JP2010218640A - Method for producing metal magnetic powder - Google Patents
Method for producing metal magnetic powder Download PDFInfo
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- JP2010218640A JP2010218640A JP2009065510A JP2009065510A JP2010218640A JP 2010218640 A JP2010218640 A JP 2010218640A JP 2009065510 A JP2009065510 A JP 2009065510A JP 2009065510 A JP2009065510 A JP 2009065510A JP 2010218640 A JP2010218640 A JP 2010218640A
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- magnetic powder
- metal magnetic
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- sodium
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- 239000006247 magnetic powder Substances 0.000 title claims abstract description 132
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 130
- 239000002184 metal Substances 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000005291 magnetic effect Effects 0.000 claims abstract description 63
- 239000002344 surface layer Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000010828 elution Methods 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 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 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 claims description 3
- 229940049920 malate Drugs 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000018341 sodium sesquicarbonate Nutrition 0.000 claims description 3
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229940001468 citrate Drugs 0.000 claims description 2
- 229940001447 lactate Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 29
- 239000000843 powder Substances 0.000 abstract description 20
- 238000005245 sintering Methods 0.000 abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 abstract description 12
- 238000002386 leaching Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 22
- 239000010410 layer Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- -1 lithium aluminum hydride Chemical compound 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- DYPHJEMAXTWPFB-UHFFFAOYSA-N [K].[Fe] Chemical compound [K].[Fe] DYPHJEMAXTWPFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000008199 coating composition Substances 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
- 230000009918 complex formation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
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- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
Description
本発明は、金属磁性粉末の製造方法に関し、特に、塗布型磁気記録媒体に使用される強磁性金属粉末の製造方法に関する。 The present invention relates to a method for producing a metal magnetic powder, and more particularly to a method for producing a ferromagnetic metal powder used in a coating type magnetic recording medium.
塗布型磁気記録媒体に使用される代表的な金属磁性粉末として、鉄を主成分として含有する鉄系磁性粉末がある。このような鉄系金属磁性粉末は、工業的には、オキシ水酸化鉄または酸化鉄を主体とした針状粉末に、形状保持のためにＳｉやＡｌなどを含有させるとともに、焼結防止のために希土類元素やアルカリ土類金属元素などを含有させて、焼成した後に還元することによって製造されている。このような鉄系金属磁性粉末を製造する従来の方法として、α−ＦｅＯＯＨにＮｉ、Ｃｏ、Ａｌ、Ｓｉおよび希土類元素の化合物を被着させ、非還元性雰囲気下で熱処理し、次いで還元性ガスで還元する方法（例えば、特許文献１参照）や、含水酸化鉄の粒子表面に希土類金属化合物やＡｌ化合物などを被着させた後、不活性ガス雰囲気において加熱脱水し、次いで還元性ガスで還元する方法（例えば、特許文献２参照）が知られている。 As a typical metal magnetic powder used for a coating type magnetic recording medium, there is an iron-based magnetic powder containing iron as a main component. Industrially, such iron-based metal magnetic powders contain needle-like powders mainly composed of iron oxyhydroxide or iron oxide to contain Si, Al, etc. in order to maintain the shape and prevent sintering. It is manufactured by adding a rare earth element, an alkaline earth metal element, or the like, firing, and then reducing. As a conventional method for producing such iron-based metal magnetic powder, α-FeOOH is coated with a compound of Ni, Co, Al, Si and a rare earth element, heat-treated in a non-reducing atmosphere, and then reducing gas. (See, for example, Patent Document 1) or after depositing rare earth metal compounds or Al compounds on the surface of hydrous iron oxide particles, followed by heat dehydration in an inert gas atmosphere and then reducing with a reducing gas There is a known method (for example, see Patent Document 2).
近年、塗布型磁気記録媒体などの磁気記録媒体では、大容量化に伴って記録密度を高めることが要求されており、磁気記録媒体の記録密度を高めるためには、磁性粉末の粒子体積を小さくすることが必要になる。 In recent years, magnetic recording media such as coating-type magnetic recording media have been required to increase the recording density as the capacity increases, and in order to increase the recording density of the magnetic recording medium, the particle volume of the magnetic powder is reduced. It becomes necessary to do.
しかし、磁性粉末を微粒子化すると、磁性粉末の粒子の形状を保持し難くなるため、形状保持のために添加するＳｉやＡｌなどの量や、焼結防止のために添加する希土類元素などの量を増加させることが必要になる。しかし、形状保持のために添加するＳｉやＡｌなどや、焼結防止のために添加する希土類元素などは、熱処理工程後には既に役割を終えており、何ら磁性に影響を及ぼすものではなく、粒子体積を大きくするだけであり、粒子性ノイズの低減のためには少ない方がよい。特に、磁性粉末の粒子の表層部に存在する希土類元素などや、ＳｉやＡｌなどの非磁性成分を除去して、粒子体積を小さくするのが望ましい。 However, when the magnetic powder is made into fine particles, it becomes difficult to maintain the shape of the magnetic powder particles. Therefore, the amount of Si or Al added to maintain the shape, the amount of rare earth elements added to prevent sintering, etc. Need to be increased. However, Si and Al added to maintain the shape, rare earth elements added to prevent sintering, etc. have already finished their roles after the heat treatment process and do not affect magnetism at all. It is only necessary to increase the volume, and it is better to reduce the particle noise. In particular, it is desirable to reduce the volume of the particles by removing rare earth elements, etc. present in the surface layer portion of the particles of the magnetic powder and nonmagnetic components such as Si and Al.
このような磁性粉末の粒子の表層部に存在する希土類元素などや、ＳｉやＡｌなどの非磁性成分を除去して、粒子体積を小さくするために、鉄または鉄とコバルトを主成分として含有する金属磁性粉末の表層部に存在する非磁性成分を溶出除去する方法が提案されている（例えば、特許文献３参照）。この方法では、金属磁性粉末の表層部の非磁性成分と錯体を形成し得る錯化剤を添加した溶液に、非磁性成分を含有する金属磁性粉末を添加して分散させた後に、還元剤を添加することによって、金属磁性粉末の表層部の非磁性成分を浸出して溶液中に溶出除去している。 In order to reduce the volume of particles by removing rare-earth elements present in the surface layer of such magnetic powder particles and nonmagnetic components such as Si and Al, it contains iron or iron and cobalt as main components. There has been proposed a method of eluting and removing nonmagnetic components present in the surface layer portion of the metal magnetic powder (see, for example, Patent Document 3). In this method, after adding a metal magnetic powder containing a nonmagnetic component to a solution containing a complexing agent capable of forming a complex with a nonmagnetic component on the surface layer of the metal magnetic powder, the reducing agent is added. By adding, the nonmagnetic component in the surface layer portion of the metal magnetic powder is leached and removed in the solution.
