JPH0448602A - Manufacture of metallic magnetic powder for magnetic recording - Google Patents
Manufacture of metallic magnetic powder for magnetic recordingInfo
- Publication number
- JPH0448602A JPH0448602A JP2155655A JP15565590A JPH0448602A JP H0448602 A JPH0448602 A JP H0448602A JP 2155655 A JP2155655 A JP 2155655A JP 15565590 A JP15565590 A JP 15565590A JP H0448602 A JPH0448602 A JP H0448602A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic powder
- acid
- metal
- metallic
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006247 magnetic powder Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002184 metal Substances 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 71
- 239000002245 particle Substances 0.000 claims abstract description 37
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 18
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- -1 nitrogen-containing compound Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 2
- 235000011054 acetic acid Nutrition 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract description 2
- 235000002906 tartaric acid Nutrition 0.000 abstract description 2
- 239000011975 tartaric acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229940011182 cobalt acetate Drugs 0.000 description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 230000005415 magnetization Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 125000001297 nitrogen containing inorganic group Chemical group 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の技術的分野）
本発明は、耐酸化性に優れた磁気記録用に好適な金属磁
性粉末の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing a metal magnetic powder having excellent oxidation resistance and suitable for magnetic recording.
磁気記録媒体は、近年高記録密度化による小型化、高性
能化の指向が一段と強まってきている。In recent years, there has been an increasing trend toward miniaturization and higher performance of magnetic recording media due to higher recording densities.
これとあいまって磁気記録用磁性粉末として、従来の酸
化鉄系磁性粉末に比し、飽和磁化が大きく、かつ高保磁
力化が容易な鉄または鉄系金属磁性粉末（以下金属磁性
粉末という）が注目されており、デジタルオーディオチ
ーブや８ ｍ／ｍビデオテープなどへの実用化がはから
れつつあるが、近時さらに高画質ビデオテープ、高記録
密度ディスク用など高性能記録媒体への通用が一層期待
されている。In conjunction with this, iron or iron-based metal magnetic powders (hereinafter referred to as metal magnetic powders) are attracting attention as magnetic powders for magnetic recording, as they have larger saturation magnetization and are easier to increase coercive force than conventional iron oxide-based magnetic powders. Although it is being put to practical use in digital audio chips and 8 m/m video tapes, it has recently become more popular for high-performance recording media such as high-definition video tapes and high-density discs. It is expected.
ところで、このような金属磁性粉末は、通常約０．５μ
ｍ以下（長径）、さらには０．３μｍ以下の微細粒子で
あるのが望ましく、かつこのものを磁気塗料としたとき
の分散性、塗膜での配向性、充填性等に優れたものであ
ることが望まれている。しかしながらこのような微細粒
子は表面活性が強く、このために経時的に酸化が進むこ
とにより、これにともなって飽和磁化、保磁力などの磁
気特性が低下し、いわゆる経時安定性（以下面１酸化性
という）の悪化がさけられなかったりする。またさらに
著しい場合には、前記酸化反応が急激に進むと自然発火
、燃焼に至るなど取扱操作、工程管理上種々のトラブル
を惹起したりする。By the way, such metal magnetic powder usually has a thickness of about 0.5μ.
Preferably, the particles are fine particles with a diameter of 1.5 m or less (longer diameter), and more preferably 0.3 μm or less, and have excellent dispersibility, orientation in a coating film, filling property, etc. when used as a magnetic coating. It is hoped that However, such fine particles have strong surface activity, and as a result, oxidation progresses over time, resulting in a decrease in magnetic properties such as saturation magnetization and coercive force. In some cases, the deterioration of the condition (called sexual) cannot be avoided. In even more severe cases, if the oxidation reaction rapidly progresses, it may lead to spontaneous combustion and combustion, causing various troubles in handling operations and process control.
これらの問題点を改良するために、既に多くの提案がな
されている。例えば、（１）還元により製造した直後の
金属磁性粉末の粒子表面を、徐酸化して薄い酸化被膜を
形成させたり、（２）金属磁性粉末の粒子表面を例えば
シリコン系化合物や高級脂肪酸系化合物等の有機物質で
被覆したり、さらには（３）金属磁性粉末の粒子表面に
、耐食性金属化合物を湿式あるいは乾式の種々の方法に
よって被着せしめる方法等が知られている。しかしなが
ら、これらの方法によっても耐酸化性が十分満足される
ものでなかったり、十分な耐酸化性を付与しようとする
と金属磁性粉末のもつ高飽和磁化、高保磁力などの優れ
た磁気特性や塗料化時の分散性などが損なわれ易かった
りするなど、未だ改善を要する問題点が少なくない。こ
とに、さらに高Ｓ／Ｎ比化、高出力化が一段と要請され
ることとあいまって、金属磁性粉末のより微粒子化が指
向されており前記問題点の解決が強く希求されている。Many proposals have already been made to improve these problems. For example, (1) the particle surface of the metal magnetic powder immediately after being produced by reduction may be slowly oxidized to form a thin oxide film, or (2) the particle surface of the metal magnetic powder may be coated with, for example, a silicon-based compound or a higher fatty acid-based compound. There are also known methods in which (3) a corrosion-resistant metal compound is deposited on the surface of the metal magnetic powder particles by various wet or dry methods. However, even with these methods, the oxidation resistance cannot be fully satisfied, and when trying to impart sufficient oxidation resistance, it is difficult to obtain the excellent magnetic properties of metal magnetic powder such as high saturation magnetization and high coercive force, or to make it into a paint. There are still many problems that need to be improved, such as the fact that the dispersibility of the liquid is easily impaired. In particular, in conjunction with the demand for higher S/N ratios and higher outputs, there is a trend toward finer particles of metal magnetic powder, and there is a strong desire to solve the above-mentioned problems.
