JP4497285B2 - 鉄系黒色粒子粉末及び該鉄系黒色粒子粉末を含有する黒色トナー - Google Patents
鉄系黒色粒子粉末及び該鉄系黒色粒子粉末を含有する黒色トナー Download PDFInfo
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- JP4497285B2 JP4497285B2 JP2004010864A JP2004010864A JP4497285B2 JP 4497285 B2 JP4497285 B2 JP 4497285B2 JP 2004010864 A JP2004010864 A JP 2004010864A JP 2004010864 A JP2004010864 A JP 2004010864A JP 4497285 B2 JP4497285 B2 JP 4497285B2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 189
- 239000002245 particle Substances 0.000 title claims description 134
- 239000000843 powder Substances 0.000 title claims description 87
- 229910052742 iron Inorganic materials 0.000 title claims description 70
- 230000005415 magnetization Effects 0.000 claims description 31
- 239000006104 solid solution Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 14
- 239000001055 blue pigment Substances 0.000 claims description 13
- 229910052596 spinel Inorganic materials 0.000 claims description 9
- 239000011029 spinel Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 18
- 238000004040 coloring Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 150000003609 titanium compounds Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 229910001566 austenite Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000007900 aqueous suspension Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- -1 organosilane compound Chemical class 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HYKDWGUFDOYDGV-UHFFFAOYSA-N 4-anilinobenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=CC=C1 HYKDWGUFDOYDGV-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 101000845012 Macrovipera lebetina Disintegrin lebein-1-alpha Proteins 0.000 description 1
- 101000845007 Macrovipera lebetina Disintegrin lebein-1-beta Proteins 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- ZZNMWGVMOBOREI-VQTJNVASSA-N chembl464952 Chemical compound C1([C@H]2OC=3C4=C(C=5C=CC(C)(C)OC=5C=3C(=O)[C@@H]2O)OC(C=C4)(C)C)=CC=CC=C1 ZZNMWGVMOBOREI-VQTJNVASSA-N 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Developing Agents For Electrophotography (AREA)
- Compounds Of Iron (AREA)
Description
本発明に係る鉄系黒色粒子粉末が黒色度に優れるのは、マグネタイト懸濁溶液にTi溶液を添加する際にpHを制御し鉄の溶解を抑えることによって、加熱処理を行っても黒色度を阻害する不要な相が生成しないことによるものと本発明者は推定している。
◎:非常に良好(未発生)
○:良好(ほとんど発生せず)
△:実用可(軽微な発生が見られる)
×:実用不可
<鉄系黒色粒子粉末の製造>
球状マグネタイト粒子粉末(平均粒子径0.06μm、BET比表面積20.8m2/g)10kgを含有する水懸濁液に、硫酸チタニル36.3molを含有する水溶液(マグネタイト粒子粉末の全Feに対してTi換算で25原子%に相当する。)を添加する。尚、添加時に反応溶液のpH値を8.5以上に保持するように該混合液中にNaOHを添加した。次いで、混合溶液のpH値を8.0に調整してマグネタイト粒子の粒子表面にチタンの含水酸化物を沈着させた後、濾別、水洗、乾燥して粒子表面がチタンの含水酸化物で被覆されている球状黒色磁性酸化鉄粒子粉末を得た。
