JP3532417B2 - Method for producing multilayer film-coated powder - Google Patents
Method for producing multilayer film-coated powderInfo
- Publication number
- JP3532417B2 JP3532417B2 JP20818498A JP20818498A JP3532417B2 JP 3532417 B2 JP3532417 B2 JP 3532417B2 JP 20818498 A JP20818498 A JP 20818498A JP 20818498 A JP20818498 A JP 20818498A JP 3532417 B2 JP3532417 B2 JP 3532417B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- metal
- powder
- coated
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 title claims description 117
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 91
- 239000002184 metal Substances 0.000 claims description 91
- 238000000034 method Methods 0.000 claims description 47
- 229910044991 metal oxide Inorganic materials 0.000 claims description 44
- 150000004706 metal oxides Chemical class 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 230000009467 reduction Effects 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- 239000002923 metal particle Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 12
- 150000004692 metal hydroxides Chemical class 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000011817 metal compound particle Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000007888 film coating Substances 0.000 claims description 6
- 238000009501 film coating Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 223
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 84
- 239000002245 particle Substances 0.000 description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 62
- 239000010410 layer Substances 0.000 description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 41
- 239000000377 silicon dioxide Substances 0.000 description 41
- 239000002585 base Substances 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 31
- 239000002994 raw material Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 239000007853 buffer solution Substances 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000005291 magnetic effect Effects 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 150000004703 alkoxides Chemical class 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 230000003064 anti-oxidating effect Effects 0.000 description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- -1 iron carbonate Chemical compound 0.000 description 9
- 235000019353 potassium silicate Nutrition 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000010908 decantation Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000006247 magnetic powder Substances 0.000 description 7
- 230000005415 magnetization Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000007790 solid phase Substances 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
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 229910001337 iron nitride Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Description
【０００１】[0001]
【発明の属する技術分野】本発明は基体粒子の表面を別
の物質で多層に被覆し、複合機能を発揮する多層膜被覆
粉体の製造方法に関するものであり、詳しくは、原料と
して危険性があり、かつ高価な金属粉、金属アルコキシ
ド、有機溶媒等を用いず、操作性が簡易で低コストの水
系成膜によって得られる多層膜被覆粉体の製造方法に関
するものである。The present invention relates to the coated multilayer surface of substrate particles in a different material, and a method of manufacturing a multilayer-coated powder that exhibits multiple functions, specifically, the risk as a raw material There, and expensive metal powder, a metal alkoxide without using an organic solvent or the like, operability to a method for manufacturing a multilayer-coated powder obtained by the low cost of water formed by simple.
【０００２】[0002]
【従来の技術】粉体の表面を他の物質の膜で被覆するこ
とにより、その粉体の性質を改善したり、その性質に多
様性を与えることが知られ、従来そのための方法として
種々の手段が提案されている。例えば、物体の表面に保
護や装飾のために膜を形成する被覆技術には、塗着法、
沈着法、スパッタリング、真空蒸着法、電着法や陽極酸
化法等多くの手段が知られている。しかし、塗着法や沈
着法では膜の厚みを均一にすることが困難であり、スパ
ッタリングや真空蒸着法では膜厚の厚い被膜を得ること
が困難である。また、電着法や陽極酸化法は被処理物を
電極とする関係上粉体の処理には向かないという問題点
を有している。種々の技術分野における進歩に伴い、特
異な性質を備えた粉体、特に金属粉体或は金属化合物粉
体を求める要望が増しており、粉体、特に金属粉体また
は金属化合物粉体だけが備える性質の他に別の性質を合
わせ持ち、複合した機能を有する粉体が求められてい
る。これらの粉体を製造するには、基体粒子の上に均一
な厚さの金属酸化物膜等を複数層設けることが考えられ
た。2. Description of the Related Art It is known that by coating the surface of a powder with a film of another substance, the properties of the powder can be improved or the properties can be diversified. Means have been proposed. For example, a coating technique for forming a film on the surface of an object for protection or decoration includes a coating method,
Many means are known such as a deposition method, a sputtering method, a vacuum vapor deposition method, an electrodeposition method and an anodic oxidation method. However, it is difficult to make the film thickness uniform by the coating method or the deposition method, and it is difficult to obtain a thick film by the sputtering or vacuum deposition method. Further, the electrodeposition method and the anodic oxidation method have a problem that they are not suitable for the treatment of powder because of the use of the object to be treated as an electrode. With the progress in various technical fields, there is an increasing demand for powders having unique properties, particularly metal powders or metal compound powders, and only powders, particularly metal powders or metal compound powders, are required. There is a demand for a powder having not only the properties provided but also other properties and having a composite function. In order to produce these powders, it was considered to provide a plurality of metal oxide films having a uniform thickness on the base particles.
【０００３】上記のような新しい要求に応えられる複合
した性質を有し、複合した機能を果たし得る粉体、特に
金属または金属化合物粉体を提供するための金属酸化物
の形成方法の有用なものとして、先に、本発明者らは、
金属粉体又は金属酸化物粉体を金属アルコキシド溶液中
に分散し、該金属アルコキシドを加水分解することによ
り、金属酸化物の皮膜を形成し、金属または金属化合物
の基体の表面に、均一な０．０１〜２０μｍの厚みの、
前記基体を構成する金属とは異種の金属を成分とする金
属酸化物膜を有する粉体を発明した（特開平６ー２２８
６０４号公報）。[0003] A useful method of forming a metal oxide for providing a powder having complex properties capable of fulfilling the above-mentioned new requirements and capable of fulfilling a complex function, particularly a metal or metal compound powder. As mentioned above, the present inventors
A metal powder or a metal oxide powder is dispersed in a metal alkoxide solution, and the metal alkoxide is hydrolyzed to form a metal oxide film. With a thickness of 0.01 to 20 μm,
Invented a powder having a metal oxide film containing a metal different from the metal constituting the substrate (Japanese Patent Laid-Open No. 6-228).
No. 604).
【０００４】この粉体において、前記の金属酸化物膜を
複数層設ける場合には、前記膜の各層の厚さを調整する
ことにより特別の機能を与えることができるものであっ
て、例えば、基体の表面に、屈折率の異なる被覆膜を、
光の４分の１波長に相当する厚さで設けるようにする
と、光はすべて反射される。この手段を鉄、コバルト、
ニッケルなどの金属粉末或は金属の合金粉末、或いは窒
化鉄の粉末などの磁性体を基体とするものに適用する
と、光を全反射して白色に輝く磁性トナー用磁性粉体を
得ることができる。さらに、その粉体の上に着色層を設
け、その上に樹脂層を設ければ、カラー磁性トナーが得
られることを開示している（特開平７ー９０３１０号公
報）。When a plurality of layers of the above metal oxide film are provided in this powder, a special function can be given by adjusting the thickness of each layer of the film. Coating film with different refractive index on the surface of
If it is provided with a thickness corresponding to a quarter wavelength of light, all the light will be reflected. This means iron, cobalt,
When it is applied to a base material of a magnetic substance such as a metal powder of nickel or the like, an alloy powder of the metal, or an iron nitride powder, it is possible to obtain a magnetic powder for a magnetic toner that totally reflects light and shines white. . Further, it is disclosed that a color magnetic toner can be obtained by providing a colored layer on the powder and a resin layer on the colored layer (JP-A-7-90310).
【０００５】更に、本発明者らは多層膜の物質の組み合
わせおよび膜厚を制御することにより、多層膜の反射光
干渉波形を調製できることを見出し、染料や顔料を用い
ずとも、長期保存においても安定な色調を有する多層膜
被覆粉体を提供することを開示した（ＷＯ９６／２８２
６９）。Furthermore, the present inventors have found that the reflected light interference waveform of the multilayer film can be adjusted by controlling the combination of the materials of the multilayer film and the film thickness, and even in the case of long-term storage without using dyes or pigments. It has been disclosed to provide a multilayer film-coated powder having a stable color tone (WO96 / 282).
69).