本発明は、前記問題点を解決し、耐酸化性に優れた磁気
記録媒体用に好適な金属磁性粉末の製造方法を提供する
ことにある。An object of the present invention is to solve the above-mentioned problems and provide a method for producing metal magnetic powder suitable for use in magnetic recording media with excellent oxidation resistance.
本発明は、本発明者等がかねてより、金属磁性粉末本来
の優れた特性を損なうことなく、前記問題点を解決すべ
く種々検討を進めてきており、先に、特定の金属水酸化
物と、特定の有機金属化合物を形成するたとえば錯化剤
や、特定の金属錯化合物とを金属磁性粉末粒子と加熱接
触させて、金属錯体を生成させつつ、かつ該生成金属錯
体を熱分解せしめて、その熱分解残渣物を金属磁性粉末
粒子表面に担持させることにより、効率的に耐酸化性の
改善をはかることについて提案している。The present invention has been carried out by the present inventors for some time in order to solve the above-mentioned problems without impairing the inherent excellent properties of metal magnetic powder. , for example, a complexing agent that forms a specific organometallic compound or a specific metal complex compound is heated and brought into contact with metal magnetic powder particles to generate a metal complex, and the generated metal complex is thermally decomposed, It is proposed to efficiently improve oxidation resistance by supporting the thermal decomposition residue on the surface of metal magnetic powder particles.
本発明者等は、前記の提案に関しその工業的適用の最適
化についてさらに検討を進めた結果、金属磁性粉末の基
体粒子表面上でアンミン錯体金属化合物を熱分解させる
ことによって、その熱分解残渣物を該粒子表面に担持せ
しめる場合には、加熱分解処理温度を比較的低下せしめ
ることができ、粒子形状崩れや、担持金属の基体粒子内
部への拡散を抑制して磁気特性や耐酸化性効果を損なう
ことなく、経済的有利に耐酸化性の優れた金属磁性粉を
製造し得ることの知見を得、本発明を完成したものであ
る。すなわち、本発明は、
有機酸もしくは無機酸の金属塩および含窒素アルカリ性
化合物、（２）有機酸もしくは無機酸、含窒素アルカリ
性化合物および金属水酸化物、または（３）有機酸もし
くは無機酸の含窒素化合物および金属水酸化物を、金属
磁性粉末と接触させかつ加熱分解して該構成金属のアン
ミン錯体の熱分解残渣物を、該金属磁性粉末の粒子表面
に担持処理することを特徴とする磁気記録用金属磁性粉
末の製造方法に関する。As a result of further studies regarding the optimization of industrial application of the above proposal, the present inventors have found that by thermally decomposing the ammine complex metal compound on the surface of the base particle of metal magnetic powder, the thermal decomposition residue can be removed. When supported on the particle surface, the thermal decomposition temperature can be relatively lowered, suppressing particle shape deformation and diffusion of the supported metal into the base particle, improving magnetic properties and oxidation resistance. The present invention was completed based on the knowledge that metal magnetic powder with excellent oxidation resistance can be produced economically and advantageously without any damage to the powder. That is, the present invention provides a metal salt of an organic or inorganic acid and a nitrogen-containing alkaline compound, (2) an organic or inorganic acid, a nitrogen-containing alkaline compound, and a metal hydroxide, or (3) a metal salt of an organic or inorganic acid. A magnetism characterized by bringing a nitrogen compound and a metal hydroxide into contact with a metal magnetic powder and thermally decomposing it to carry a thermal decomposition residue of an ammine complex of the constituent metal on the particle surface of the metal magnetic powder. The present invention relates to a method for producing metal magnetic powder for recording.
本発明において、被処理物として使用する金属磁性粉末
（以下基体構成粒子という）は、種々の方法によって製
造される鉄または鉄を主体とする鉄系合金類の金属磁性
粉末であって、もっとも−船釣には針状晶の形状のもの
であるが、さらに前記針状晶形状のもののほか、例えば
紡錘状、米粒状、球状、棒状、平板状、サイコロ状など
種々の形状のものを使用することができる。なお、これ
らの基体構成粒子は、担持処理に先立って、必要に応じ
たとえば酸素含有ガスで徐酸化処理しておくこともでき
る。In the present invention, the metal magnetic powder (hereinafter referred to as substrate constituent particles) used as the object to be processed is a metal magnetic powder of iron or an iron-based alloy mainly composed of iron, which is manufactured by various methods, and most For boat fishing, needle-shaped crystals are used, but in addition to the above-mentioned needle-shaped crystals, various other shapes such as spindle-shaped, rice-grain-shaped, spherical, rod-shaped, plate-shaped, dice-shaped, etc. are also used. be able to. Note that, prior to the supporting treatment, these substrate constituent particles may be subjected to a gradual oxidation treatment, for example, with an oxygen-containing gas, if necessary.