しかし、特許文献３の方法では、金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去する際に、溶液中に還元剤を添加する必要があり、また、還元能力が弱い還元剤を使用すると磁性元素の溶出が起こり易くなるので、溶液中にヒドラジン（Ｎ２Ｈ２）、リチウムアルミニウムハイドライド（ＬｉＡｌＨ４）、ナトリウムボロンハイドライド（ＮａＢＨ４）などの強還元剤を添加する必要がある。そのため、金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去する工程がやや煩雑になり、また、強還元剤を使用して金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去した後の廃液の処理を行うために特殊な貯蔵方法が必要になる。 However, in the method of Patent Document 3, it is necessary to add a reducing agent to the solution when eluting and removing the nonmagnetic component of the surface layer portion of the metal magnetic powder into the solution, and a reducing agent having a weak reducing ability is used. If used, elution of the magnetic element is likely to occur, so it is necessary to add a strong reducing agent such as hydrazine (N 2 H 2 ), lithium aluminum hydride (LiAlH 4 ), sodium boron hydride (NaBH 4 ) to the solution. As a result, the process of eluting and removing the non-magnetic components of the surface layer of the metal magnetic powder into the solution becomes somewhat complicated, and the non-magnetic components of the surface layer of the metal magnetic powder are eluted into the solution using a strong reducing agent. A special storage method is required to treat the waste liquid after the removal.
したがって、本発明は、金属磁性粉末の粒子を小さくするために金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去する際に、還元剤を使用しなくても簡便に金属磁性粉末の表層部の非磁性成分を溶出除去することができる、金属磁性粉末の製造方法を提供することを目的とする。 Therefore, in the present invention, when the nonmagnetic component on the surface portion of the metal magnetic powder is eluted and removed in the solution in order to reduce the particle size of the metal magnetic powder, the metal magnetic powder can be easily obtained without using a reducing agent. It aims at providing the manufacturing method of a metal magnetic powder which can elute and remove the nonmagnetic component of a surface layer part.
本発明者らは、上記課題を解決するために鋭意研究した結果、金属磁性粉末の表層部の非磁性成分と錯体を形成し得る錯化剤を添加するとともにアルカリを添加してｐＨ１０〜１４に調整した溶液に、非磁性成分を含有する金属磁性粉末を添加して分散させることによって、金属磁性粉末の粒子を小さくするために金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去する際に、還元剤を使用しなくても簡便に金属磁性粉末の表層部の非磁性成分を溶出除去することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have added a complexing agent capable of forming a complex with the non-magnetic component of the surface layer portion of the metal magnetic powder and added an alkali to adjust the pH to 10-14. In order to reduce the particle size of the metal magnetic powder, the nonmagnetic component in the surface layer of the metal magnetic powder is eluted and removed in the solution by adding and dispersing the metal magnetic powder containing the nonmagnetic component to the prepared solution. At this time, it was found that the nonmagnetic component in the surface layer portion of the metal magnetic powder can be easily eluted and removed without using a reducing agent, and the present invention has been completed.
すなわち、本発明による金属磁性粉末の製造方法は、鉄または鉄とコバルトを主成分として含有し且つ非磁性成分を含有する金属磁性粉末を製造する工程と、この金属磁性粉末の表層部の非磁性成分と錯体を形成し得る錯化剤を添加するとともにアルカリを添加してｐＨ１０〜１４に調整した溶液に、非磁性成分を含有する金属磁性粉末を添加して分散させることによって、金属磁性粉末の表層部の非磁性成分を浸出して溶液中に溶出除去する工程とを備えている。 That is, the method for producing a metal magnetic powder according to the present invention comprises a step of producing a metal magnetic powder containing iron or iron and cobalt as main components and a nonmagnetic component, and a nonmagnetic property of the surface layer portion of the metal magnetic powder. A metal magnetic powder containing a non-magnetic component is added to and dispersed in a solution adjusted to pH 10 to 14 by adding a complexing agent capable of forming a complex with the component and adding alkali. And a step of leaching and removing the non-magnetic component of the surface layer portion into the solution.
この金属磁性粉末の製造方法において、非磁性成分が、（イットリウムを含む）希土類元素、アルミニウムおよび珪素からなる群から選ばれる１種以上であるのが好ましい。また、錯化剤が、酒石酸塩、クエン酸塩、リンゴ酸塩および乳酸塩からなる群から選ばれる１種以上であるのが好ましい。また、アルカリが、水酸化ナトリウムまたは水酸化カリウムであるのが好ましい。さらに、溶出除去の際に溶液の温度を１０〜５０℃にするのが好ましい。 In this metal magnetic powder production method, the nonmagnetic component is preferably at least one selected from the group consisting of rare earth elements (including yttrium), aluminum and silicon. The complexing agent is preferably at least one selected from the group consisting of tartrate, citrate, malate and lactate. The alkali is preferably sodium hydroxide or potassium hydroxide. Furthermore, the temperature of the solution is preferably 10 to 50 ° C. during elution removal.
また、上記の金属磁性粉末の製造方法は、金属磁性粉末の表層部の非磁性成分を溶出除去した後の金属磁性粉末の表面を洗浄する工程を含むのが好ましい。この場合、金属磁性粉末の表面の洗浄が、アルカリ溶液からなる洗浄液を使用して行われるのが好ましく、アルカリ溶液が、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、セスキ炭酸ナトリウム、リン酸三ナトリウム、ピロリン酸ナトリウム、トリポリリン酸ナトリウム、テトラリン酸ナトリウム、ヘキサメタリン酸ナトリウム、アンモニア、エチルアミンおよびテトラメチルアンモニウムヒドロキシドからなる群から選ばれる１種以上の溶液であるのが好ましく、金属磁性粉末の表面の洗浄がｐＨ１２以上で行われるのが好ましい。 Moreover, it is preferable that the manufacturing method of said metal magnetic powder includes the process of wash | cleaning the surface of the metal magnetic powder after eluting and removing the nonmagnetic component of the surface layer part of metal magnetic powder. In this case, the surface of the metal magnetic powder is preferably cleaned using a cleaning solution made of an alkaline solution, and the alkaline solution is sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium sesquicarbonate, or trisodium phosphate. It is preferably one or more solutions selected from the group consisting of sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, ammonia, ethylamine and tetramethylammonium hydroxide, and the surface of the metal magnetic powder is washed. Is preferably carried out at a pH of 12 or more.
また、上記の金属磁性粉末の製造方法は、金属磁性粉末の表層部の非磁性成分を溶出除去した後の金属磁性粉末の表面に酸化膜を形成する工程を含むのが好ましく、酸化膜を形成した金属磁性粉末を還元処理した後に酸化処理する工程を含むのが好ましい。 In addition, the metal magnetic powder manufacturing method preferably includes a step of forming an oxide film on the surface of the metal magnetic powder after elution and removal of the non-magnetic component of the surface portion of the metal magnetic powder. It is preferable to include a step of subjecting the metal magnetic powder to a reduction treatment followed by an oxidation treatment.
本発明によれば、金属磁性粉末の粒子を小さくするために金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去する際に、還元剤を使用しなくても簡便に金属磁性粉末の表層部の非磁性成分を溶出除去することができる。 According to the present invention, in order to reduce the particle size of the metal magnetic powder, the nonmagnetic component of the surface portion of the metal magnetic powder is eluted and removed into the solution without using a reducing agent. It is possible to elute and remove non-magnetic components in the surface layer portion.
