnetic iron oxide powder for magnetic recording.
イトの中間体まで酸化する微酸化であることを特徴とす
る請求項３記載の磁気記録用強磁性酸化鉄粉末の製造方
法。4. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to claim 3, wherein said oxidation is a slight oxidation in which an intermediate between magnetite and maghemite is oxidized.
む溶液で処理し、加熱脱水、還元し、微酸化し、鉄総量
に対して０．１〜１９原子重量％のマンガン、及び鉄総
量に対して３〜１９原子重量％の亜鉛を含有させた中間
体粒子とし、その後非酸化性雰囲気下にて４００℃〜ヘ
マタイトへの転移が生じない上限温度で熱処理すること
を特徴とする磁気記録用強磁性酸化鉄粉末の製造方法。5. The hydrated iron oxide particles are treated with a solution containing manganese and zinc, heated, dehydrated, reduced, and slightly oxidized, and the manganese and the total amount of iron are 0.1 to 19 atomic weight% with respect to the total amount of iron. Magnetic particles containing 3 to 19 atomic% by weight of zinc, and then heat-treated in a non-oxidizing atmosphere at 400 ° C. to an upper limit temperature at which the transition to hematite does not occur. Of producing ferromagnetic iron oxide powder for use.
イトとすることを特徴とする請求項５記載の磁気記録用
強磁性酸化鉄粉末の製造方法。6. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to claim 5, wherein after the heat treatment is further oxidized to maghemite.
し、さらにマンガン、亜鉛及び鉄を含む溶液で処理し、
鉄総量に対して０．１〜１９原子重量％のマンガン、及
び鉄総量に対して３〜１９原子重量％の亜鉛を含有させ
たマグヘマイト粒子とし、その後還元して中間体粒子と
し、さらに非酸化性雰囲気下にて４００℃〜ヘマタイト
への転移が生じない上限温度で熱処理する工程をさらに
含むことを特徴とする請求項３又は請求項６記載の磁気
記録用強磁性酸化鉄粉末の製造方法。7. The maghemite is washed with a dilute acidic solution, and further treated with a solution containing manganese, zinc and iron,
Maghemite particles containing manganese in an amount of 0.1 to 19 atomic% by weight based on the total amount of iron and zinc in an amount of 3 to 19 atomic% by weight based on the total amount of iron, and then reduced to intermediate particles, and further non-oxidized 7. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to claim 3, further comprising a step of performing a heat treatment at 400 ° C. to an upper limit temperature at which a transition to hematite does not occur in a neutral atmosphere.
らにマンガン、亜鉛及び鉄を含む溶液で処理し、鉄総量
に対して０．１〜１９原子重量％のマンガン、及び鉄総
量に対して３〜１９原子重量％の亜鉛を含有させた中間
体粒子とし、さらに非酸化性雰囲気下にて４００℃〜ヘ
マタイトへの転移が生じない上限温度で熱処理する工程
をさらに含むことを特徴とする請求項４又は請求項５記
載の磁気記録用強磁性酸化鉄粉末の製造方法。8. The intermediate is washed with a dilute acidic solution, further treated with a solution containing manganese, zinc and iron, and 0.1 to 19 atomic weight% of manganese based on the total amount of iron, and Intermediate particles containing 3 to 19 atomic% by weight of zinc, and a heat treatment in a non-oxidizing atmosphere at 400 ° C. to an upper limit temperature at which the transition to hematite does not occur. A method for producing a ferromagnetic iron oxide powder for magnetic recording according to claim 4 or 5.
塩の化合物を含む溶液で処理する工程をさらに含む請求
項１乃至請求項８のいずれか１項に記載の磁気記録用強
磁性酸化鉄粉末の製造方法。9. The ferromagnetic iron oxide powder for magnetic recording according to claim 1, further comprising a step of treating with a solution containing a cobalt compound or a compound of cobalt and a ferrous salt. Production method.