本発明において、使用する有機酸または無機酸、それら
の金属塩もしくはそれらの含窒素化合物としては、種々
のものを使用し得るが、（１１有機酸としては、たとえ
ば通常、酢酸、蓚酸、酒石酸、マロン酸などが挙げられ
る。In the present invention, various organic acids or inorganic acids, metal salts thereof, or nitrogen-containing compounds thereof may be used. Examples of organic acids include acetic acid, oxalic acid, tartaric acid, Examples include malonic acid.
（２）有機酸金属塩としては、たとえばＣｏ、Ｎｉ、Ｃ
ｕ、月ｎ。(2) Examples of organic acid metal salts include Co, Ni, C
u, month n.
Ｃｒ、 Ｍｇ、 Ｃａ、 Ｚｎ、 Ｔｔ ＋ Ａ Ｉ＋
Ｚｒ等の金属の酢酸塩、蓚酸塩、酒石酸塩、マロン酸
塩などが挙げられる。Cr, Mg, Ca, Zn, Tt + A I+
Examples include acetates, oxalates, tartrates, and malonates of metals such as Zr.
（３）有機酸の含窒素化合物としては、たとえば酢酸ア
ンモニウム、蓚酸アンモニウム、酒石酸アンモニウムな
どが挙げられる。(3) Examples of the nitrogen-containing organic acid compound include ammonium acetate, ammonium oxalate, and ammonium tartrate.
また（４）無機酸としては、たとえば塩酸、硫酸、硝酸
、炭酸、臭化水素酸、沃化水素酸などが挙げられる。Examples of the inorganic acid (4) include hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, hydrobromic acid, and hydroiodic acid.
（５）無機酸の金属塩としては、たとえばＣｏ＋Ｎｉ＋
Ｃｕ＋Ｍｎ、Ｃｒ、Ｍｇ、Ｃａ、Ｚｎ、Ｔｉ、ＡＩ、Ｚ
ｒなどの塩化物、硫酸塩、硝酸塩、炭酸塩、臭化物、沃
化物などが挙げられる。(5) Examples of metal salts of inorganic acids include Co+Ni+
Cu+Mn, Cr, Mg, Ca, Zn, Ti, AI, Z
Examples include chlorides, sulfates, nitrates, carbonates, bromides, iodides, etc. of r.
（６）無機酸の含窒素化合物としては、たとえば塩化ア
ンモニウム、硫酸アンモニウム、炭酸アンモニウム、臭
化アンモニウム、沃化アンモニウムなどが挙げられる。(6) Examples of the nitrogen-containing inorganic acid compound include ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bromide, and ammonium iodide.
次に（７）含窒素アルカリ性化合物としては、たとえば
アンモニア、アンモニア水、エチレンジアミンなどの有
機アミン類、ヒドラジン、ピリジン、ジピリジルなどが
挙げられる。さらに（８）金属水酸化物としては、たと
えばＣｏ、Ｎｉ、Ｃｕ、Ｍｎ＋Ｃｒ、 Ｍｇ＋ Ｃａ、
Ｚｎ＋ Ｔｔ ＋ ＡＩ ＋ Ｚｒ等の金属の水酸化
物などが挙げられる。Examples of the nitrogen-containing alkaline compound (7) include ammonia, aqueous ammonia, organic amines such as ethylenediamine, hydrazine, pyridine, and dipyridyl. Furthermore, (8) metal hydroxides include, for example, Co, Ni, Cu, Mn+Cr, Mg+Ca,
Examples include metal hydroxides such as Zn+Tt+AI+Zr.
本発明において、担持金属で構成されるアンミン錯体の
熱分解残渣物を前記基体構成粒子表面に担持処理させる
には、該基体構成粒子粉末を液相系で、（１）有機酸も
しくは無機酸の金属塩および含窒素アリカリ性化合物、
（２）有機酸もしくは無機酸、含窒素アルカリ性化合物
および金属水酸化物または（３）有機酸もしくは無機酸
の含窒素化合物および金属水酸化物を、接触させるとと
もに加熱処理して該構成金属のアンミン錯体を生成させ
つつ、かつ該生成アンミン錯体を熱分解させることによ
っておこなうことができる。前記液相系処理に用いる溶
媒としては、たとえば脂肪族炭化水素類、芳香族炭化水
素類、ケトン類、エーテル類、アルコール類など種々の
ものを使用することができる。In the present invention, in order to support the thermal decomposition residue of the ammine complex composed of the supported metal on the surface of the base constituent particles, the base constituent particle powder is treated in a liquid phase by (1) organic acid or inorganic acid. metal salts and nitrogen-containing alkaline compounds,
(2) An organic or inorganic acid, a nitrogen-containing alkaline compound, and a metal hydroxide, or (3) a nitrogen-containing compound of an organic or inorganic acid, and a metal hydroxide are brought into contact with each other and heat-treated to form ammines of the constituent metals. This can be carried out by generating a complex and thermally decomposing the generated ammine complex. As the solvent used in the liquid phase treatment, various solvents can be used, such as aliphatic hydrocarbons, aromatic hydrocarbons, ketones, ethers, and alcohols.