本発明による金属磁性粉末の製造方法の実施の形態は、形状保持や焼結防止のために非磁性成分が添加された原料粉末を焼成した後に還元して、鉄または鉄とコバルトを主成分として含有し且つ形状保持や焼結防止のために添加された非磁性成分を含有する金属磁性粉末を製造する金属磁性粉末製造工程と、この金属磁性粉末の表層部の非磁性成分と錯体を形成し得る錯化剤を添加するとともにアルカリを添加してｐＨ１０〜１４に調整した溶液中に、金属磁性粉末の表層部の非磁性成分を浸出して溶出除去する溶出処理工程と、この溶出処理工程で表層部の非磁性成分を溶出除去した後の金属磁性粉末の表面に酸化膜を形成する酸化処理工程と、この酸化処理工程で酸化膜を形成した金属磁性粉末を還元処理した後に酸化処理する再還元・安定化処理工程と、この再還元・安定化処理工程で還元処理した後に酸化処理した金属磁性粉末の表面を洗浄する洗浄工程とを備えている。以下、これらの工程について説明する。 In the embodiment of the method for producing a metal magnetic powder according to the present invention, the raw material powder to which a nonmagnetic component is added is sintered for shape retention and sintering prevention, and then reduced, and iron or iron and cobalt are the main components. A metal magnetic powder manufacturing process for manufacturing a metal magnetic powder containing a nonmagnetic component that is contained and added for shape retention and sintering prevention, and forms a complex with the nonmagnetic component of the surface layer portion of the metal magnetic powder. In the elution treatment step of leaching and removing the nonmagnetic components of the surface portion of the metal magnetic powder in a solution adjusted to pH 10 to 14 by adding the obtained complexing agent and adding alkali, and in this elution treatment step An oxidation treatment process for forming an oxide film on the surface of the metal magnetic powder after elution and removal of the non-magnetic components in the surface layer portion, and a reduction treatment of the metal magnetic powder on which the oxide film has been formed in this oxidation treatment process, followed by an oxidation treatment. reduction· And Joka process, and a cleaning step of cleaning the surface of the metallic magnetic powder oxidized after reduction treatment in this re-reduction and stabilization process. Hereinafter, these steps will be described.
（金属磁性粉末製造工程）
形状保持や焼結防止のために非磁性成分が添加された原料粉末を焼成した後に還元して、鉄または鉄とコバルトを主成分として含有し且つ形状保持や焼結防止のために添加された非磁性成分を含有する金属磁性粉末を製造するまでの工程としては、一般的な金属磁性粉末の製造工程を採用することができる。例えば、コバルトおよび焼結防止のために添加した希土類元素などを含有するオキシ水酸化鉄を２５０〜７５０℃で焼成して、α−Ｆｅ２Ｏ３などの鉄酸化物にした後、この鉄酸化物を気相還元によって加熱還元して、α−Ｆｅを主成分として含有し且つ希土類元素などの非磁性成分を含有する金属磁性粉末（中間製品としての金属磁性粉末）を得る。
(Metal magnetic powder manufacturing process)
Raw material powder with non-magnetic components added for shape retention and sintering prevention was reduced after firing, and contained iron or iron and cobalt as main components and added for shape retention and sintering prevention As a process until a metal magnetic powder containing a nonmagnetic component is manufactured, a general process for manufacturing a metal magnetic powder can be employed. For example, iron oxyhydroxide containing cobalt and rare earth elements added to prevent sintering is baked at 250 to 750 ° C. to form iron oxides such as α-Fe 2 O 3, and the iron oxidation The product is heated and reduced by vapor phase reduction to obtain a metal magnetic powder containing α-Fe as a main component and a nonmagnetic component such as a rare earth element (metal magnetic powder as an intermediate product).
（溶出処理工程）
このようにして得られた金属磁性粉末に含まれる希土類元素（イットリウムを含む）、アルミニウム（Ａｌ）および珪素（Ｓｉ）の少なくとも１種以上と錯体を形成し得る化合物（錯化剤）を溶解した溶液を処理液として用意する。この処理液は、室温付近の温度で調整することができる。錯化剤としては、無電解めっきにおいて錯化剤として通常使用されている薬品、例えば、酒石酸ナトリウムのような酒石酸塩、クエン酸ナトリウムのようなクエン酸塩、リンゴ酸塩、乳酸塩などを使用することができる。錯化剤の濃度は、０．０１〜１０モル／Ｌ程度でよい。
(Elution process)
A compound (complexing agent) capable of forming a complex with at least one of rare earth elements (including yttrium), aluminum (Al), and silicon (Si) contained in the metal magnetic powder thus obtained was dissolved. A solution is prepared as a processing solution. This treatment liquid can be adjusted at a temperature around room temperature. As the complexing agent, chemicals commonly used as complexing agents in electroless plating, such as tartrate such as sodium tartrate, citrate such as sodium citrate, malate, lactate, etc. are used. can do. The concentration of the complexing agent may be about 0.01 to 10 mol / L.
また、この処理液にアルカリを添加してｐＨ１０〜１４の強アルカリ領域に調整する。このように処理液のｐＨを１０〜１４に調整することにより、従来のように強還元剤を使用しなくても、錯化剤による非磁性成分の浸出が起こり易くなる。この処理液に添加するアルカリとして、水酸化ナトリウムや水酸化カリウムなどを使用するのが好ましく、ｐＨを確認しながらアルカリを添加するのが好ましい。 Further, an alkali is added to the treatment liquid to adjust to a strong alkali region of pH 10-14. By adjusting the pH of the treatment liquid to 10 to 14 in this way, leaching of nonmagnetic components by the complexing agent is likely to occur without using a strong reducing agent as in the conventional case. It is preferable to use sodium hydroxide or potassium hydroxide as the alkali to be added to the treatment liquid, and it is preferable to add the alkali while checking the pH.
次に、このようにｐＨ１０〜１４に調整した処理液に金属磁性粉末を添加する。金属磁性粉末の添加量は、多過ぎると反応が不均一になる可能性があるので、処理液１Ｌ当たり１〜１００ｇ程度であるのが好ましく、５〜５０ｇ程度であるのがさらに好ましい。また、液中の反応の均一性を維持するため、撹拌または強制分散（例えば、超音波分散など）を行うのが好ましい。 Next, the metal magnetic powder is added to the treatment liquid adjusted to pH 10 to 14 in this way. If the addition amount of the metal magnetic powder is too large, the reaction may become non-uniform, so that it is preferably about 1 to 100 g, more preferably about 5 to 50 g, per liter of the treatment liquid. Further, in order to maintain the uniformity of the reaction in the liquid, it is preferable to perform stirring or forced dispersion (for example, ultrasonic dispersion).
処理液中に金属磁性粉末を均一に分散させた後、液温を１０〜５０℃、好ましくは１５〜４０℃に保持しながら、１０〜３００分間浸出操作を行う。この液温が高過ぎると、金属磁性粉末の粒子の表層部から非磁性成分が除去されるだけでなく、粒子の形状が崩壊して、磁気特性を維持することができなくなる場合がある。この浸出操作によって処理液中に非磁性成分が溶出し、金属磁性粉末の粒子中における磁性元素の量が相対的に上昇する。なお、この反応は、不活性ガス雰囲気において行うのが好ましい。 After the metal magnetic powder is uniformly dispersed in the treatment liquid, a leaching operation is performed for 10 to 300 minutes while maintaining the liquid temperature at 10 to 50 ° C., preferably 15 to 40 ° C. If the liquid temperature is too high, not only the nonmagnetic component is removed from the surface layer of the metal magnetic powder particles, but also the shape of the particles may collapse and the magnetic properties may not be maintained. By this leaching operation, the nonmagnetic component is eluted in the treatment liquid, and the amount of the magnetic element in the particles of the metal magnetic powder is relatively increased. This reaction is preferably performed in an inert gas atmosphere.