マグネタイトの種類、チタン化合物の添加量、加熱焼成処理の温度を種々変化させた以外は前記実施例1と同様にして鉄系黒色粒子粉末を得た。
粒状マグネタイト粒子粉末(平均粒子径0.2μm、磁化値85.0emu/g)100gをTiOSO4を0.26mol含有する水溶液中(Ti/Fe=20.0原子%に相当する。)に分散混合し、次いで、該混合液中にNaOHを添加して中和し、pH8において粒子表面にTiの水酸化物を沈着させた後、濾別、乾燥した。得られた粒子表面がTiの水酸化物で被覆されている粒状マグネタイト粒子粉末のTi(IV)量は、蛍光X線分析の結果、Fe(II)及びFe(III)に対し21.0原子%であった。
前記実施例1乃至3の粉砕処理時に各青色顔料を添加した以外は前記実施例1乃至5と同様にして非磁性黒色粒子粉末を得た。
<電子写真用トナーの製造>
実施例1で得た鉄系黒色粒子粉末を用いて、下記混合割合でヘンシェルミキサーにより混合した組成物を、二軸押し出し混練機(栗本鉄鋼社製 商品名:S−1)を用いて溶融混練し、混練物を冷却後、微粉砕した。これを体積平均粒子径8〜10μm(コールカウンター社製 商品名:Multisizerで測定)に分級し、さらに得られたトナー粉100重量部に対して、疎水性シリカ微粉末(日本アエロジル社製 商品名:RX−200)0.5重量部を外添処理し、電子写真用トナーを得た。
(ハイマーSB−308:三洋化成工業株式会社製)
鉄系黒色粒子粉末 25重量部、
負荷電制御剤 0.5重量部、
(BONTRON E−84:オリエント化学工業株式会社製)
低分子量ワックス 5重量部。
(ビスコール550−P:三洋化成工業株式会社製)
非磁性黒色粒子粉末の種類を種々変化させた以外は、前記実施例7と同様にして非磁性トナーを得た。
Claims (3)
- FeTiO3―Fe2O3固溶体又はFeTiO3―Fe2O3固溶体とスピネル型構造を有する鉄系酸化物との混合組成から成り、Ti含有量が全Feに対してTi換算で12.0〜40.0原子%であり、飽和磁化値が5Am2/kg未満であり、黒色度L*値が6〜13であることを特徴とする鉄系黒色粒子粉末。
- (1)FeTiO3−Fe2O3固溶体又はFeTiO3−Fe2O3固溶体とスピネル型構造を有する鉄系酸化物との混合組成物80〜99.9重量および(2)青色顔料0.1〜20重量から成り、Ti含有量が全Feに対してTi換算で12.0〜40.0原子%であり、飽和磁化値が5Am2/kg未満であり、黒色度L*値が6〜13である鉄系黒色粒子粉末。
- 請求項1又は請求項2記載の鉄系黒色粒子粉末を用いることを特徴とする黒色トナー。
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JP2004010864A JP4497285B2 (ja) | 2004-01-19 | 2004-01-19 | 鉄系黒色粒子粉末及び該鉄系黒色粒子粉末を含有する黒色トナー |
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JP2005200285A JP2005200285A (ja) | 2005-07-28 |
JP4497285B2 true JP4497285B2 (ja) | 2010-07-07 |
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EP1875313B1 (en) * | 2005-04-15 | 2013-06-19 | Canon Kabushiki Kaisha | Black toner |
US7833935B2 (en) * | 2006-11-08 | 2010-11-16 | Rockwood Italia S.P.A. | Iron oxide containing precipitated crystalline titanium dioxide and process for the manufacture thereof |
CN112492869B (zh) * | 2020-12-15 | 2023-06-23 | 合肥工业大学 | 一种普鲁士蓝氧化还原衍生的铁基吸波材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH032276A (ja) * | 1989-05-30 | 1991-01-08 | Toda Kogyo Corp | 黒色顔料粒子粉末 |
JPH0834617A (ja) * | 1994-07-22 | 1996-02-06 | Toda Kogyo Corp | 黒色磁性酸化鉄粒子粉末 |
JP2005170688A (ja) * | 2003-12-05 | 2005-06-30 | Mitsui Mining & Smelting Co Ltd | 黒色複合酸化鉄粒子 |
-
2004
- 2004-01-19 JP JP2004010864A patent/JP4497285B2/ja not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH032276A (ja) * | 1989-05-30 | 1991-01-08 | Toda Kogyo Corp | 黒色顔料粒子粉末 |
JPH0834617A (ja) * | 1994-07-22 | 1996-02-06 | Toda Kogyo Corp | 黒色磁性酸化鉄粒子粉末 |
JP2005170688A (ja) * | 2003-12-05 | 2005-06-30 | Mitsui Mining & Smelting Co Ltd | 黒色複合酸化鉄粒子 |
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