【０００６】前記したように、本発明者らは金属粉体又
は金属化合物粉体の表面に金属酸化物や金属の被膜を形
成して、基体になる金属又は金属化合物粉体が備えてい
る性質の他に別の性質を付与して機能性の高い金属又は
金属化合物粉体を開発することに努めてきた。なお、前
記金属粉体又は金属化合物粉体の表面に金属酸化物の被
膜を形成するためには、前記の通り金属アルコキシドの
加水分解による製膜方法が用いられていた。しかしなが
ら、この金属アルコキシドの加水分解による方法は、溶
媒として、引火性の高い有機系のもの（アルコール等）
を使用し、また原料として、高価な化合物である金属ア
ルコキシドを使用するためコスト高となる。更に引火性
の高い有機溶媒を用いるためには、製造装置を防爆設備
としたり、温度、湿度の管理が厳しく、それを用いて製
造した製品の価格も総合的に当然高価なものとなる問題
がある。As described above, the inventors of the present invention form a metal oxide or a metal coating film on the surface of the metal powder or the metal compound powder, and have the property that the metal or metal compound powder to be the base has. In addition to the above, it has been endeavored to develop a highly functional metal or metal compound powder by imparting another property. In order to form a metal oxide film on the surface of the metal powder or the metal compound powder, the film forming method by hydrolysis of the metal alkoxide has been used as described above. However, the method by hydrolysis of this metal alkoxide is a highly flammable organic-based solvent (alcohol, etc.)
In addition, since metal alkoxide, which is an expensive compound, is used as a raw material, the cost becomes high. Furthermore, in order to use highly flammable organic solvents, the manufacturing equipment must be explosion-proof equipment and the temperature and humidity must be controlled strictly, and the price of products manufactured using them is naturally expensive overall. is there.
【０００７】他方、上記の問題の解決法として、コスト
的に有利である水溶液中で被膜を形成する、金属塩水溶
液からの沈殿で被膜を形成する方法がある。しかし、こ
の方法では、基体粒子となる粉体粒子が特に金属の場
合、それらの反応剤や副生物である酸やアルカリに侵さ
れるために溶けてしまうという欠点がある。そこで本発
明者らは、極めて緻密で、不活性で、耐久性の面からも
好ましい金属酸化物膜を基体粒子上に、前記の金属アル
コキシドの加水分解法により製膜し、その層の上に、水
溶液中での金属塩の反応により金属水酸化物膜あるいは
金属酸化物膜を製膜する方法を開示した（特開平１０−
１７０２号公報）。基体粒子が金属アルコキシドの加水
分解法による金属酸化物膜で被覆されているものである
ならば、金属塩水溶液からの沈殿法を使用しても、その
沈殿法の反応条件が基体粒子を侵すことがない。しかし
ながら、この方法においても、金属アルコキシドの加水
分解による金属酸化物膜の製膜が必須であり、十分な低
コスト化が達成されていない。On the other hand, as a solution to the above problem, there is a method of forming a film in an aqueous solution, which is advantageous in terms of cost, and forming a film by precipitation from an aqueous solution of a metal salt. However, this method has a drawback that when the powder particles serving as the base particles are particularly metals, they are dissolved by being attacked by their reactants or by-products such as acids and alkalis. Therefore, the present inventors formed a metal oxide film, which is extremely dense, inert, and preferable from the viewpoint of durability, on the substrate particles by the above-mentioned metal alkoxide hydrolysis method, and then formed on the layer. Have disclosed a method for forming a metal hydroxide film or a metal oxide film by reacting a metal salt in an aqueous solution (JP-A-10-
1702). If the substrate particles are coated with a metal oxide film by a metal alkoxide hydrolysis method, even if the precipitation method from an aqueous solution of a metal salt is used, the reaction conditions of the precipitation method can attack the substrate particles. There is no. However, even in this method, it is essential to form a metal oxide film by hydrolysis of a metal alkoxide, and sufficient cost reduction has not been achieved.
【０００８】本発明者らは、上記の欠点を解決するため
種々検討し、基体粒子が金属の場合でも、製膜反応溶媒
として、緩衡溶液を用い、ｐＨ一定条件の水系溶媒を用
いることにより、液相中に固相のみを析出させることな
く、かつ粒子の凝集を抑制しながら、基体粒子表面に固
相膜を均一に製膜することを見出し、その膜被覆粉体お
よびその製造方法を開示した（特願平９−２９８７１７
号）。上記のように、ｐＨ一定条件の水系溶媒を用いる
ならば、基体粒子が金属の場合でも、金属塩水溶液から
の沈殿法の反応条件が基体粒子を侵すことがないことが
判明した。The inventors of the present invention have conducted various studies to solve the above-mentioned drawbacks. Even when the substrate particles are metal, by using a buffer solution as the film-forming reaction solvent and an aqueous solvent having a constant pH condition, It has been found that a solid phase film can be uniformly formed on the surface of a substrate particle while suppressing the aggregation of particles without precipitating only the solid phase in the liquid phase. Disclosed (Japanese Patent Application No. 9-298717)
issue). As described above, if an aqueous solvent having a constant pH is used, it was found that the reaction conditions of the precipitation method from an aqueous solution of a metal salt do not attack the base particles even when the base particles are metal.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、上記の
方法においては金属基体の原料として金属粉を用いる点
が、更なる改良が望まれる問題として、指摘されてい
る。金属粉は大気中で劣化・反応し易く、その中でも、
特に鉄粉などは発火性を有し、消防法では危険物第２類
可燃性固体に分類され、取扱が困難であり、また高価で
あり、この点から解決が望まれていた。従って、本発明
の目的は、上記従来技術の問題を解決し、多層膜被覆粉
体を製造する場合に、取扱いの容易な基体粒子原料を用
い、製膜法としては、低コスト化が達成できる水系溶媒
を用いる金属塩水溶液からの沈殿法を適用し、製造装置
も防爆設備を必要とせず、温度、湿度の管理も容易であ
り、総合的に製品の価格も安価に得られ、かつ基体粒子
として金属粒子を用いた場合と同様に機能性の高い、多
層膜被覆粉体の製造方法を提供することにある。However, it has been pointed out that the use of metal powder as the raw material of the metal substrate in the above method is a problem that requires further improvement. Metal powder easily deteriorates and reacts in the atmosphere.
In particular, iron powder and the like have ignitability, are classified as Class 2 combustible solids by the Fire Service Law, are difficult to handle, and are expensive. From this point, a solution is desired. Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art, and when manufacturing a multilayer film-coated powder, use a substrate particle raw material that is easy to handle, and achieve cost reduction as a film-forming method. Applying the precipitation method from aqueous metal salt solution using aqueous solvent, manufacturing equipment does not need explosion-proof equipment, temperature and humidity can be easily controlled, and the product price can be obtained at a low cost. Another object of the present invention is to provide a method for producing a multi-layered film-coated powder, which has high functionality as in the case of using metal particles.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、基体粒子
の原料として、金属化合物粒子を用い、その表面上に金
属塩水溶液からの沈殿法で酸化物膜を形成し、この酸化
物膜を被覆した粉体を還元すると、該基体粒子は還元に
より金属粒子となり、酸化物膜は酸化防止膜となること
を見出した。また、金属の基体粒子がこの酸化防止膜に
より被覆されているものであるならば、金属塩水溶液か
らの沈殿法を使用しても、金属基体粒子が侵されること
がないことを見出した。本発明者らはこれらの見出した
知見に基づいて本発明に到達した。The present inventors have used metal compound particles as a raw material for base particles, and formed an oxide film on the surface thereof by a precipitation method from an aqueous solution of a metal salt. It was found that when the powder coated with is reduced, the base particles become metal particles by the reduction, and the oxide film becomes an antioxidant film. It was also found that if the metal base particles are covered with this antioxidant film, the metal base particles will not be attacked even if the precipitation method from an aqueous metal salt solution is used. The present inventors have arrived at the present invention based on these findings.
【００１１】すなわち、本発明の多層膜被覆粉体の製造
方法は下記の構成である。 That is, the method for producing a multilayer film-coated powder of the present invention has the following constitution .