（酸化処理工程）
次に、必要に応じて、溶出処理した金属磁性粉末の粒子の表面に酸化膜を形成する酸化処理工程を行う。この酸化処理工程は、溶出処理後の液に酸化物を投入して湿式法で酸化処理する工程でもよいし、溶出処理後の液から分離して抽出した金属磁性粉末を乾式法で酸化処理する工程でもよい。
(Oxidation process)
Next, if necessary, an oxidation treatment step for forming an oxide film on the surface of the particles of the eluted metal magnetic powder is performed. This oxidation treatment step may be a step in which an oxide is added to the liquid after the elution treatment and is oxidized by a wet method, or the metal magnetic powder separated and extracted from the liquid after the elution treatment is oxidized by a dry method. It may be a process.
（再還元・安定化処理工程）
次に、必要に応じて、酸化処理した金属磁性粉末に再度還元処理を施し、その後、再度酸化雰囲気に曝す安定化処理を施す。この再還元・安定化処理工程によって先端部が丸みを帯びた粒子が得られ易くなるので好ましい。再還元工程は、水素ガスなどの還元雰囲気下において熱処理することによって行うことができる。熱処理温度は、１５０℃以上であるのが好ましいが、高温になり過ぎると粒子間焼結が起こり易くなるので、３５０℃以下にする必要があり、３００℃以下にするのが好ましい。また、安定化処理は、酸化性ガス雰囲気において熱処理することによって行うことができる。この場合も、温度が高過ぎると焼結が生じ易いので、約１５０〜３５０℃で行うのが好ましい。
(Re-reduction / stabilization process)
Next, if necessary, the oxidized metal magnetic powder is subjected to reduction treatment again, and then subjected to stabilization treatment that is again exposed to an oxidizing atmosphere. This re-reduction / stabilization treatment step is preferable because it is easy to obtain particles with rounded tips. The re-reduction step can be performed by heat treatment in a reducing atmosphere such as hydrogen gas. The heat treatment temperature is preferably 150 ° C. or higher. However, if the temperature is too high, inter-particle sintering is likely to occur. Therefore, the heat treatment temperature needs to be 350 ° C. or lower, and preferably 300 ° C. or lower. The stabilization treatment can be performed by heat treatment in an oxidizing gas atmosphere. In this case as well, sintering is likely to occur if the temperature is too high, so it is preferable to carry out at about 150 to 350 ° C.
（洗浄工程）
最後に、溶出処理後または再還元・安定化処理後の金属磁性粉末を洗浄液に浸漬して、錯体形成時に金属磁性粉末の粒子の表面に付着した錯化剤の有機酸の量を減少させる。この洗浄液として、純水を使用してもよいが、有機酸の量をさらに減少させるために、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、セスキ炭酸ナトリウム、リン酸三ナトリウム、ピロリン酸ナトリウム、トリポリリン酸ナトリウム、テトラリン酸ナトリウム、ヘキサメタリン酸ナトリウム、アンモニア、エチルアミン、テトラメチルアンモニウムヒドロキシドなどのアルカリを含有する水溶液を使用するのが好ましい。
(Washing process)
Finally, the metal magnetic powder after the elution treatment or after the re-reduction / stabilization treatment is immersed in a cleaning solution to reduce the amount of the complexing agent organic acid adhering to the surface of the metal magnetic powder particles during complex formation. Pure water may be used as the cleaning solution, but in order to further reduce the amount of organic acid, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, trisodium phosphate, sodium pyrophosphate, tripolyphosphate It is preferable to use an aqueous solution containing an alkali such as sodium acid, sodium tetraphosphate, sodium hexametaphosphate, ammonia, ethylamine, tetramethylammonium hydroxide.
なお、この洗浄時のｐＨが１２以上であれば、洗浄により有機酸を剥離する効果がより顕著になるので好ましい。また、この洗浄時の温度は、反応条件を最適に調整することができるように、できるだけ室温に近い方がよい。 In addition, if the pH at the time of this washing | cleaning is 12 or more, since the effect which peels an organic acid by washing | cleaning becomes more remarkable, it is preferable. The temperature at the time of washing should be as close to room temperature as possible so that the reaction conditions can be adjusted optimally.
このように、金属磁性粉末の表層部に存在する非磁性成分を溶出除去した後に、金属磁性粉末の表面を洗浄して表面に付着した錯化剤の有機酸を除去することにより、金属磁性粉末の粒子を小さくしても、粒子同士の凝集を防止するとともに、分散性を向上させることができる。 Thus, after eluting and removing the non-magnetic components present on the surface portion of the metal magnetic powder, the surface of the metal magnetic powder is washed to remove the organic acid of the complexing agent adhering to the surface, thereby removing the metal magnetic powder. Even if the particles are made smaller, aggregation of the particles can be prevented and dispersibility can be improved.
このように、本発明による金属磁性粉末の製造方法の実施の形態は、金属磁性粉末の表層部に存在する（焼結防止剤のために添加した）希土類元素や（形状保持のために添加した）ＡｌやＳｉのような直接磁気特性への関与が薄い非磁性成分を選択的に溶出除去する工程と、この溶出の際に金属磁性粒子の表面に付着した錯化剤の有機酸を除去する工程とを備えているので、個々の粒子の分散を保持し易い金属磁性粉末を製造することができる。 As described above, the embodiment of the method for producing the metal magnetic powder according to the present invention includes the rare earth element (added for the sintering inhibitor) present in the surface layer portion of the metal magnetic powder (added for maintaining the shape). ) Selectively elute and remove non-magnetic components that are not directly involved in direct magnetic properties such as Al and Si, and remove the organic acid of the complexing agent adhering to the surface of the metal magnetic particles during this elution A metal magnetic powder that can easily maintain the dispersion of individual particles.