しかして前記処理方法としては、種々の方法によってお
こなうことができるが、たとえば（ａ）前記（１）〜（
３）の場合の各県の処理剤を、予め前記溶媒中で懸濁せ
しめるとともに、該懸濁液中へ前記基体構成粒子粉末を
添加し、次いで窒素ガスなどの不活性ガスを通気させな
がら必要に応じ加熱処理して混合するか、あるいは（ｂ
ｌ前記（１）〜（３）の場合の各県の処理剤を、窒素ガ
スなどの不活性ガスを通気させながら必要に応じ加熱処
理して予め前記溶媒中で構成金属のアンミン錯体を形成
せしめ、次いで前記基体構成粒子粉末を添加し、しかる
後前記（ａ）または（ｂｌの処理物を所定温度で加熱処
理する。The treatment method can be carried out by various methods, such as (a) (1) to (1) above.
In the case of 3), the processing agent of each prefecture is suspended in the above-mentioned solvent in advance, and the base material constituent particle powder is added to the suspension, and then an inert gas such as nitrogen gas is aerated as necessary. Depending on the conditions, heat treatment and mixing or (b
l The treatment agent of each prefecture in the cases of (1) to (3) above is heat-treated as necessary while passing an inert gas such as nitrogen gas to form an ammine complex of the constituent metal in the solvent in advance. Next, the base material forming particle powder is added, and the treated product of (a) or (bl) is then heat-treated at a predetermined temperature.
前記加熱処理は、密閉系反応容器中でおこなってもよい
が、密閉系の場合は、通常５０〜２００℃、好ましくは
１００〜１５０℃で１〜８時間加熱処理する。The heat treatment may be performed in a closed system reaction vessel, but in the case of a closed system, the heat treatment is usually performed at 50 to 200°C, preferably 100 to 150°C for 1 to 8 hours.
また開放系の場合は、通常５０℃以上、好ましくは７０
℃以上で、１〜８時間加熱処理する。これによって、構
成金属のアンミン錯体を形成しかつこのものが、該基体
構成粒子粉末の粒子表面で熱分解されてその熱分解残渣
物が担持される。In addition, in the case of an open system, it is usually 50°C or higher, preferably 70°C or higher.
Heat treatment is performed at a temperature of 1 to 8 hours at a temperature of 1 to 8 hours. As a result, an ammine complex of the constituent metals is formed, which is thermally decomposed on the particle surface of the base constituent particle powder, and its thermal decomposition residue is supported.
本発明において、前記熱分解残渣物の担持量は、基体構
成粒子の金属磁性粉末の粒子の形状、大きさ、比表面積
などによって異なり、−概に言えないが、該基体構成粒
子の重量基準に対して金属として１〜２０％、望ましく
は３〜１５％である。担持量が前記範囲より少なきにす
ぎると所望の効果がもたらされず、また前記範囲より多
きにすぎると飽和磁化などの磁気特性や塗料化時の分散
性などが損なわれ易かったりする。なお前記の熱分解残
渣物を担持処理した金属磁性粉末は、さらに必要に応じ
該粒子表面を窒素含有ガス雰囲気下で加熱処理したり、
あるいは該粒子表面を酸化性ガス雰囲気中で徐酸化した
り、さらにそれらを併せおこなったりすることによって
、耐酸化性を一層好ましいものとすることができる。In the present invention, the amount of the thermal decomposition residue supported varies depending on the shape, size, specific surface area, etc. of the metal magnetic powder particles constituting the base body particles, and although it cannot be generalized, it is based on the weight of the base body particles. In contrast, the amount of metal is 1 to 20%, preferably 3 to 15%. If the supported amount is too small than the above range, the desired effect will not be produced, and if the supported amount is too large, magnetic properties such as saturation magnetization, dispersibility when forming into a paint, etc. may be easily impaired. Note that the metal magnetic powder that has been treated to support the thermal decomposition residue may be further heat-treated on the particle surface in a nitrogen-containing gas atmosphere, if necessary, or
Alternatively, the oxidation resistance can be made more preferable by slowly oxidizing the surface of the particles in an oxidizing gas atmosphere, or by carrying out a combination of these.