を第二鉄塩中に添加、溶解し、該第二鉄塩溶液とアルカ
リ性溶液とをｐＨ１０〜１３の範囲に保ちながら同時添
加して、鉄総量に対して０．１〜５原子重量％のマンガ
ン、及び鉄総量に対して０．４〜２０原子重量％の亜鉛
を含有させたアルカリ性懸濁液とし、該アルカリ性懸濁
液を５０〜１００℃で加熱熟成した後、水溶性ケイ酸塩
もしくは水溶性リン酸塩を添加して、鉄総量に対して
０．１〜２．５原子重量％のケイ素もしくはリンを含有
させ、水熱処理、加熱脱水を行った後、３００〜４００
℃で還元してマグネタイト粒子とし、さらに非酸化性雰
囲気下にて４００℃〜ヘマタイトへの転移が生じない上
限温度で熱処理を施し、その後、２５０℃以下で微酸化
して鉄総量に対して３１原子重量％以下の第一鉄を含有
させることを特徴とする磁気記録用強磁性酸化鉄粉末の
製造方法。10. A water-soluble manganese salt and a water-soluble zinc salt are added and dissolved in a ferric salt, and the ferric salt solution and the alkaline solution are simultaneously added while maintaining the pH in the range of 10 to 13, An alkaline suspension containing 0.1 to 5 atomic% by weight of manganese with respect to the total amount of iron and 0.4 to 20 atomic% by weight of zinc with respect to the total amount of iron. After heat aging at 100 ° C., a water-soluble silicate or a water-soluble phosphate is added to contain 0.1 to 2.5 atomic% by weight of silicon or phosphorus based on the total amount of iron, and hydrothermal treatment is performed. After performing heat dehydration, 300-400
° C to magnetite particles, and further subjected to a heat treatment in a non-oxidizing atmosphere at 400 ° C to an upper limit temperature at which the transition to hematite does not occur. A method for producing a ferromagnetic iron oxide powder for magnetic recording, characterized by containing ferrous iron of at most atomic weight%.
を第二鉄塩中に添加、溶解し、該第二鉄塩溶液とアルカ
リ性溶液とをｐＨ１０〜１３の範囲に保ちながら同時添
加して、鉄総量に対して０．１〜５原子重量％のマンガ
ン、及び鉄総量に対して０．４〜２０原子重量％の亜鉛
を含有させたアルカリ性懸濁液とし、該アルカリ性懸濁
液を５０〜１００℃で加熱熟成した後、水溶性ケイ酸塩
もしくは水溶性リン酸塩を添加して、鉄総量に対して
０．１〜２．５原子重量％のケイ素もしくはリンを含有
させ、水熱処理、加熱脱水を行った後、３００〜４００
℃で還元、さらに２５０℃以下で微酸化して鉄総量に対
して３１原子重量％以下の第一鉄を含有させた中間体粒
子とし、該中間体粒子を非酸化性雰囲気下にて４００℃
〜ヘマタイトへの転移が生じない上限温度で熱処理を施
すことを特徴とする磁気記録用強磁性酸化鉄粉末の製造
方法。11. A water-soluble manganese salt and a water-soluble zinc salt are added and dissolved in a ferric salt, and the ferric salt solution and the alkaline solution are simultaneously added while maintaining the pH in the range of 10 to 13, An alkaline suspension containing 0.1 to 5 atomic% by weight of manganese with respect to the total amount of iron and 0.4 to 20 atomic% by weight of zinc with respect to the total amount of iron. After heat aging at 100 ° C., a water-soluble silicate or a water-soluble phosphate is added to contain 0.1 to 2.5 atomic% by weight of silicon or phosphorus based on the total amount of iron, and hydrothermal treatment is performed. After performing heat dehydration, 300-400
Reduced at 250 ° C., and then slightly oxidized at 250 ° C. or less to form intermediate particles containing ferrous iron at 31% by weight or less based on the total amount of iron.
A method for producing a ferromagnetic iron oxide powder for magnetic recording, comprising performing heat treatment at an upper limit temperature at which no transition to hematite occurs.