上述した本発明による金属磁性粉末の製造方法の実施の形態により製造された金属磁性粉末は、鉄または鉄とコバルトを主成分とする金属磁性相を有する粒子からなる金属磁性粉末である。すなわち、金属磁性相を構成する磁性元素（例えば、鉄、コバルト）のうち、鉄または鉄とコバルトの合計の原子割合が５０％以上の金属磁性粉末である。この金属磁性粉末の表面には酸化膜が形成されており、鉄（Ｆｅ）とコバルト（Ｃｏ）を主成分として含有する金属磁性粉末では、酸化膜と金属磁性相を含む金属磁性粉末の粒子全体に存在する元素のモル比として「Ｃｏ含有量（ａｔ％）／Ｆｅ含有量（ａｔ％）×１００」で表される、Ｆｅに対するＣｏの原子割合（以下「Ｃｏ／Ｆｅ原子比」という）が、０〜５０ａｔ％であるのが好ましく、５〜４５ａｔ％であるのがさらに好ましく、１０〜４０ａｔ％であるのが最も好ましい。このような範囲であれば、安定した磁気特性が得られ易く、耐候性も良好になる。なお、酸化膜として鉄酸化物が検出されるが、その他の元素の酸化物が同時に存在してもよい。 The metal magnetic powder produced by the embodiment of the method for producing metal magnetic powder according to the present invention described above is a metal magnetic powder composed of particles having a metal magnetic phase mainly composed of iron or iron and cobalt. That is, it is a metal magnetic powder in which the total atomic ratio of iron or iron and cobalt among the magnetic elements (for example, iron and cobalt) constituting the metal magnetic phase is 50% or more. An oxide film is formed on the surface of the metal magnetic powder. In the metal magnetic powder containing iron (Fe) and cobalt (Co) as main components, the entire metal magnetic powder particles including the oxide film and the metal magnetic phase are used. The atomic ratio of Co to Fe (hereinafter referred to as “Co / Fe atomic ratio”) expressed as “Co content (at%) / Fe content (at%) × 100” as the molar ratio of the elements present in 0 to 50 at% is preferable, 5 to 45 at% is more preferable, and 10 to 40 at% is most preferable. Within such a range, stable magnetic characteristics can be easily obtained and weather resistance is also improved. Although iron oxide is detected as the oxide film, oxides of other elements may be present at the same time.
また、金属磁性粉末製造工程では、焼結防止のために（イットリウム（Ｙ）を含む）希土類元素（Ｒ）、Ａｌ、Ｓｉなどの非磁性成分が添加されているが、金属磁性粉末の表層部の非磁性成分は、溶出処理工程において除去されているので、（Ｒ＋Ｓｉ＋Ａｌ）／（Ｆｅ＋Ｃｏ）原子比が、２０ａｔ％以下になり、好ましくは１５ａｔ％以下、さらに好ましくは１３ａｔ％以下、最も好ましくは１２ａｔ％以下にすることができる。このように表層部の非磁性成分を除去することによって、従来の微粉化された金属磁性粉末と比べて、粒子体積が小さい割に飽和磁化が大きい粉末を得ることができる。 In addition, in the magnetic metal powder manufacturing process, non-magnetic components such as rare earth elements (R), Al and Si (including yttrium (Y)) are added to prevent sintering. Since the nonmagnetic component is removed in the elution treatment step, the (R + Si + Al) / (Fe + Co) atomic ratio is 20 at% or less, preferably 15 at% or less, more preferably 13 at% or less, and most preferably 12 at%. % Or less. Thus, by removing the nonmagnetic component in the surface layer portion, it is possible to obtain a powder having a large saturation magnetization for a small particle volume as compared with a conventional finely divided metal magnetic powder.
また、金属磁性粉末の粒子サイズについては、平均長軸長が１０〜５０ｎｍであるのが好ましく、１０〜４０ｎｍであるのがさらに好ましく、１０〜３５ｎｍであるのが最も好ましい。平均長軸長が５０ｎｍを超えると、粒子体積が大きくなってしまい、磁気記録の高記録密度化に十分対応することが難しくなる。 In addition, regarding the particle size of the metal magnetic powder, the average major axis length is preferably 10 to 50 nm, more preferably 10 to 40 nm, and most preferably 10 to 35 nm. When the average major axis length exceeds 50 nm, the particle volume becomes large, and it becomes difficult to sufficiently cope with the increase in recording density of magnetic recording.
上述した本発明による金属磁性粉末の製造方法の実施の形態により製造された金属磁性粉末は、重層塗布型磁気記録媒体の磁性層に使用することができる。重層塗布型磁気記録媒体は、ベースフィルムの上に、下層として非磁性層を有し、その上に上層として磁性層を有するが、金属磁性粉末は、上層の磁性層を形成するための塗料中に配合させて使用することができる。 The metal magnetic powder produced by the embodiment of the method for producing metal magnetic powder according to the present invention described above can be used for the magnetic layer of the multilayer coating type magnetic recording medium. The multilayer coating type magnetic recording medium has a nonmagnetic layer as a lower layer on a base film and a magnetic layer as an upper layer on the base film, but the metal magnetic powder is contained in a paint for forming an upper magnetic layer. Can be used in combination.
なお、上層および下層のいずれの塗料も、各材料を所定組成となるような割合で配合し、ニーダーやサンドグラインダーを用いて混練・分散させる方法により調合することができる。ベースフィルムへの塗料の塗布は、下層が湿潤なうちに可及的に速やかに上層の磁性層を塗布する、所謂ウエット・オン・ウエット方式で行うことが好ましい。 It should be noted that both the upper layer paint and the lower layer paint can be blended by a method in which the respective materials are blended at a ratio such that a predetermined composition is obtained and kneaded and dispersed using a kneader or a sand grinder. The coating is preferably applied to the base film by a so-called wet-on-wet method in which the upper magnetic layer is applied as quickly as possible while the lower layer is wet.
重層塗布型磁気記録媒体では、ベースフィルムとして、例えば、ポリエチレンテレフタラート、ポリエチレンナフタレートなどのポリエステル類、ポリオレフィン類、セルローストリアセテート、ポリカーボネイト、ポリアミド、ポリイミド、ポリアミドイミド、ポリスルフォンアラミド、芳香族ポリアミドなどの樹脂フィルムを使用することができる。また、下層の非磁性層用塗料として、例えば、非磁性粉末（ＤＯＷＡエレクトロニクス（株）製のα−酸化鉄、平均長軸粒子径８０ｎｍ）８５質量部と、カーボンブラック２０質量部と、アルミナ３質量部と、塩化ビニル樹脂（日本ゼオン（株）製の塩化ビニル系バインダーＭＲ−１１０）１５質量部と、ポリウレタン樹脂（東洋紡（株）製のポリウレタン樹脂ＵＲ−８２００）１５質量部と、メチルエチルケトン１９０質量部と、シクロヘキサノン８０質量部と、トルエン１１０質量部とからなる組成の非磁性塗料を使用することができる。さらに、上層の磁性層用塗料として、例えば、金属磁性粉末１００質量部と、カーボンブラック５質量部と、アルミナ３質量部と、塩化ビニル樹脂（日本ゼオン（株）製のＭＲ−１１０）１５質量部と、ポリウレタン樹脂（東洋紡（株）製のＵＲ−８２００）１５質量部と、ステアリン酸１質量部と、アセチルアセトン１質量部と、メチルエチルケトン１９０質量部と、シクロヘキサノン８０質量部と、トルエン１１０質量部とからなる組成の磁性塗料を使用することができる。 In the multilayer coating type magnetic recording medium, as the base film, for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, cellulose triacetate, polycarbonate, polyamide, polyimide, polyamideimide, polysulfone aramid, aromatic polyamide, etc. A resin film can be used. Examples of the coating material for the lower nonmagnetic layer include, for example, 85 parts by mass of nonmagnetic powder (α-iron oxide manufactured by DOWA Electronics Co., Ltd., average major axis particle size of 80 nm), 20 parts by mass of carbon black, and alumina 3 15 parts by mass of vinyl chloride resin (vinyl chloride binder MR-110 manufactured by Nippon Zeon Co., Ltd.), 15 parts by mass of polyurethane resin (polyurethane resin UR-8200 manufactured by Toyobo Co., Ltd.), and methyl ethyl ketone 190 A nonmagnetic paint having a composition composed of part by mass, 80 parts by mass of cyclohexanone, and 110 parts by mass of toluene can be used. Further, as the magnetic layer coating for the upper layer, for example, 100 parts by mass of metal magnetic powder, 5 parts by mass of carbon black, 3 parts by mass of alumina, and 15 parts by mass of vinyl chloride resin (MR-110 manufactured by Nippon Zeon Co., Ltd.) Parts, 15 parts by mass of polyurethane resin (UR-8200 manufactured by Toyobo Co., Ltd.), 1 part by mass of stearic acid, 1 part by mass of acetylacetone, 190 parts by mass of methyl ethyl ketone, 80 parts by mass of cyclohexanone, and 110 parts by mass of toluene A magnetic coating composition having the following composition can be used.