本発明において、使用する金属のアンミン錯体の熱分解
残渣物とは、該金属アンミン錯体の熱分解によって、基
体構成粒子の金属磁性粉末の粒子表面に形成される実質
的に当該構成金属成分よりなる耐食性金属あるいはその
金属化合物の表面層のことを謂うものである。前記の熱
分解残渣物の担持処理によって奏される本発明の耐酸化
性等のきわめて優れた特性の改善がもたらされる作用機
作は、未だ十分解明するには至っていないが、均一膜厚
の緻密な耐食性被膜が形成され易いためではないかと推
定される。また前記熱分解残渣物を担持処理した金属磁
性粉末を、酸化性ガス雰囲気中や窒素ガスなどの不活性
ガス雰囲気中で加熱処理することによって金属磁性粉末
の耐酸化性が一層増大し得ることの所以は、前記基体構
成粒子表面の耐食性被膜がより緻密化されたり、さらに
はより安定な酸化被膜が形成されたりすることによるの
ではないかとみられる。In the present invention, the thermal decomposition residue of the metal ammine complex to be used refers to the thermal decomposition residue of the metal ammine complex that is formed on the particle surface of the metal magnetic powder of the base particle and consists essentially of the constituent metal component. It refers to the surface layer of a corrosion-resistant metal or its metal compound. Although the mechanism by which the extremely excellent properties such as oxidation resistance of the present invention are brought about by the above-mentioned supporting treatment of thermal decomposition residues has not yet been fully elucidated, It is presumed that this is because a corrosion-resistant film is easily formed. Furthermore, the oxidation resistance of the metal magnetic powder can be further increased by heat-treating the metal magnetic powder that has been treated to support the thermal decomposition residue in an oxidizing gas atmosphere or an inert gas atmosphere such as nitrogen gas. The reason seems to be that the corrosion-resistant film on the surface of the substrate constituent particles becomes more dense, and that a more stable oxide film is formed.
前記の本発明の方法にもとづいて製造される金属磁性粉
末は、種々のバインダー樹脂、例えば塩化ビニル−酢酸
ビニル共重合体系樹脂、ポリウレタン系樹脂、ポリエス
テル系樹脂、アクリル系樹脂、セルローズ系樹脂などの
バインダー成分と、種々の添加剤、例えば分散剤、潤滑
剤、研磨剤、帯電防止剤などを添加して磁性塗料を調製
し、ポリエチレンテレフタレートフィルム、アセテート
フィルムなど種々の非磁性支持体上に、所定厚み（通常
は乾燥後の厚み２〜５μｍ）に塗布し、配向処理後乾燥
して磁性層を形成し、さらにカレンダー処理、スリッテ
ィング加工を経て磁気記録媒体、例えば磁気テープを得
ることができる。なお、前記磁気テープは、必要に応じ
さらに帯電防止、走行安定性等をはかるべく、該支持体
の磁性層側の反対の面に、いわゆるバックコート層を形
成してもよい。The metal magnetic powder produced according to the method of the present invention described above can be made of various binder resins, such as vinyl chloride-vinyl acetate copolymer resins, polyurethane resins, polyester resins, acrylic resins, cellulose resins, etc. A magnetic paint is prepared by adding a binder component and various additives, such as a dispersant, a lubricant, an abrasive, an antistatic agent, etc., and applied onto various non-magnetic supports such as polyethylene terephthalate film and acetate film. A magnetic recording medium such as a magnetic tape can be obtained by applying the magnetic layer to a thickness (usually 2 to 5 μm thick after drying) and drying after orientation treatment to form a magnetic layer, followed by calendering and slitting. In addition, the magnetic tape may be provided with a so-called back coat layer on the opposite surface of the support from the magnetic layer side in order to further improve antistatic properties, running stability, etc., if necessary.
以下に実施例及び比較例を挙げて本発明をさらに説明す
る。The present invention will be further explained by giving examples and comparative examples below.
ｃ本発明の実施例〕
実施例１
硫酸第一鉄水溶液を水酸化ナトリウム水溶液で中和し、
さらに酸化性ガスを導入し酸化してα−Ｆｅ００Ｈを生
成し、次いでこのものを加熱脱水してα−Ｆｅ００Ｈと
し、しかる後水素気流中で加熱還元して針状の金属鉄磁
性粉末（比表面積（ＢＥＴ） ６５．５ｍ”７ｇ、平均
長軸粒子径０．１６μ、平均軸比９、保磁力１ 、３０
００ ｅ、飽和磁化１８２．４ｇｍｕ／ｇ、角形比０．
４８２）を得た。このものの１５ｇを基体構成粒子とし
、エチルセロソルブ５００ｄ、濃アンモニア水（Ｎ）１
３として２８％）１６．４−および酢酸コバルト（Ｇｏ
（Ｃ８３ＣＯＯ） ｚ・４ＦｉｚＯ） １０ｇを仕込
んだオートクレーブ中に添加して懸濁液を得、ここに窒
素ガスを導入して非酸化性雰囲気を保持しながら、攪拌
上昇温し、１３０℃で２時間、加熱処理した。しかる後
、室温まで冷却し、該懸濁液を濾過し、さらにエチルセ
ロソルブで洗浄して、コバルトのアンミン錯体の熱分解
残渣物を粒子表面に担持した金属磁性粉末のケーキを得
た。次いで該ケーキを、管状電気炉中で窒素ガスを通気
しながら５００℃で２時間加熱処理して、目的の金属磁
性粉末を得た（試料Ａ）。c Examples of the present invention] Example 1 A ferrous sulfate aqueous solution was neutralized with a sodium hydroxide aqueous solution,
Further, an oxidizing gas is introduced and oxidized to produce α-Fe00H, which is then heated and dehydrated to form α-Fe00H, and then heated and reduced in a hydrogen stream to form an acicular metallic iron magnetic powder (specific surface area: (BET) 65.5m” 7g, average major axis particle diameter 0.16μ, average axial ratio 9, coercive force 1, 30
00 e, saturation magnetization 182.4 gmu/g, squareness ratio 0.