を第二鉄塩中に添加、溶解し、該第二鉄塩溶液とアルカ
リ性溶液とをｐＨ１０〜１３の範囲に保ちながら同時添
加して、鉄総量に対して０．１〜５原子重量％のマンガ
ン、及び鉄総量に対して０．４〜２０原子重量％の亜鉛
を含有させたアルカリ性懸濁液とし、該アルカリ性懸濁
液を５０〜１００℃で加熱熟成した後、水溶性ケイ酸塩
もしくは水溶性リン酸塩を添加して、鉄総量に対して
０．１〜２．５原子重量％のケイ素もしくはリンを含有
させ、水熱処理、加熱脱水を行った後、３００〜４００
℃で還元、２５０℃以下で酸化してマグヘマイト粒子と
し、再び３００〜４００℃で還元して鉄総量に対して３
１原子重量％以下の第一鉄を含有させた中間体粒子と
し、該中間体粒子を非酸化性雰囲気下にて４００℃〜ヘ
マタイトへの転移が生じない上限温度で熱処理を施すこ
とを特徴とする磁気記録用強磁性酸化鉄粉末の製造方
法。12. A water-soluble manganese salt and a water-soluble zinc salt are added and dissolved in a ferric salt, and the ferric salt solution and the alkaline solution are simultaneously added while maintaining the pH in the range of 10 to 13, An alkaline suspension containing 0.1 to 5 atomic% by weight of manganese with respect to the total amount of iron and 0.4 to 20 atomic% by weight of zinc with respect to the total amount of iron. After heat aging at 100 ° C., a water-soluble silicate or a water-soluble phosphate is added to contain 0.1 to 2.5 atomic% by weight of silicon or phosphorus based on the total amount of iron, and hydrothermal treatment is performed. After performing heat dehydration, 300-400
Reduced at 250 ° C., oxidized at 250 ° C. or less to maghemite particles, reduced again at 300-400 ° C., and reduced to 3
Intermediate particles containing 1 atomic weight% or less of ferrous iron, and subjecting the intermediate particles to heat treatment in a non-oxidizing atmosphere at a temperature of 400 ° C. to an upper limit temperature at which the transition to hematite does not occur. Of producing ferromagnetic iron oxide powder for magnetic recording.
鉄塩の化合物を含む溶液で処理する工程をさらに含む請
求項１０乃至請求項１２のいずれか１項記載の磁気記録
用強磁性酸化鉄粉末の製造方法。13. The method for producing a ferromagnetic iron oxide powder for magnetic recording according to claim 10, further comprising a step of treating with a solution containing a cobalt compound or a compound of cobalt and a ferrous salt. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04065874A JP3129823B2 (en) | 1992-03-24 | 1992-03-24 | Method for producing ferromagnetic iron oxide powder for magnetic recording |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04065874A JP3129823B2 (en) | 1992-03-24 | 1992-03-24 | Method for producing ferromagnetic iron oxide powder for magnetic recording |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05267029A JPH05267029A (en) | 1993-10-15 |
| JP3129823B2 true JP3129823B2 (en) | 2001-01-31 |
Family
ID=13299566
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|---|---|---|---|
| JP04065874A Expired - Fee Related JP3129823B2 (en) | 1992-03-24 | 1992-03-24 | Method for producing ferromagnetic iron oxide powder for magnetic recording |
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|---|---|---|---|---|
| JPH07118704A (en) * | 1993-10-25 | 1995-05-09 | Matsushita Electric Ind Co Ltd | Hydrogen storage alloy powder, nickel-hydrogen battery having the powder in negative electrode active material and production of the powder |
| JP6146889B2 (en) * | 2012-07-20 | 2017-06-14 | 小林 博 | Method for producing magnetic powder having an insulated surface |
| CN103694746B (en) * | 2013-12-27 | 2015-11-18 | 广东维诺珠光颜料有限公司 | A kind of preparation method of multifunctional magnetic synthetic mica pearlescent pigment |
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1992
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