以下、本発明による金属磁性粉末の製造方法の実施例について詳細に説明する。 Hereinafter, the Example of the manufacturing method of the metal magnetic powder by this invention is described in detail.
まず、５０００ｍＬのビーカーに純水３０００ｍＬを入れた後、温調機で３０℃に維持しながら、０．０３モル／Ｌの硫酸コバルト（特級試薬）溶液と０．１５モル／Ｌの硫酸第一鉄（特級試薬）水溶液をＣｏ：Ｆｅ＝１：４の混合割合になるように混合した。この混合溶液５００ｍＬに、Ｆｅ＋Ｃｏに対して炭酸が３当量になる量の顆粒状の炭酸ナトリウムを直接添加し、液中温度が４０±５℃の範囲を超えないように調整しながら、炭酸鉄を主体とする懸濁液を作製した。この懸濁液を９０分間熟成させた後、Ｆｅイオンの酸化率が２０％になるように調整した量の空気を５０ｍＬ／分の流量で添加して核晶を形成させ、６０℃まで昇温させ、純酸素を５０ｍＬ／分の流量で通気して６０分間酸化を継続した。その後、純酸素を窒素に切り替えて、３０分間程度熟成した。 First, after adding 3000 mL of pure water to a 5000 mL beaker, maintaining at 30 ° C. with a temperature controller, a 0.03 mol / L cobalt sulfate (special grade reagent) solution and 0.15 mol / L sulfuric acid first An aqueous solution of iron (special grade reagent) was mixed so as to have a mixing ratio of Co: Fe = 1: 4. To 500 mL of this mixed solution, granulated sodium carbonate in an amount of 3 equivalents of Fe + Co was directly added, and the temperature in the liquid was adjusted so as not to exceed the range of 40 ± 5 ° C. A main suspension was prepared. After aging this suspension for 90 minutes, air adjusted to an oxidation rate of Fe ions of 20% was added at a flow rate of 50 mL / min to form nuclei, and the temperature was raised to 60 ° C. Then, pure oxygen was aerated at a flow rate of 50 mL / min and oxidation was continued for 60 minutes. Thereafter, the pure oxygen was switched to nitrogen and aged for about 30 minutes.
次に、液温を４０℃まで降温させて温度が安定した後、１．０質量％のＡｌの硫酸アルミニウム水溶液を５．０ｇ／分の添加速度で２０分間添加し続けてオキシ水酸化鉄を成長させた。その後、純酸素を５０ｍＬ／分の流量で流し続け、酸化を完結させた。なお、酸化の終点の確認は、上澄み液を少量分取し、ヘキサシアノ酸鉄カリウム溶液を添加して、液色が変化しないことを確認することによって行った。 Next, after the liquid temperature was lowered to 40 ° C. and the temperature was stabilized, 1.0 mass% Al aluminum sulfate aqueous solution was continuously added at an addition rate of 5.0 g / min for 20 minutes, and iron oxyhydroxide was added. Grown up. Thereafter, pure oxygen was kept flowing at a flow rate of 50 mL / min to complete the oxidation. The end point of the oxidation was confirmed by taking a small amount of the supernatant and adding an iron potassium hexacyanoate solution to confirm that the liquid color did not change.
次に、酸化終了後の液に（イットリウムとして２．０質量％含有する）酸化イットリウムの硫酸水溶液３００ｇを添加して、Ａｌを固溶させ、イットリウムが表面に被着したオキシ水酸化鉄の粉末（ケーキ）を得た。 Next, 300 g of an aqueous solution of sulfuric acid of yttrium oxide (containing 2.0% by mass as yttrium) is added to the liquid after completion of oxidation to dissolve Al, and the iron oxyhydroxide powder deposited on the surface of yttrium (Cake) was obtained.
このオキシ水酸化鉄のケーキを濾過し、水洗した後、１３０℃で６時間乾燥させ、オキシ水酸化鉄の乾燥固形物を得た。この乾燥固形物１０ｇをバケットに入れ、水の流量として１．０ｇ／分で水蒸気を添加しながら大気中において４００℃で焼成し、α−酸化鉄（ヘマタイト）を主成分とする鉄系酸化物を得た。 The iron oxyhydroxide cake was filtered, washed with water, and dried at 130 ° C. for 6 hours to obtain a dried solid product of iron oxyhydroxide. 10 g of this dry solid is put into a bucket and fired at 400 ° C. in the atmosphere while adding water vapor at a flow rate of 1.0 g / min, and an iron-based oxide mainly composed of α-iron oxide (hematite) Got.
このα−酸化鉄を主成分とする鉄系酸化物を通気可能なバケット内に投入した後、バケットを貫通型還元炉内に装入し、水素ガスを４０Ｌ／分の流量で通気するとともに、水の流量として１．０ｇ／分で水蒸気を添加しながら、４００℃で３０分間焼成させて還元処理を行った。この還元処理が終了した後、水蒸気の供給を停止し、水素雰囲気下において昇温速度１０℃／分で６００℃まで昇温させた。その後、水の流量として１．０ｇ／分で水蒸気を添加しながら６０分間高温還元処理を行い、鉄系合金粉末（中間製品としての金属磁性粉末）を得た。 After charging the iron-based oxide containing α-iron oxide as a main component into a bucket that can be ventilated, the bucket is charged into a through-type reduction furnace, and hydrogen gas is vented at a flow rate of 40 L / min. While water vapor was added at a flow rate of 1.0 g / min, the reduction treatment was performed by baking at 400 ° C. for 30 minutes. After the reduction treatment was completed, the supply of water vapor was stopped, and the temperature was raised to 600 ° C. at a temperature rising rate of 10 ° C./min in a hydrogen atmosphere. Thereafter, high-temperature reduction treatment was performed for 60 minutes while adding water vapor at a flow rate of water of 1.0 g / min to obtain an iron-based alloy powder (metal magnetic powder as an intermediate product).
次に、この粉末の溶出処理を行うために使用する処理液として、純水９００ｍＬに対して、錯化剤として酒石酸ナトリウムを０．０３モル／Ｌ、緩衝剤として硫酸アンモニウムを０．０５モル／Ｌになるように混合し、水酸化ナトリウムを加えてｐＨ１３程度に調整した処理液を用意した。この処理液に還元処理後の粉末１０ｇを投入し、３０℃で３０分間撹拌しながら反応させてスラリーを得た。このスラリーを固液分離し、固形分を水洗し、濾過して濾過物を得た。 Next, as a treatment liquid used for the elution treatment of the powder, 0.03 mol / L of sodium tartrate as a complexing agent and 0.05 mol / L of ammonium sulfate as a buffering agent with respect to 900 mL of pure water. Then, a treatment liquid prepared by adding sodium hydroxide and adjusting the pH to about 13 was prepared. 10 g of the powder after the reduction treatment was added to this treatment liquid and reacted with stirring at 30 ° C. for 30 minutes to obtain a slurry. This slurry was subjected to solid-liquid separation, and the solid content was washed with water and filtered to obtain a filtrate.