【００１２】[0012]
【００１３】（１） 金属基体の表面に多層の金属酸化
物膜または金属水酸化物膜を有する粉体の製造方法にお
いて、金属化合物粒子の表面上に酸化物膜を形成し、こ
の酸化物膜を形成した金属化合物粒子を還元して酸化防
止膜被覆金属粒子とし、該酸化防止膜被覆金属粒子の表
面に、水溶液中での金属塩の反応により、厚さが１０ｎ
ｍ〜１０μｍの金属水酸化物膜または金属酸化物膜を形
成し、干渉色により着色することを特徴とする多層膜被
覆粉体の製造方法。
（２） 前記酸化防止膜の厚さが１ｎｍ〜２００μｍで
あることを特徴とする前記（１）に記載の多層膜被覆粉
体の製造方法。
（３） 前記還元が、水素雰囲気下で行われることを特
徴とする前記（１）に記載の多層膜被覆粉体の製造方
法。( 1 ) In a method for producing a powder having a multilayer metal oxide film or metal hydroxide film on the surface of a metal substrate, an oxide film is formed on the surface of metal compound particles, and the oxide film is formed. The metal compound particles formed with are reduced to form anti-oxidation film-coated metal particles, and the surface of the anti-oxidation film-coated metal particles has a thickness of 10 n due to the reaction of a metal salt in an aqueous solution.
A method for producing a multilayer film-coated powder , which comprises forming a metal hydroxide film or a metal oxide film having a thickness of m to 10 μm and coloring the film with an interference color . ( 2 ) The method for producing a multilayer film-coated powder according to ( 1 ), wherein the thickness of the antioxidant film is 1 nm to 200 μm. ( 3 ) The method for producing a multilayer film-coated powder according to ( 1 ), wherein the reduction is performed in a hydrogen atmosphere.
【００１４】（４） 前記還元の温度が３５０〜１１０
０℃であることを特徴とする前記（１）に記載の多層膜
被覆粉体の製造方法。
（５） 前記還元の時間が３０分〜１０時間であること
を特徴とする前記（１）に記載の多層膜被覆粉体の製造
方法。
（６） 前記水溶液中での金属塩の反応により形成され
た金属水酸化物膜または金属酸化物膜が、その形成後に
加熱処理してなる被覆膜であることを特徴とする前記
（１）に記載の多層膜被覆粉体の製造方法。 ( 4 ) The reduction temperature is 350 to 110.
It is 0 degreeC, The manufacturing method of the multilayer film coating powder as described in said ( 1 ) characterized by the above-mentioned. ( 5 ) The method for producing a multilayer film-coated powder according to ( 1 ), wherein the reduction time is 30 minutes to 10 hours. ( 6 ) The metal hydroxide film or the metal oxide film formed by the reaction of the metal salt in the aqueous solution is a coating film formed by heat treatment after the formation ( 1 ) The method for producing a multilayer film-coated powder according to item 1 .
【００１５】本発明は上記のように、基体粒子の原料と
して劣化・反応し易く危険物である金属粉を用いずに、
取扱いの容易な金属化合物粉を用い、製膜法としては、
低コスト化が達成できる水系溶媒および水溶性原料を用
いる金属塩水溶液からの沈殿法を用いて、厚さが均一
で、所望の膜厚を有する多層膜被覆粉体を容易に製造す
ることを可能とすることができた。As described above, the present invention does not use a metal powder, which is a dangerous substance, which easily deteriorates and reacts as a raw material of the base particles,
Using a metal compound powder that is easy to handle, as a film forming method,
It is possible to easily produce a multi-layer film-coated powder having a uniform thickness and a desired film thickness by using a precipitation method from an aqueous solution of a metal salt using an aqueous solvent and a water-soluble raw material that can achieve cost reduction. I was able to
【００１６】[0016]
【発明の実施の形態】本発明において、前記本発明の多
層膜被覆粉体を製造する場合の基体の原料としては、
鉄、コバルト、ニッケル、クロム、チタン、アルミニウ
ム、サマリウム等の金属、またはこれらの合金の化合物
からなる粉体が使用できる。前記化合物としては、金属
酸化物、例えば鉄、コバルト、ニッケル、クロム、チタ
ン、アルミニウム、ケイ素（この場合ケイ素は金属に分
類するものとする）、サマリウム等の酸化物の他、カル
シウム、マグネシウム、バリウム等のアルカリ土類金属
酸化物あるいはこれらの複合酸化物、複合化合物等が挙
げられる。本発明においては、その目的の一つがカラー
磁性トナーやカラー磁性インクのような磁性を有する粉
体を製造することにあるので、その場合本発明の多層膜
被覆粉体の基体としては強磁性体を使用することが好ま
しい。従って、金属鉄を基体とする場合の原料として
は、四三酸化鉄、二三酸化鉄等の鉄酸化物や水酸化鉄、
炭酸鉄、炭化鉄、窒化鉄などの鉄化合物、コバルトを基
体とする場合の原料としては、酸化コバルト、炭酸コバ
ルト、水酸化コバルト等のコバルトの化合物が好まし
い。電気分極、導電性などの電気特性を有する金属を基
体とする場合の原料としては、酸化銀、硝酸銀、塩化
銀、酸化銅、炭酸銅、酸化亜鉛、酸化鉛あるいは前記金
属化合物の複合化合物が好ましい。粉体の電気分極、導
電性などの電気特性を考慮すると、銀、銅、金、アルミ
ニウムやそれらの合金の化合物が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as a raw material of a substrate in the case of producing the multilayer film-coated powder of the present invention,
Powders made of metals such as iron, cobalt, nickel, chromium, titanium, aluminum, samarium, or compounds of these alloys can be used. Examples of the compound include metal oxides such as iron, cobalt, nickel, chromium, titanium, aluminum, silicon (in this case, silicon is classified as a metal), samarium, and calcium, magnesium, barium. Examples thereof include alkaline earth metal oxides and the like, or complex oxides and complex compounds thereof. In the present invention, one of the purposes is to produce a magnetic powder such as a color magnetic toner or a color magnetic ink. In that case, a ferromagnetic material is used as the substrate of the multilayer film-coated powder of the present invention. Is preferably used. Therefore, as a raw material in the case of using metallic iron as a base, iron oxides such as ferric tetroxide and ferric oxide or iron hydroxide,
Iron compounds such as iron carbonate, iron carbide, and iron nitride, and a raw material when cobalt is used as a base material are preferably cobalt compounds such as cobalt oxide, cobalt carbonate, and cobalt hydroxide. As a raw material when a metal having electric characteristics such as electric polarization and conductivity is used as a base material, silver oxide, silver nitrate, silver chloride, copper oxide, copper carbonate, zinc oxide, lead oxide or a complex compound of the above metal compounds is preferable. . Considering the electric properties of the powder such as electric polarization and conductivity, silver, copper, gold, aluminum and compounds of their alloys are preferable.
【００１７】本発明の多層膜被覆粉体において、酸化防
止膜とは、前記多層膜被覆粉体の基体である金属成分の
酸化を長期にまたは半永久的に防止するものである。酸
化防止膜の物質としては、前記多層膜被覆粉体の金属成
分の酸化を長期にまたは半永久的に防止するものであれ
ば特に限定されないが、緻密な酸化物等が挙げられ、強
度、成膜性等の点から金属酸化物が好ましい。前記酸化
防止膜に適用される金属酸化物としては、ケイ素、チタ
ン、アルミニウム、ジルコニウム、錫、鉄、マンガン、
ニッケル、クロム、亜鉛、カドミウム、鉛、リチウム、
インジウム、ネオジウム、ビスマス、セリウム、アンチ
モン、カルシウム、マグネシウム、バリウム等の金属の
酸化物が挙げられる。In the multi-layer film-coated powder of the present invention, the anti-oxidation film is for preventing the metal component, which is the base of the multi-layer film-coated powder, from being oxidized for a long term or semi-permanently. The material of the antioxidant film is not particularly limited as long as it can prevent the metal component of the multilayer film-coated powder from being oxidized for a long period of time or semi-permanently. A metal oxide is preferable in terms of properties and the like. As the metal oxide applied to the antioxidant film, silicon, titanium, aluminum, zirconium, tin, iron, manganese,
Nickel, chromium, zinc, cadmium, lead, lithium,
Examples thereof include oxides of metals such as indium, neodymium, bismuth, cerium, antimony, calcium, magnesium and barium.