482) was obtained. 15 g of this material was used as the base constituent particles, 500 d of ethyl cellosolve, and 1 liter of concentrated ammonia water (N).
3 (28%) 16.4- and cobalt acetate (Go
(C83COO) z・4FizO) was added to an autoclave containing 10 g to obtain a suspension, and while nitrogen gas was introduced thereto to maintain a non-oxidizing atmosphere, the temperature was stirred and raised to 130°C for 2 hours. , heat treated. Thereafter, the suspension was cooled to room temperature, filtered, and further washed with ethyl cellosolve to obtain a cake of metal magnetic powder in which the thermal decomposition residue of the cobalt ammine complex was supported on the particle surface. The cake was then heat-treated at 500° C. for 2 hours in a tubular electric furnace while nitrogen gas was passed through it to obtain the desired metal magnetic powder (Sample A).
実施例２
実施例１において、得られたコバルトのアンミン錯体の
熱分解残渣物を粒子表面に担持した金属磁性粉のケーキ
を、窒素気流中で加熱処理することなく、さらにエタノ
ールで洗浄し、ひきつづきトルエンで洗浄した後風乾し
て、目的の金属磁性粉末を得た（試料Ｂ）。Example 2 In Example 1, the cake of metal magnetic powder carrying the thermal decomposition residue of the cobalt ammine complex on the particle surface was further washed with ethanol without being heat-treated in a nitrogen stream, and then further washed with ethanol. The desired metal magnetic powder was obtained by washing with toluene and air drying (Sample B).
実施例３
実施例１において、酢酸コバルトの代わりに酢酸ニッケ
ル（Ｎｉ （Ｃ１ｌ：＋Ｃ００） ｚ・４１１□Ｏ）１
０ｇを用いたことおよびオートクレーブでの加熱処理温
度を１１０℃としたことのほかは、同例の場合と同様に
処理して、目的の金属磁性粉末を得た（試料ｃ）。Example 3 In Example 1, nickel acetate (Ni (C1l:+C00) z・411□O)1 was used instead of cobalt acetate.
The desired metal magnetic powder was obtained by processing in the same manner as in the same example, except that 0 g was used and the heat treatment temperature in the autoclave was 110° C. (sample c).
実施例４
実施例１において、酢酸コバルトの代わりに、酢酸量（
Ｃｕ（ＣＬＣＯＯ） ！ ・ＩＩｚＯ） ８．０４ｇを
用いたことおよびオートクレーブでの加熱処理を１１０
℃としたことのほかは同例の場合と同様に処理して、目
的の金属磁性粉末を得た（試料Ｄ）。Example 4 In Example 1, the amount of acetic acid (
Cu(CLCOO)!・IIzO) 8.04g was used and heat treatment in an autoclave was
The desired metal magnetic powder was obtained by processing in the same manner as in the same example except that the temperature was changed to 0.degree. C. (Sample D).
実施例５
実施例１において、濃アンモニア水および酢酸コバルト
の代わりに、水酸化第一コパル） （Ｃｏ（ＯＨ） ２
）３．６ｇと、掘アンモニア水（Ｎｌｈとして２８％’
ｌ ５．５ｄおよび酢酸（ＣＨ３ＣＯＯ１１） ４．６
１ｎｌを用いたことのほかは同例の場合と同様に処理し
て、目的の金属磁性粉末を得た（試料Ｅ）。Example 5 In Example 1, instead of concentrated aqueous ammonia and cobalt acetate, copal hydroxide) (Co(OH) 2
) 3.6g and ammonia water (28% as Nlh)
l 5.5d and acetic acid (CH3COO11) 4.6
The desired metal magnetic powder was obtained by processing in the same manner as in the same example except that 1 nl was used (sample E).
実施例６
実施例１において、濃アンモニア水および酢酸コバルト
の代わりに、水酸化第一コバルト（Ｃｏ （０１１）
２）３．６ｇと酢酸アンモニウム（ＣＨ：＋Ｃ００ＮＬ
）６．２ ｇを用いたことのほかは同例の場合と同様に
処理して、目的の金属磁性粉末を得た（試料Ｆ）。Example 6 In Example 1, cobaltous hydroxide (Co(011)) was used instead of concentrated ammonia water and cobalt acetate.
2) 3.6g and ammonium acetate (CH:+C00NL
) 6.2 g was used, but the same treatment as in the same example was carried out to obtain the desired metal magnetic powder (Sample F).
実施例７
実施例１において、エチルセロソルブ５００ｄ、濃アン
モニア水（Ｎ）Ｉｆｆとして２８％）１６．４−および
酢酸コバルト１０ｇをオートクレーブに仕込む前に、こ
れらを撹拌機を付した四ツロフラスコに入れ、窒素ガス
を導入しながら１１０℃まで昇温加熱し、得られた濃縮
物をエチルセロソルブで希釈して５００−としたものを
オートクレーブに仕込んだほかは同例の場合と同様に処
理して、目的の金属磁性粉末を得た（試料Ｇ）。Example 7 In Example 1, before charging 500 d of ethyl cellosolve, concentrated aqueous ammonia (N) (28% as Iff) 16.4-, and 10 g of cobalt acetate into the autoclave, they were placed in a four-way flask equipped with a stirrer, The temperature was raised to 110°C while introducing nitrogen gas, and the resulting concentrate was diluted with ethyl cellosolve to give a 500-. A metal magnetic powder was obtained (Sample G).