次に、得られた濾過物を通気可能なバケット内に入れた後、バケットを貫通型還元炉内に装入し、５０Ｌ／分の流量で窒素を導入しながら９０℃で乾燥させて粉末を得た。その後、窒素と純酸素をそれぞれ５０Ｌ／分および４００ｍＬ／分の流量で混合したガスを炉内に添加し、水の流量として１．０ｇ／分で水蒸気を添加しながら、水蒸気と酸素と窒素の混合雰囲気中において、粉末の表面に酸化膜を形成し、表面の酸化による発熱が抑制された段階で純酸素の流量を徐々に増加することによって、混合雰囲気中における酸素濃度を上昇させ、最終的な純酸素の流量を２．０Ｌ／分にした。なお、炉内に導入されるガスの総量は、窒素の流量を調整することによってほぼ一定に保たれるようにし、この酸化処理は、約９０℃に維持される雰囲気下において１時間行った。 Next, after putting the obtained filtrate in a bucket that can be ventilated, the bucket is placed in a through-type reducing furnace, and dried at 90 ° C. while introducing nitrogen at a flow rate of 50 L / min to obtain a powder. Obtained. Thereafter, a gas in which nitrogen and pure oxygen are mixed at a flow rate of 50 L / min and 400 mL / min, respectively, is added to the furnace, and water vapor is added at a flow rate of 1.0 g / min. In the mixed atmosphere, an oxide film is formed on the surface of the powder, and the oxygen concentration in the mixed atmosphere is increased and finally increased by gradually increasing the flow rate of pure oxygen at the stage where heat generation due to surface oxidation is suppressed. The flow rate of pure oxygen was 2.0 L / min. The total amount of gas introduced into the furnace was kept substantially constant by adjusting the flow rate of nitrogen, and this oxidation treatment was performed for 1 hour in an atmosphere maintained at about 90 ° C.
次に、表面に酸化膜を形成した粉末を２５０℃の水素雰囲気下に３０分間曝すことによって再還元処理を行った後、上記の酸化処理と同様の方法によって安定化処理を行った。 Next, after performing re-reduction treatment by exposing the powder having an oxide film formed on the surface in a hydrogen atmosphere at 250 ° C. for 30 minutes, stabilization treatment was performed by the same method as the oxidation treatment described above.
この安定化処理後の粉末をｐＨ１３程度に調整した０．１モル／Ｌの水酸化ナトリウム水溶液に浸漬し、３０℃で３０分間撹拌して、表面に付着した有機酸を剥離し、得られたスラリーから固形分を回収した。 The powder after stabilization treatment was immersed in a 0.1 mol / L sodium hydroxide aqueous solution adjusted to about pH 13, and stirred at 30 ° C. for 30 minutes to peel off the organic acid adhering to the surface. Solids were recovered from the slurry.
このようにして得られた金属磁性粉末（最終製品としての金属磁性粉末）について、組成分析および磁気特性の測定を行った。 The thus obtained metal magnetic powder (metal magnetic powder as a final product) was subjected to composition analysis and measurement of magnetic properties.
粉末の組成は、金属磁性相と酸化膜を含む粒子全体の質量分析を行うことによって求めた。なお、Ｃｏ、Ａｌおよび希土類元素（Ｙを含む）の定量は、日本ジャーレルアッシュ株式会社製の高周波誘導プラズマ発光分析装置ＩＣＰ（ＩＲＩＳ／ＡＰ）を使用し、Ｆｅの定量は、平沼産業株式会社製の平沼自動滴定装置（ＣＯＮＴＩＭＥ−９８０型）を使用して行った。また、粉末の磁気特性は、東英工業株式会社製のＶＳＭ装置（ＶＳＭ−７Ｐ）を使用して外部磁場１０ｋＯｅ（７９５．８ｋＡ／ｍ）で測定した。その結果を表１および表２に示す。 The composition of the powder was determined by performing mass analysis of the entire particle including the metal magnetic phase and the oxide film. Co, Al and rare earth elements (including Y) were quantified using a high frequency induction plasma emission analyzer ICP (IRIS / AP) manufactured by Nippon Jarrel Ash Co., and Fe was quantified by Hiranuma Sangyo Co., Ltd. This was carried out using a Hiranuma automatic titrator (CONTIME-980 type). The magnetic properties of the powder were measured with an external magnetic field of 10 kOe (795.8 kA / m) using a VSM device (VSM-7P) manufactured by Toei Kogyo Co., Ltd. The results are shown in Tables 1 and 2.
表１に示すように、金属磁性粉末中のＦｅ、Ｃｏ、Ａｌ、Ｙの含有量は、それぞれ５６．３質量％、１２．４質量％、２．２質量％、６．５質量％であった。また、表２に示すように、金属磁性粉末の保磁力は２１２２Ｏｅ（１６８．９ｋＡ／ｍ）、飽和磁化は１１３．９Ａｍ２／ｋｇ、角形比は０．５１、保磁力分布ＳＦＤは１．１９であった。 As shown in Table 1, the contents of Fe, Co, Al, and Y in the metal magnetic powder were 56.3% by mass, 12.4% by mass, 2.2% by mass, and 6.5% by mass, respectively. It was. Moreover, as shown in Table 2, the coercive force of the metal magnetic powder is 2122 Oe (168.9 kA / m), the saturation magnetization is 113.9 Am 2 / kg, the squareness ratio is 0.51, and the coercive force distribution SFD is 1.19. Met.
次に、得られた金属磁性粉末（最終製品としての金属磁性粉末）０.３５ｇを秤量して（内径４５ｍｍ、深さ１３ｍｍの）ポットに入れ、蓋を開けた状態で１０分間放置した後、マイクロピペットでビヒクル（東洋紡製の塩化ビニル系樹脂ＭＲ−１１０（２２質量％）と、シクロヘキサノン（３８.７質量％）と、アセチルアセトン（０.３質量％）と、ステアリン酸−ｎ−ブチル（０.３質量％）と、メチルエチルケトン（３８.７質量％）の混合溶液）０.７ｍＬを添加し、その直後にスチールボール（２φ）３０ｇ、ナイロンボール（８φ）１０個をポットに加えて、蓋を閉じた状態で１０分間静置した。その後、ポットを遠心式ボールミル（ＦＲＩＴＳＨ Ｐ−６）にセットし、ゆっくりと回転数を上げて６００ｒｐｍに調整し、６０分間分散させた。遠心式ボールミルを停止した後、ポットを取り出し、予めメチルエチルケトンとトルエンを１：１で混合した調整液１.８ｍＬをマイクロピペットで添加した。その後、再びポットを遠心式ボールミルにセットし、６００ｒｐｍで５分間分散させ、磁性塗料を作製した。 Next, 0.35 g of the obtained metal magnetic powder (metal magnetic powder as a final product) was weighed and placed in a pot (inner diameter 45 mm, depth 13 mm) and left for 10 minutes with the lid open, A vehicle with a micropipette (vinyl chloride resin MR-110 (22% by mass), cyclohexanone (38.7% by mass), acetylacetone (0.3% by mass), stearic acid-n-butyl (0% by Toyobo) .3 mass%) and methyl ethyl ketone (38.7 mass%) mixed solution (0.7 mL) are added. Immediately thereafter, 30 g of steel balls (2φ) and 10 nylon balls (8φ) are added to the pot, Was allowed to stand for 10 minutes in a closed state. Thereafter, the pot was set on a centrifugal ball mill (FRITSH P-6), and the number of revolutions was slowly increased to 600 rpm and dispersed for 60 minutes. After stopping the centrifugal ball mill, the pot was taken out, and 1.8 mL of a preliminarily mixed solution of methyl ethyl ketone and toluene at 1: 1 was added with a micropipette. Thereafter, the pot was set again on the centrifugal ball mill, and dispersed at 600 rpm for 5 minutes to produce a magnetic paint.