【００１８】本発明の多層膜被覆粉体を製造する場合の
中間体である酸化防止膜被覆金属粒子、即ち、酸化防止
膜で被覆された金属基体粒子を製造するには、金属基体
粒子の原料となる金属化合物粒子の表面に酸化物膜を形
成し、この酸化物膜を形成した金属化合物粒子を還元す
る方法が採られる。この方法について、以下に詳細に説
明する。金属基体粒子の原料となる金属化合物粒子（以
下、単に基体原料粒子ともいう）とは、還元により金属
の単体または合金になるものである。この基体原料粒子
の具体例としては、前記の通りであるが、特にマグネタ
イトやＣｏフェライト、Ｎｉフェライトに代表されるフ
ェライト粒子および複合金属フェライト粒子を挙げるこ
とができる。これら基体原料粒子は、公知の共沈法や金
属イオンの還元法、ＣＶＤ法等により作成可能である。
特に、フェライト粒子の場合には共沈法で作成すること
により、粒径数ｎｍ〜数十ｎｍ程度の粒径の揃った微粒
子を得ることができる。In order to produce an antioxidant film-coated metal particle which is an intermediate for producing the multilayer film-coated powder of the present invention, that is, a metal substrate particle coated with an antioxidant film, a raw material for the metal substrate particle is used. A method is employed in which an oxide film is formed on the surface of the metal compound particles to be formed, and the metal compound particles having the oxide film formed thereon are reduced. This method will be described in detail below. The metal compound particles (hereinafter, also simply referred to as base material particles), which is a raw material of the metal base particles, is a metal simple substance or alloy by reduction. Specific examples of the base material particles are as described above, but in particular, ferrite particles represented by magnetite, Co ferrite, Ni ferrite and composite metal ferrite particles can be mentioned. These base material particles can be prepared by a known coprecipitation method, a metal ion reduction method, a CVD method, or the like.
In particular, in the case of ferrite particles, fine particles having a uniform particle diameter of several nm to several tens of nm can be obtained by preparing them by the coprecipitation method.
【００１９】前記基体原料粒子の表面に酸化物膜を形成
するには、水溶液中で金属塩類を中和、加水分解する方
法などがある。この方法としては、金属塩の反応のう
ち、最も一般的である金属塩水溶液の反応による沈殿処
理がある。この処理に用いられる金属塩についていう
と、金属の酸性塩の場合が特に問題となる。金属塩の反
応においては、中和や熱分解が代表的に用いられるが、
それ以外の反応でもよい。本発明において、金属塩とし
て使用される金属は、鉄、ニッケル、クロム、チタン、
亜鉛、アルミニウム、カドミウム、ジルコニウム、ケイ
素、錫、鉛、マンガン、リチウム、インジウム、ネオジ
ウム、ビスマス、セリウム、アンチモン等の他、カルシ
ウム、マグネシウム、バリウム等が挙げられる。To form an oxide film on the surface of the base material particles, there is a method of neutralizing and hydrolyzing metal salts in an aqueous solution. As this method, there is a precipitation treatment by a reaction of an aqueous metal salt solution, which is the most general reaction among the reactions of metal salts. Regarding the metal salt used in this treatment, the case of an acid salt of a metal is particularly problematic. In the reaction of the metal salt, neutralization and thermal decomposition are typically used,
Other reactions may be used. In the present invention, the metal used as the metal salt is iron, nickel, chromium, titanium,
Other than zinc, aluminum, cadmium, zirconium, silicon, tin, lead, manganese, lithium, indium, neodymium, bismuth, cerium, antimony, calcium, magnesium, barium and the like can be mentioned.
【００２０】また、これら金属の塩としては、硫酸、硝
酸、塩酸、シュウ酸、炭酸やカルボン酸の塩が挙げられ
る。さらにまた、前記金属のキレート錯体も含まれる。
本発明において使用される金属塩の種類は、その粉体の
表面に付与しようとする性質や製造に際して適用する手
段に応じてそれに適するものが選択される。酸化物膜は
基体の還元された金属と容易に反応しない組合わせがよ
い。特に多層干渉膜の場合には基体粒子と反応により光
学特性が変化しないものが好ましい。例えば、鉄の基体
に対しては、珪素、アルミニウム、亜鉛、鉛等の金属酸
化物が、反応し形成される物質の反応温度が高いため好
ましい。従って、後記の熱処理温度である、３５０〜１
１００℃、好ましくは４００〜９００℃、より好ましく
は４５０〜８００℃で反応生成物が形成されないことが
必要である。Examples of salts of these metals include salts of sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid and carboxylic acids. Furthermore, chelate complexes of the above metals are also included.
The kind of the metal salt used in the present invention is selected in accordance with the properties to be imparted to the surface of the powder and the means applied in the production. The oxide film preferably has a combination that does not easily react with the reduced metal of the substrate. Particularly, in the case of a multilayer interference film, it is preferable that the optical characteristics do not change due to the reaction with the base particles. For example, for iron substrates, metal oxides such as silicon, aluminum, zinc, and lead are preferable because the reaction temperature of the substance formed by the reaction is high. Therefore, the heat treatment temperature, which will be described later, is 350 to 1
It is necessary that no reaction product is formed at 100 ° C, preferably 400-900 ° C, more preferably 450-800 ° C.
【００２１】上記のごとく処理することにより、基体原
料粒子の表面に酸化物膜を形成した粉体粒子が得られ
る。そして、以上のようにして得られた酸化物膜被覆基
体原料粒子を含む溶液を静置して液相と固相とに相分離
させ、液相中に浮遊する超微粒子のみを採取する。ここ
で、遠心分離器を用いて超微粒子のみを採取することも
できる。この超微粒子は平均粒径１０ｎｍ程度であり、
再分散の際に、沈降することなく優れた分散性が得られ
る。By the above treatment, powder particles having an oxide film formed on the surface of the base material particles can be obtained. Then, the solution containing the oxide film-coated substrate raw material particles obtained as described above is allowed to stand to cause phase separation into a liquid phase and a solid phase, and only ultrafine particles floating in the liquid phase are collected. Here, it is also possible to collect only ultrafine particles using a centrifuge. The ultrafine particles have an average particle size of about 10 nm,
Upon re-dispersion, excellent dispersibility can be obtained without sedimentation.
【００２２】この酸化物膜を被覆した基体原料粒子を還
元し、基体を金属化して磁性を強くし、酸化物膜を完全
な酸化防止膜とした磁性金属粒子を得ることができる。
前記還元は、還元雰囲気として、水素、一酸化炭素など
用いられるが、水素が最も膜透過性に適しており、水素
ガス雰囲気に保った炉の中で、温度範囲３５０〜１１０
０℃、好ましくは４００〜９００℃、より好ましくは４
５０〜８００℃で焼成を行う。３５０℃未満では還元が
不十分であり、１１００℃を超えた温度では粒子同志が
焼結することがあり、共に不適である。この炉中での還
元時間は膜の厚さにより変わるが、３０分〜１０時間、
好ましくは１〜７時間、より好ましくは２〜５時間であ
る。３０分未満では還元が不十分であり、１０時間を超
えると熱量、還元ガスを必要以上に消費し不経済であ
り、また粒子同志が焼結することがあり、共に不適であ
る。It is possible to obtain magnetic metal particles having the oxide film as a complete anti-oxidation film by reducing the base material particles coated with the oxide film and metallizing the base to strengthen the magnetism.
In the reduction, hydrogen, carbon monoxide, or the like is used as a reducing atmosphere, but hydrogen is most suitable for the membrane permeability, and the temperature range of 350 to 110 is set in the furnace kept in the hydrogen gas atmosphere.