実施例８
実施例１において、濃アンモニア水（ＮＨ，とじて２８
％） １６．４−を仕込む代わりに、アンモニアガスを
吹き込んだほかは、同例の場合と同様に処理して、目的
の金属磁性粉末を得た（試料Ｈ）。Example 8 In Example 1, concentrated ammonia water (NH, total 28
%) 16.4-, except that ammonia gas was blown into the sample, and the same process as in the same example was carried out to obtain the desired metal magnetic powder (Sample H).
実施例９
実施例１において、濃アンモニア水（ＮＨ３として２８
％） １６．、ｉ＊の代わりに、エチレンジアミン８．
１ｔｒｉを用いたことおよびオートクレーブでの加熱処
理温度を１４０℃としたことのほかは、同例の場合と同
様に処理して、目的の金属磁性粉末を得た（試料Ｉ）。Example 9 In Example 1, concentrated ammonia water (NH3 as 28
%) 16. , i* instead of ethylenediamine8.
The desired metal magnetic powder was obtained by processing in the same manner as in the same example, except that 1tri was used and the heat treatment temperature in the autoclave was 140° C. (Sample I).
実施例１０
実施例１において、酢酸コバルトおよび濃アンモニア水
の代わりに、塩化コバルト（ＣｏＣＩ□・６Ｈ２０）
９．６ ｇとエチレンジアミン８．ｌｖ＋１を用いたこ
とおよびオートクレーブでの加熱処理温度を１４０℃と
したことのほかは、同例の場合と同様に処理して、目的
の金属磁性粉末を得た（試料Ｊ）。Example 10 In Example 1, cobalt chloride (CoCI□・6H20) was used instead of cobalt acetate and concentrated ammonia water.
9.6 g and 8. ethylenediamine. The desired metal magnetic powder was obtained by processing in the same manner as in the same example, except that lv+1 was used and the heat treatment temperature in the autoclave was 140° C. (Sample J).
実施例１１
実施例工において、酢酸コバルトの代わりに、硫酸コバ
ルト（ＣＯＳＯ４・７８ｚＯ） １１．３ｇを用いたこ
とおよびオートクレーブでの加熱処理温度を１４０℃と
したことのほかは、同例の場合と同様に処理して、目的
の金属磁性粉末を得た（試料Ｋ）。Example 11 The same procedure was carried out as in the same example except that 11.3 g of cobalt sulfate (COSO4.78zO) was used instead of cobalt acetate and the heat treatment temperature in the autoclave was 140°C. The desired metal magnetic powder was obtained by the same treatment (Sample K).
比較例１
実施例１において、オートクレーブでの加熱処理の代わ
りに、撹拌機を付した四ツ目フラスコ中で、窒素ガスを
導入しながら撹拌下４０℃まで昇温し、２時間加熱処理
したことのほかは、同例の場合と同様に処理して、金属
磁性粉末を得た（試料Ｌ）。Comparative Example 1 In Example 1, instead of the heat treatment in an autoclave, the temperature was raised to 40°C with stirring while introducing nitrogen gas in a four-eye flask equipped with a stirrer, and heat treatment was performed for 2 hours. Other than this, the same treatment as in the same example was carried out to obtain a metal magnetic powder (sample L).
比較例２
実施例１において、濃アンモニア水（ＮＨ３とし、て２
８％＞ １６．４ｉｄおよび酢酸コバルト（Ｃｏ（ＣＨ
ｚＣＯＯ） ｔ・４）１２０） １０ ｇの添加を行わ
なかったことのほかは、同例の場合と同様に処理して、
金属磁性粉末を得た（試料Ｍ）。Comparative Example 2 In Example 1, concentrated ammonia water (NH3,
8%>16.4id and cobalt acetate (Co(CH
zCOO) t・4)120) The same process as in the same example was carried out, except that 10 g was not added.
A metal magnetic powder was obtained (sample M).
比較例３
基体構成粒子の金属磁性粉末Ｌｏｇをトルエン３００ｄ
に浸漬後、室温で風乾した（試料Ｎ）。Comparative Example 3 Metal magnetic powder Log of base material particles was mixed with toluene 300d
After soaking in water, it was air-dried at room temperature (sample N).