次に、ポットの蓋を開けてナイロンボールを取り除き、スチールボールごと磁性塗料をアプリケータ（５５０μｍ）に入れ、ベースフィルム（東レ株式会社製のポリエチレンフィルム１５Ｃ−Ｂ５００、膜厚１５μｍ）上に磁性塗料を塗布し、迅速に５.５ｋＧの配向器のコイル中心に置いて磁場配向させた後、乾燥させて磁気テープを作製した。なお、ここでは金属磁性粉末の効果をより鮮明に確認するため、非磁性層を設けず、磁性層単層のテープを作製した。 Next, the pot lid is opened to remove the nylon ball, and the magnetic paint is put together with the steel ball into the applicator (550 μm), and the magnetic paint is applied on the base film (Toray Industries, Inc. polyethylene film 15C-B500, film thickness 15 μm). Was quickly placed on the center of the coil of a 5.5 kG aligner and magnetically oriented, and then dried to produce a magnetic tape. Here, in order to confirm the effect of the metal magnetic powder more clearly, a tape having a single magnetic layer was prepared without providing a nonmagnetic layer.
このようにして作製した媒体としての磁気テープについて、東英工業株式会社製のＶＳＭ装置（ＶＳＭ−７Ｐ）を使用して磁気測定を行い、保磁力Ｈｃ、保磁力分布ＳＦＤ、角形比、配向比を求めた。その結果を表３に示す。 The magnetic tape as the medium thus prepared was subjected to magnetic measurement using a VSM device (VSM-7P) manufactured by Toei Kogyo Co., Ltd., and coercive force Hc, coercive force distribution SFD, squareness ratio, orientation ratio. Asked. The results are shown in Table 3.
表３に示すように、磁気テープの保磁力Ｈｃは２６１０Ｏｅ（２０７．７ｋＡ／ｍ）、保磁力分布ＳＦＤは０．４７、角形比は０．８７、配向比は２．６８であった。 As shown in Table 3, the magnetic tape had a coercive force Hc of 2610 Oe (207.7 kA / m), a coercive force distribution SFD of 0.47, a squareness ratio of 0.87, and an orientation ratio of 2.68.
また、比較例として、水酸化ナトリウムを加えてｐＨ１３程度に調整した処理液の代わりにアンモニアを加えてｐＨ９に調整した処理液を使用し、この処理液に還元処理後の粉末を投入して３０℃に保持した後に、還元剤として水素化ホウ素ナトリウムを０．３モル／Ｌになるように添加した以外は、実施例と同様の処理により、金属磁性粉末および磁気テープを作製し、実施例と同様の測定を行った。その結果を表１〜表３に示す。 Further, as a comparative example, instead of the treatment liquid adjusted to about pH 13 by adding sodium hydroxide, a treatment liquid adjusted to pH 9 by adding ammonia was used, and the powder after reduction treatment was added to this treatment liquid. A metal magnetic powder and a magnetic tape were prepared by the same treatment as in the Example except that sodium borohydride was added as a reducing agent to a concentration of 0.3 mol / L after being held at 0 ° C. Similar measurements were made. The results are shown in Tables 1 to 3.
表１に示すように、金属磁性粉末中のＦｅ、Ｃｏ、Ａｌ、Ｙの含有量は、それぞれ５６．１質量％、１２．９質量％、２．２質量％、６．３質量％であった。また、表２に示すように、金属磁性粉末の保磁力は２１００Ｏｅ（１６７．１ｋＡ／ｍ）、飽和磁化は１１３．３Ａｍ２／ｋｇ、角形比は０．５０、保磁力分布ＳＦＤは１．２２であった。さらに、表３に示すように、磁気テープの保磁力Ｈｃは２６２８Ｏｅ（２０９．１ｋＡ／ｍ）、保磁力分布ＳＦＤは０．５１、角形比は０．８６、配向比は２．６８であった。 As shown in Table 1, the contents of Fe, Co, Al, and Y in the metal magnetic powder were 56.1% by mass, 12.9% by mass, 2.2% by mass, and 6.3% by mass, respectively. It was. Further, as shown in Table 2, the coercive force of the metal magnetic powder is 2100 Oe (167.1 kA / m), the saturation magnetization is 113.3 Am 2 / kg, the squareness ratio is 0.50, and the coercive force distribution SFD is 1.22. Met. Furthermore, as shown in Table 3, the coercive force Hc of the magnetic tape was 2628 Oe (209.1 kA / m), the coercive force distribution SFD was 0.51, the squareness ratio was 0.86, and the orientation ratio was 2.68. .
上述したように、実施例と比較例で得られた金属磁性粉末の磁気特性には大きな変化がなく、その粒子の形状も大きな違いは確認されなかった。これらの結果から、金属磁性粉末の表層部の非磁性成分と錯体を形成し得る錯化剤を添加するとともにアルカリを添加して強アルカリ領域（ｐＨ１０〜１４）に調整した溶液に、非磁性成分を含有する金属磁性粉末を添加して分散させることによって、金属磁性粉末の粒子を小さくするために金属磁性粉末の表層部の非磁性成分を溶液中に溶出除去する際に、還元剤を使用しなくても簡便に金属磁性粉末の表層部の非磁性成分を溶出除去することができることがわかった。 As described above, there was no significant change in the magnetic properties of the metal magnetic powders obtained in the examples and comparative examples, and no significant difference was observed in the shape of the particles. From these results, a non-magnetic component was added to a solution prepared by adding a complexing agent capable of forming a complex with a non-magnetic component on the surface portion of the metal magnetic powder and adding alkali to a strong alkali region (pH 10-14). In order to reduce the particles of the metal magnetic powder, the reducing agent is used to elute and remove the nonmagnetic components in the surface layer of the metal magnetic powder into the solution by adding and dispersing the metal magnetic powder containing It was found that the nonmagnetic component in the surface layer portion of the metal magnetic powder can be easily eluted and removed without the need.
Claims (10)
The method for producing a metal magnetic powder according to any one of claims 1 to 5, further comprising a step of forming an oxide film on the surface of the metal magnetic powder after the nonmagnetic component in the surface layer portion of the metal magnetic powder has been eluted and removed.
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