0 ° C, preferably 400 to 900 ° C, more preferably 4
Baking is performed at 50 to 800 ° C. If the temperature is lower than 350 ° C, the reduction is insufficient, and if the temperature is higher than 1100 ° C, the particles may sinter, which is not suitable. The reduction time in this furnace varies depending on the thickness of the film, but 30 minutes to 10 hours,
It is preferably 1 to 7 hours, more preferably 2 to 5 hours. If the time is less than 30 minutes, the reduction is insufficient, and if the time exceeds 10 hours, the calorific value and the reducing gas are consumed more than necessary, which is uneconomical, and the particles may sinter.
【００２３】本発明では、前記還元・焼成処理により、
基体原料粒子が金属に還元されると同時に、高温による
前記酸化物膜の固化と前記金属基体粒子の表面の溶融化
が同時に進行し、酸化物膜と金属基体粒子の界面におい
て結合が生じ、この結果、酸化物膜が完全な酸化防止膜
になるものと思われる。また、前記還元・焼成処理の
際、酸化防止膜は還元処理中の焼結防止膜としても働
く。In the present invention, by the reduction / calcination treatment,
At the same time when the base material particles are reduced to a metal, solidification of the oxide film due to high temperature and melting of the surface of the metal base particles proceed at the same time, and bonding occurs at the interface between the oxide film and the metal base particles. As a result, it seems that the oxide film becomes a perfect antioxidant film. Further, during the reduction / firing process, the antioxidant film also functions as a sintering preventive film during the reduction process.
【００２４】上記の還元・焼成処理条件は、それ自体公
知の方法であるが、主に磁気記録媒体用として好適に使
用することができる磁気特性の優れたマグネタイト、マ
グヘマイト、金属鉄などの針状の磁性粉末（長軸：０．
１〜０．３μｍ）を得るための処理として用いられてき
た（例えば、特開昭５９−２１３６２６号公報、特開昭
５８−１６１７０９号公報）。しかし本発明において
は、基体原料粒子を還元して金属化し、磁性を強くした
酸化防止膜被覆金属粒子を得ることが目的であり、平均
粒径が、５〜２０ｎｍである超微粒子に適用し、優れた
結果を得ることができた。Although the above-mentioned reduction / calcination treatment conditions are known per se, they are needle-shaped such as magnetite, maghemite, metallic iron, etc., which can be suitably used mainly for magnetic recording media and have excellent magnetic properties. Magnetic powder (long axis: 0.
1 to 0.3 μm) (for example, JP-A-59-213626 and JP-A-58-161709). However, in the present invention, the purpose is to reduce the base material particles to metallize them to obtain anti-oxidation film-coated metal particles having strong magnetism, and to apply to ultrafine particles having an average particle size of 5 to 20 nm, Excellent results have been obtained.
【００２５】酸化防止膜で被覆された金属化合物粒子の
平均粒径の範囲は、５〜２０ｎｍであり、好ましくは６
〜１５ｎｍ、さらに好ましくは７〜１２ｎｍであり、８
〜１０ｎｍならば最適である。５ｎｍ未満では磁性が弱
くなり、２０ｎｍを超えて大きくなると、再分散の際、
液中で沈降が生じ、共に不適である。酸化防止膜で被覆
された金属粒子（還元後）の飽和磁化の数値範囲は、７
０〜２００ｅｍｕ／ｇであり、好ましくは１００〜２０
０ｅｍｕ／ｇである。The average particle size of the metal compound particles coated with the antioxidant film is 5 to 20 nm, preferably 6
-15 nm, more preferably 7-12 nm, 8
The optimum value is -10 nm. If it is less than 5 nm, the magnetism becomes weak, and if it exceeds 20 nm, it becomes large when re-dispersing.
Sedimentation occurs in the liquid, both of which are unsuitable. The numerical range of the saturation magnetization of the metal particles (after reduction) coated with the antioxidant film is 7
0 to 200 emu / g, preferably 100 to 20
It is 0 emu / g.
【００２６】また、酸化防止膜は干渉膜として利用でき
ることが多層膜干渉に必要であり、一回で干渉に十分な
厚さを得ることが理想である。しかし、あまり厚くなる
と水素等還元ガスによる還元効率が悪くなったり、製膜
に長時間を要する。このため、酸化防止膜の膜厚は、１
〜２００ｎｍ、好ましくは１〜１５０ｎｍ、より好まし
くは１〜５０ｎｍである。１ｎｍ未満では酸化防止膜と
ならず、２００ｎｍを超えて厚くなると干渉膜とならな
い。また、還元は還元ガスの酸化防止膜に対する透過・
拡散速度できまるため酸化防止膜が厚すぎると還元効率
が著しく悪くなり、基体粒子の中心部が還元されないの
で原料芯が残ることがある。なお、酸化防止膜としてシ
リカ膜を、金属粒子の金属成分として鉄を用いた場合に
は、ＳｉＯ2 とＦｅの重量割合（ＳｉＯ2 ／Ｆｅ）が
０．１〜２０ｗｔ％、好ましくは０．１〜１０ｗｔ％、
さらに好ましくは０．５〜７ｗｔ％である。酸化防止膜
または磁性金属粒子の金属成分として、それぞれ別のも
のを適用する場合には、適宜好ましい重量割合を設定す
ればよい。Further, it is necessary for the anti-oxidation film to be usable as an interference film for the multilayer film interference, and it is ideal to obtain a sufficient thickness for the interference at one time. However, if it is too thick, the reduction efficiency with a reducing gas such as hydrogen will be poor, and it will take a long time for film formation. Therefore, the thickness of the antioxidant film is 1
-200 nm, preferably 1-150 nm, more preferably 1-50 nm. If it is less than 1 nm, it does not become an antioxidant film, and if it exceeds 200 nm, it does not become an interference film. In addition, reduction is achieved by permeating the reducing gas through the anti-oxidation film.
If the antioxidant film is too thick due to the diffusion rate, the reduction efficiency will be remarkably deteriorated, and the center of the base particles will not be reduced, so that the raw material core may remain. When a silica film is used as the antioxidant film and iron is used as the metal component of the metal particles, the weight ratio of SiO 2 and Fe (SiO 2 / Fe) is 0.1 to 20 wt%, preferably 0.1. -10 wt%,
More preferably, it is 0.5 to 7 wt%. When different materials are applied as the antioxidant film or the metal component of the magnetic metal particles, a preferable weight ratio may be set appropriately.
【００２７】本発明においては、上記酸化防止膜被覆金
属粒子の酸化防止膜上に、前記酸化物膜の形成と同様
に、水溶液中での金属塩の反応により、金属水酸化物膜
あるいは金属酸化物膜を製膜する。この方法により、屈
折率が互いに異なる複数の被膜層を用い、各被膜層の屈
折率および層厚を適宜選択して被覆し、その干渉色によ
り着色された粉体とすることができる。前記したよう
に、酸化防止膜被覆金属粒子の表面上に水溶液中での金
属塩の反応により金属水酸化物膜あるいは金属酸化物膜
を析出させる。固相析出反応の溶媒として、水を用いる
が、好ましくは緩衡溶液を用い、ある一定のｐＨで適当
な速さで析出させることが好ましい。In the present invention, the metal hydroxide film or the metal oxide film is formed on the antioxidant film of the metal particles coated with the antioxidant film by the reaction of the metal salt in the aqueous solution, similarly to the formation of the oxide film. The material film is formed. By this method, it is possible to use a plurality of coating layers having different refractive indexes, select the coating layers by appropriately selecting the refractive index and the layer thickness, and obtain a powder colored by the interference color. As described above, the metal hydroxide film or the metal oxide film is deposited on the surface of the antioxidant-coated metal particles by the reaction of the metal salt in the aqueous solution. Water is used as the solvent for the solid phase precipitation reaction, but it is preferable to use a buffer solution and perform precipitation at a certain pH and at an appropriate rate.