前記実施例及び比較例の金属磁性粉末試料と、前記試料
中、Ａ−ＨおよびＬ−Ｎの試料を用いて、下記の配合組
成物を混合分散させて磁性塗料を調製し、次いで、前記
磁性塗料をポリエステルフィルム上に、乾燥膜厚１０μ
ｍとなるように塗布し、配向処理後乾燥して作製した磁
気テープとについて、常法により飽和磁化（σｓ ：
ｅｍｕ／ｇ）、保磁力（Ｈｃ ： Ｏｅ）、飽和磁束密
度（Ｂ ｍ ： Ｇａｕｓｓ）、角形比（Ｒｓ、 Ｓ
Ｑ）を測定した。また酸化安定性を評価するために、温
度６０℃、相対湿度８０％の環境下で、４週間放置して
σ５ＳＨＣ％ Ｒ５，Ｂｍについて促進経時変化を測定
し、飽和磁化の劣化率ΔσＳ （％）、ΔＢｍ（％）を
下記の式によって求めた。これらの結果を表１ （粉末
特性）及び表２ （テープ特性）に示す。A magnetic paint was prepared by mixing and dispersing the following blended composition using the metal magnetic powder samples of the Examples and Comparative Examples and the samples A-H and L-N among the samples. Apply the paint onto the polyester film to a dry film thickness of 10 μm.
The saturation magnetization (σs:
emu/g), coercive force (Hc: Oe), saturation magnetic flux density (Bm: Gauss), squareness ratio (Rs, S
Q) was measured. In addition, in order to evaluate the oxidation stability, the accelerated aging change of σ5SHC%R5,Bm was measured after leaving it for 4 weeks in an environment with a temperature of 60°C and a relative humidity of 80%, and the deterioration rate of saturation magnetization ΔσS (%) , ΔBm (%) were determined by the following formula. These results are shown in Table 1 (powder properties) and Table 2 (tape properties).
磁性粉末 ５ 重量部分散剤
０．２５ 〃ポリウレタン樹脂 （
３０％溶液） ２．９６−混合溶媒”
１３．４ 〃” トルエン／ＭＥ
Ｋ／ンクロヘキサノン（４，５／４．５／１）（式中、
σｓ０は経時前のσＳであり、σＳ経時後のσＳである
）
は
（式中、Ｂｍ’は経時前のＢｍであり、Ｂｍ’ は経時
後のＢｍである）
〔発明の効果〕
本発明によって得られる金属錯体の熱分解残渣物を担持
した金属磁性粉末は、耐酸化性が著しく改善されたもの
であり、したがって優れた磁気特性を長期間保持し得る
とともに、それ自体貯蔵安定性に優れ、取扱い操作上、
工程管理上甚だ好ましいものであること、さらに媒体へ
の分散性も良好なものであって高出力の高記録密度磁気
媒体を製造する上で極めて好適なものである。また本発
明は、比較的簡素な手段でもって粒子表面に耐酸化性付
与金属成分を均一に担持することができ、優れた性能の
磁性粉末を経済的に有利に製造することができるもので
あり、甚だ工業的意義の大きいものである。Magnetic powder 5 Weight part dispersant
0.25 Polyurethane resin (
30% solution) 2.96-Mixed solvent”
13.4 〃” Toluene/ME
K/nclohexanone (4,5/4.5/1) (in the formula,
σs0 is σS before aging, σS is σS after aging) (In the formula, Bm' is Bm before aging, and Bm' is Bm after aging.) The obtained metal magnetic powder supporting the thermal decomposition residue of the metal complex has significantly improved oxidation resistance, and therefore can maintain excellent magnetic properties for a long period of time, and has excellent storage stability. During handling,
It is extremely preferable in terms of process control, and has good dispersibility into the medium, making it extremely suitable for producing high-output, high-recording-density magnetic media. In addition, the present invention enables the oxidation resistance imparting metal component to be uniformly supported on the particle surface using relatively simple means, and enables the economically advantageous production of magnetic powder with excellent performance. , is of great industrial significance.
Claims (1)
カリ性化合物、（２）有機酸もしくは無機酸、含窒素ア
ルカリ性化合物および金属水酸化物、または（３）有機
酸もしくは無機酸の含窒素化合物および金属水酸化物を
、金属磁性粉末と接触させかつ加熱分解して該構成金属
のアンミン錯体の熱分解残渣物を、該金属磁性粉末の粒
子表面に担持処理することを特徴とする磁気記録用金属
磁性粉末の製造方法。(1) a metal salt of an organic or inorganic acid and a nitrogen-containing alkaline compound; (2) an organic or inorganic acid, a nitrogen-containing alkaline compound and a metal hydroxide; or (3) a nitrogen-containing compound of an organic or inorganic acid; A metal for magnetic recording, characterized in that a metal hydroxide is brought into contact with a metal magnetic powder and thermally decomposed to carry a thermal decomposition residue of an ammine complex of the constituent metal on the particle surface of the metal magnetic powder. Method for producing magnetic powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2155655A JPH0448602A (en) | 1990-06-14 | 1990-06-14 | Manufacture of metallic magnetic powder for magnetic recording |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2155655A JPH0448602A (en) | 1990-06-14 | 1990-06-14 | Manufacture of metallic magnetic powder for magnetic recording |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0448602A true JPH0448602A (en) | 1992-02-18 |
Family
ID=15610713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2155655A Pending JPH0448602A (en) | 1990-06-14 | 1990-06-14 | Manufacture of metallic magnetic powder for magnetic recording |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0448602A (en) |
-
1990
- 1990-06-14 JP JP2155655A patent/JPH0448602A/en active Pending
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