【００２８】これらの水溶液中での金属塩の反応による
金属酸化物等の膜は、複数層形成してもよく、またそれ
らの金属酸化物等の膜の上に、必要により他の製膜方法
による金属酸化物等の膜を形成することもできる。この
ようにして、酸化防止膜被覆金属粒子は、その上に水溶
液中での金属塩の反応による金属酸化物等の膜を形成し
ても、その形成処理の際に粉体粒子に悪影響を与えない
ので、簡単な操作でかつ安価な原料である金属塩を用い
て金属酸化物等の膜を多層に形成することができる。し
かもその際、各層が所定の厚さをもつように形成条件を
設定することにより、目的とする特性を得ることができ
るようにすることができる。特に、高価な金属アルコキ
シドを原料として用いることなく、多層膜被覆粉体とす
ることができる点は重要な利点である。A film of a metal oxide or the like formed by the reaction of a metal salt in these aqueous solutions may be formed in a plurality of layers, and if necessary, another film forming method may be formed on the film of the metal oxide or the like. It is also possible to form a film of a metal oxide or the like. In this way, the anti-oxidation film-coated metal particles have an adverse effect on the powder particles during the formation process even when a film of metal oxide or the like is formed on the anti-oxidation film by the reaction of the metal salt in the aqueous solution. Since it does not exist, it is possible to form a multi-layered film of metal oxide or the like by using a metal salt which is an inexpensive raw material with a simple operation. Moreover, at this time, by setting the forming conditions so that each layer has a predetermined thickness, it is possible to obtain the desired characteristics. In particular, it is an important advantage that a multilayer film-coated powder can be obtained without using an expensive metal alkoxide as a raw material.
【００２９】本発明の多層膜被覆粉体を製造する方法で
は、多層被覆膜を連続した工程として製作しても良く、
また、各被覆膜を１層ずつ製膜、あるいは単層製膜と複
層連続製膜を組み合わせるなど種々の方法で製膜するこ
とができる。本発明に係わる多層膜被覆粉体の粒径は、
特に限定されず、目的に応じて適宜調整することができ
るが、通常は０．０１μｍ〜数ｍｍの範囲である。In the method for producing the multi-layer coating powder of the present invention, the multi-layer coating film may be manufactured as a continuous process,
Further, each coating film can be formed by various methods such as forming each layer one by one, or combining a single layer film formation and a multi-layer continuous film formation. The particle size of the multilayer film-coated powder according to the present invention is
It is not particularly limited and may be appropriately adjusted depending on the purpose, but is usually in the range of 0.01 μm to several mm.
【００３０】本発明において、その１回の製膜処理で形
成させる金属酸化物膜の膜の厚さとしては、５ｎｍ〜１
０μｍの範囲とすることが可能であり、従来の製膜法よ
り厚くすることができる。複数回に分けて製膜する金属
酸化物膜の合計の厚さとしては、カラー磁性粉体の場
合、その干渉による反射率が良い金属酸化物膜を形成す
るためには、１０ｎｍ〜１０μｍの範囲が好ましく、さ
らに好ましくは２０ｎｍ〜５μｍの範囲とすることであ
る。粒径が制限されるなど特に薄い膜厚で可視光を干渉
反射させるためには０．０２〜２．０μｍの範囲とする
ことが好ましい。金属酸化物膜の合計の厚さが１０ｎｍ
未満であれば干渉による反射が起こらなかったり、また
は小さく、１０μｍを超えて厚くなると完全反射とな
り、共に不適である。In the present invention, the thickness of the metal oxide film formed by the single film forming treatment is 5 nm to 1
The thickness can be in the range of 0 μm, and can be made thicker than the conventional film forming method. In the case of color magnetic powder, the total thickness of the metal oxide film formed in a plurality of times is in the range of 10 nm to 10 μm in order to form a metal oxide film having good reflectance due to interference. Is preferable, and more preferably in the range of 20 nm to 5 μm. In order to cause interference reflection of visible light with a particularly thin film thickness such as a limited particle size, the range is preferably 0.02 to 2.0 μm. The total thickness of the metal oxide film is 10 nm
If it is less than the above range, reflection due to interference does not occur, or if it is small and becomes thicker than 10 μm, perfect reflection occurs, and both are unsuitable.
【００３１】前記したようにして製造した酸化防止膜被
覆金属粒子の表面に金属酸化物膜等を有する粉体は、選
択した基体粒子の材質、及びその表面に被覆した膜の金
属酸化物の材質により、種々の性質を賦与することがで
きるので、それぞれの目的の用途に適用することができ
る。例えば、基体粒子として磁性体の金属鉄の原料であ
る、窒化鉄、四三酸化鉄などを用い、その上の膜として
前記磁性体に比べて屈折率のより低い酸化ケイ素（シリ
カともいう）を被覆し、その外膜としてより屈折率の高
い酸化チタン（チタニアともいう）の層を被覆すれば、
白色度の高い磁性粉が得られる。また、基体粒子として
銀、銅あるいはアルミニウム等の導体を用い、該金属層
の上に金属酸化物として例えば酸化アルミニウムのよう
な電気絶縁性の被覆膜を被覆すれば、電気絶縁性の表面
層を有する熱伝導性粉体が得られる。The powder having a metal oxide film or the like on the surface of the anti-oxidation film-coated metal particles produced as described above is the material of the selected base particles and the material of the metal oxide of the film coated on the surface. According to the above, various properties can be imparted, and therefore, they can be applied to their respective intended uses. For example, as the base particles, iron nitride, triiron tetraoxide, etc., which is a raw material of magnetic metallic iron, are used, and silicon oxide (also referred to as silica) having a lower refractive index than that of the magnetic material is used as a film thereon. If you coat it and coat a layer of titanium oxide (also called titania) with a higher refractive index as its outer film,
Magnetic powder with high whiteness can be obtained. If a conductor such as silver, copper or aluminum is used as the base particles and an electrically insulating coating film such as aluminum oxide is coated as the metal oxide on the metal layer, the electrically insulating surface layer is formed. A heat conductive powder having is obtained.
【００３２】また、例えば、酸化防止膜被覆金属粒子の
表面に、屈折率の異なる被覆を、膜の物質の屈折率と膜
の厚さとの積が電磁波の４分の１に相当するようにその
厚さを調製すると、干渉により光は大部分反射（フレネ
ル反射）される。この作用を利用し、例えば前記酸化防
止膜被覆金属粒子の表面に、銀あるいはコバルト等の高
い反射率の金属層を設け、さらにその外側に前記金属よ
り屈折率の低い酸化ケイ素のような酸化物層を酸化物の
屈折率と膜の厚さとの積が可視光の４分の１波長に相当
するように、厚さを調製して設け、さらにその上に物質
の屈折率と膜の厚さとの積が可視光の４分の１波長に相
当するようにその厚さを調整した酸化チタンのような屈
折率の高い酸化物層を被覆することにより、光を反射し
て、白色に輝いた磁性トナー用磁性粉体を製造すること
ができる。また、製造された粉体を不活性ガス雰囲気の
中で温度２００℃〜８００℃で熱処理することにより、
さらに強固で白色度の高い粉体とすることができる。上
記、粉体を熱処理する場合、熱処理された粉体の各層に
おいて膜構成物質の屈折率と膜の厚さとの積が可視光の
４分の１波長に相当するような膜の厚さになる条件が満
たされなければならない。Further, for example, a coating having a different refractive index is provided on the surface of the metal particles coated with an antioxidant film so that the product of the refractive index of the material of the film and the thickness of the film corresponds to a quarter of the electromagnetic wave. When the thickness is adjusted, light is mostly reflected (Fresnel reflection) due to interference. By utilizing this action, for example, a metal layer having a high reflectance such as silver or cobalt is provided on the surface of the metal particles coated with an antioxidant film, and an oxide such as silicon oxide having a refractive index lower than that of the metal is provided outside the metal layer. The layer is adjusted in thickness so that the product of the refractive index of the oxide and the thickness of the film corresponds to a quarter wavelength of visible light, and the refractive index of the substance and the thickness of the film are provided on the layer. By coating an oxide layer having a high refractive index such as titanium oxide, the thickness of which is adjusted so that the product of the two corresponds to a quarter wavelength of visible light, light is reflected and it shines white. A magnetic powder for magnetic toner can be manufactured. In addition, by heat-treating the produced powder in an inert gas atmosphere at a temperature of 200 ° C to 800 ° C,
Further, it is possible to obtain a powder that is strong and has high whiteness. When the powder is heat-treated, the thickness of the film is such that the product of the refractive index of the film-forming substance and the film thickness in each layer of the heat-treated powder corresponds to a quarter wavelength of visible light. The conditions must be met.
【００３３】さらにその粉体の上に着色層を設け、さら
にその上に樹脂層を設ければ、カラー磁性トナーを製造
することができる。なお、可視光の波長は幅があるの
で、磁性トナーを構成する粉体の各被覆膜層の厚さが、
各膜構成物質の屈折率と厚さとの積が可視光の４分の１
波長に相当する範囲で多少異なるようにしたものを、交
互に複数設けてもよい。多層膜被覆粉体を干渉反射で着
色するカラー粉体とする場合には、目的の分光波長の光
が反射されるように、高屈折率膜と低屈折率膜を交互に
フレネル干渉に必要な膜の厚みに製膜する。If a colored layer is further provided on the powder and a resin layer is further provided thereon, a color magnetic toner can be manufactured. Since the wavelength of visible light has a range, the thickness of each coating film layer of the powder that constitutes the magnetic toner is
The product of the refractive index and the thickness of each film constituent substance is 1/4 of visible light.
A plurality of elements that are slightly different in the range corresponding to the wavelength may be provided alternately. When the multi-layer coating powder is a color powder that is colored by interference reflection, high-refractive index films and low-refractive index films are required for Fresnel interference alternately so that light of the target spectral wavelength is reflected. Form the film to the thickness of the film.
【００３４】次に一例として、高屈折率の金属酸化物と
低屈折率の金属酸化物の交互多層膜を形成する方法につ
いて具体的に説明する。まず、酸化チタンあるいは酸化
ジルコニウムなどの被膜を形成する場合、酢酸／酢酸ナ
トリウム系等の緩衡溶液中に粉体を浸漬し分散し、チタ
ンあるいはジルコニウムなどの金属塩である硫酸チタ
ン、硫酸ジルコニウム等を原料とし、これら金属塩の水
溶液を反応系に緩やかに滴下し、生成する金属水酸化物
あるいは金属酸化物を粉体のまわりに析出させることに
より行うことができる。この滴下反応の間、ｐＨは上記
緩衡溶液のｐＨ（３．６）に保持される。反応終了後、
この粉体を固液分離し、洗浄・乾燥後、熱処理を施す。
乾燥手段としては真空乾燥、自然乾燥のいずれでもよ
い。また、不活性雰囲気中で噴霧乾燥機などの装置を用
いることも可能である。なお、この場合の被覆膜である
酸化チタンの形成は下記の反応式で示される。
Ｔｉ（ＳＯ4 ) 2 ＋２Ｈ2Ｏ→ＴｉＯ2 ＋４Ｈ2 （ＳＯ4
) 2 Next, as an example, a method of forming an alternating multilayer film of a metal oxide having a high refractive index and a metal oxide having a low refractive index will be specifically described. First, in the case of forming a film of titanium oxide or zirconium oxide, the powder is dipped and dispersed in a buffer solution such as acetic acid / sodium acetate, and titanium sulfate, zirconium sulfate, etc., which is a metal salt of titanium or zirconium, etc. Can be carried out by slowly dropping an aqueous solution of these metal salts into the reaction system using the above as a raw material and precipitating the produced metal hydroxide or metal oxide around the powder. During this dropping reaction, the pH is maintained at the pH of the buffer solution (3.6). After the reaction,
This powder is subjected to solid-liquid separation, washed and dried, and then heat treated.
The drying means may be vacuum drying or natural drying. It is also possible to use a device such as a spray dryer in an inert atmosphere. The formation of titanium oxide, which is the coating film in this case, is represented by the following reaction formula. Ti (SO 4 ) 2 + 2H 2 O → TiO 2 + 4H 2 (SO 4
) 2
【００３５】続いて、酸化ケイ素あるいは酸化アルミニ
ウムなどの被膜を形成する場合、ＫＣｌ／Ｈ3ＢＯ3系等
にＮａＯＨを加えた緩衡溶液中に上記のチタニアコート
粉体を浸漬し分散し、ケイ素あるいはアルミニウムなど
の金属塩であるケイ酸ナトリウム、塩化アルミニウム等
を原料とし、これら金属塩の水溶液を反応系に緩やかに
滴下し、生成する金属水酸化物あるいは金属酸化物を該
粉体のまわりに析出させることにより行うことができ
る。この滴下反応の間、ｐＨは上記緩衡溶液のｐＨ
（９．０）に保持される。反応終了後、このシリカ膜被
覆粉体を固液分離し、洗浄・乾燥後、熱処理を施す。こ
の操作により、粉体の表面に屈折率の異なる２層の、金
属酸化物膜を形成する操作を繰り返すことにより、多層
の金属酸化物膜をその表面上に有する粉体が得られる。
なお、この場合の被覆膜である酸化ケイ素の形成は下記
の反応式で示される。
Ｎａ2ＳｉX Ｏ2X+1＋Ｈ2Ｏ→ＸＳｉＯ2＋２Ｎａ+＋２Ｏ
Ｈ- Subsequently, in the case of forming a film of silicon oxide or aluminum oxide, the above titania-coated powder is dipped and dispersed in a buffer solution of NaOH added to KCl / H 3 BO 3 system to obtain silicon. Alternatively, metal silicate such as aluminum, sodium silicate, aluminum chloride or the like is used as a raw material, an aqueous solution of these metal salts is slowly dropped into the reaction system, and the produced metal hydroxide or metal oxide is distributed around the powder. It can be carried out by precipitation. During the dropping reaction, the pH is the pH of the buffer solution.
It is held at (9.0). After completion of the reaction, the silica film-coated powder is subjected to solid-liquid separation, washed and dried, and then heat-treated. By this operation, the operation of forming a two-layer metal oxide film having different refractive indexes on the surface of the powder is repeated to obtain a powder having a multi-layer metal oxide film on its surface.
The formation of silicon oxide as the coating film in this case is represented by the following reaction formula. Na 2 Si X O 2X + 1 + H 2 O → XSiO 2 + 2Na + + 2O
H -
【００３６】緩衡溶液は種々の系が用いられ、特に限定
されないが、まず粉体が十分に分散できることが重要で
あり、同時に粉体の表面に析出した金属水酸化物あるい
は金属酸化物の膜被覆粉体も電気２重層の働きで分散で
き、かつ上記の緩やかな滴下反応により緻密な被膜が製
膜ができる条件を満足するように選択する必要がある。
従って、本発明の多層膜被覆粉体の製造法は従来の金属
塩溶液の反応による中和や等電点による析出、または加
熱により分解して析出させる方法とは異なるものであ
る。Various systems may be used for the buffer solution, and the system is not particularly limited, but it is important that the powder can be sufficiently dispersed, and at the same time, a metal hydroxide or a metal oxide film deposited on the surface of the powder is used. It is necessary to select the coating powder so that it can be dispersed by the action of the electric double layer and satisfy the condition that a dense coating film can be formed by the above gentle dropping reaction.
Therefore, the method for producing the multilayer film-coated powder of the present invention is different from the conventional method of neutralization by the reaction of the metal salt solution, deposition by the isoelectric point, or decomposition by heating to deposit.
【００３７】本発明に使用される緩衡溶液としては、析
出させる固相成分に依存し、特に限定されないが、Ｔｒ
ｉｓ系、ホウ酸系、グリシン系、コハク酸系、乳酸系、
酢酸系、酒石酸系、塩酸系等が挙げられる。The buffer solution used in the present invention depends on the solid phase component to be precipitated and is not particularly limited.
is type, boric acid type, glycine type, succinic acid type, lactic acid type,
Examples thereof include acetic acid type, tartaric acid type, hydrochloric acid type and the like.
【００３８】次に、本発明において使用する原料、特に
金属塩について説明する。高屈折率の膜を製膜するのに
使用する原料としては、酸化チタン膜用には、チタンの
ハロゲン化物、硫酸塩等、酸化ジルコニウム膜用には、
ジルコニウムのハロゲン化物、硫酸塩、カルボン酸塩、
シュウ酸塩、キレート錯体等、酸化セリウム膜用には、
セリウムのハロゲン化物、硫酸塩、カルボン酸塩、シュ
ウ酸塩等、酸化ビスマス膜用には、ビスマスのハロゲン
化物、硝酸塩、カルボン酸塩等、酸化インジウム膜用に
は、インジウムのハロゲン化物、硫酸塩等が好ましい。
また、低屈折率の膜を製膜するのに使用する原料として
は、酸化ケイ素膜用には、ケイ酸ソーダ、水ガラス、ケ
イ素のハロゲン化物、アルキルシリケート等の有機ケイ
素化合物とその重合体等、酸化アルミニウム膜用には、
アルミニウムのハロゲン化物、硫酸塩、キレート錯体
等、酸化マグネシウム膜用には、マグネシウムの硫酸
塩、ハロゲン化物等が好ましい。また、例えば酸化チタ
ン膜の場合には、塩化チタンに硫酸チタンを混合する
と、より低温で屈折率の高いルチル型の酸化チタン膜に
なる等の効果がある。Next, the raw materials used in the present invention, especially the metal salt, will be described. As a raw material used for forming a film having a high refractive index, titanium oxide films include titanium halides and sulfates, and zirconium oxide films include:
Zirconium halide, sulfate, carboxylate,
For cerium oxide film such as oxalate and chelate complex,
Cerium halides, sulfates, carboxylates, oxalates, etc. for bismuth oxide films, bismuth halides, nitrates, carboxylates, etc., for indium oxide films, indium halides, sulfates, etc. Etc. are preferred.
Further, as a raw material used for forming a film having a low refractive index, for a silicon oxide film, sodium silicate, water glass, a halide of silicon, an organosilicon compound such as an alkyl silicate and a polymer thereof, etc. , For aluminum oxide film,
For magnesium oxide films such as aluminum halides, sulfates and chelate complexes, magnesium sulfates and halides are preferable. Further, in the case of a titanium oxide film, for example, mixing titanium chloride with titanium sulfate has the effect of forming a rutile-type titanium oxide film having a high refractive index at a lower temperature.
【００３９】また、被覆膜の製膜の際の反応温度を、各
金属塩の種類に適した温度に管理して被覆することによ
り、より完全な酸化物膜を製作することができる。水系
溶媒中での粉体の表面への被膜形成反応（固層析出反
応）が遅すぎる場合には、反応系を加熱して固層析出反
応を促進することもできる。但し、加熱の熱処理が過剰
であると、該反応速度が速すぎて、過飽和な固層が膜に
ならず、水溶液中に析出し、ゲルあるいは微粒子を形成
し、膜厚制御が困難になる。被覆膜は製作後、蒸留水を
加えながら傾斜洗浄を繰り返して、電解質を除去した
後、乾燥・焼成等の熱処理を施し、固相中に含まれた水
を除去して、完全に酸化物膜とすることが好ましい。ま
た、製膜後の粉体を回転式チューブ炉などで熱処理する
ことにより、固着を防ぐことができ、分散された粒子を
得ることができる。Further, a more complete oxide film can be manufactured by controlling the reaction temperature at the time of film formation of the coating film to a temperature suitable for the kind of each metal salt and coating. When the film forming reaction (solid layer deposition reaction) on the surface of the powder in the aqueous solvent is too slow, the reaction system can be heated to accelerate the solid layer deposition reaction. However, if the heat treatment for heating is excessive, the reaction rate is too fast, and the supersaturated solid layer does not form a film but precipitates in an aqueous solution to form gel or fine particles, which makes it difficult to control the film thickness. After manufacturing the coating film, gradient washing is repeated while adding distilled water to remove the electrolyte, and then heat treatment such as drying and baking is performed to remove the water contained in the solid phase to completely remove the oxide. It is preferably a film. Further, by heat-treating the powder after film formation in a rotary tube furnace or the like, sticking can be prevented and dispersed particles can be obtained.
【００４０】水酸化物膜あるいは酸化物膜を形成し、そ
れを熱処理するには、各層を被覆する毎に熱処理しても
良く、また、目的の多層膜を完成後最後に熱処理しても
良い。熱処理条件は反応系により異なるが、上記の熱処
理温度としては２００〜１３００℃であり、好ましくは
４００〜１１００℃である。２００℃未満では塩類や水
分が残ってしまう事あり、１３００℃を超えて高くなる
と、隣り合う膜同志や膜と基体とが界面で反応し別の物
質となることがあり、共に不適である。熱処理時間とし
ては０．１〜１００時間であり、好ましくは０．５〜５
０時間である。To form a hydroxide film or an oxide film and heat-treat it, heat treatment may be performed each time each layer is coated, or heat treatment may be performed at the end after the target multilayer film is completed. . Although the heat treatment conditions vary depending on the reaction system, the heat treatment temperature is 200 to 1300 ° C, preferably 400 to 1100 ° C. If the temperature is lower than 200 ° C., salts and water may remain, and if the temperature is higher than 1300 ° C., the adjacent films or the films and the substrate may react at the interface and become different substances, which are both unsuitable. The heat treatment time is 0.1 to 100 hours, preferably 0.5 to 5
It's 0 hours.
【００４１】[0041]
【実施例】以下に本発明を実施例によって更に具体的に
説明するが、勿論本発明の範囲は、これらによって限定
されるものではない。
実施例１
（水ガラスを用いて酸化防止膜を形成する方法：水系２
層被膜）水ガラス４８ｇを、水１リットルに溶解し、平
均粒径０．５μｍのマグネタイト粉１２ｇを加え、超音
波により十分に分散した後、これを９５℃で加熱しなが
ら、１Ｍ硫酸４０ｍｌを１．６ｍｌ／ｍｉｎの速さで添
加し、添加後２時間反応させ、含水シリカ膜を形成し
た。シリカ膜が形成された膜被覆粉体を含む溶液に脱イ
オン水を加え、デカンテーションを繰り返すことにより
電解質を除去した。前記洗浄後、真空乾燥機で１００℃
で８時間乾燥した後、回転式チューブ炉を用い、１００
％水素雰囲気中で、４００℃で３時間保持した後、炉を
放冷し還元を行い、シリカ被覆鉄粉１１ｇを得た。得ら
れたシリカ被覆鉄粉は、それぞれの粒子が分離し、１０
ｋＯｅでの磁化は１８４ｅｍｕ／ｇであった。ＸＲＤ
（Ｘ線回折装置の略；Ｐｈｌｉｐｓ社製、ＭＰＤ−１８
８０）で解析した結果すべて鉄に還元されていた。 緑
色を目標とした１層目の光学膜厚は目標の７５ｎｍに対
し５３ｎｍであり、不足である。不足分を補うため再度
製膜した。The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto. Example 1 (Method of forming antioxidant film using water glass: water-based 2
(Layer coating) 48 g of water glass is dissolved in 1 liter of water, 12 g of magnetite powder having an average particle size of 0.5 μm is added, and the mixture is sufficiently dispersed by ultrasonic waves. While heating this at 95 ° C., 40 ml of 1M sulfuric acid is added. It was added at a rate of 1.6 ml / min, and after the addition, reaction was carried out for 2 hours to form a hydrous silica film. Deionized water was added to the solution containing the film-coated powder having the silica film formed thereon, and decantation was repeated to remove the electrolyte. After the cleaning, vacuum dryer at 100 ℃
After drying for 8 hours at 100 ° C. using a rotary tube furnace
After holding at 400 ° C. for 3 hours in a% hydrogen atmosphere, the furnace was allowed to cool and reduction was performed to obtain 11 g of silica-coated iron powder. In the obtained silica-coated iron powder, each particle was separated and
The magnetization at kOe was 184 emu / g. XRD
(Abbreviation of X-ray diffractometer; MPD-18 manufactured by Philips)
As a result of analysis in 80), all were reduced to iron. The optical thickness of the first layer, which is aimed at green, is 53 nm, which is short of the target of 75 nm. The film was formed again to make up for the shortage.
【００４２】（水ガラスを用いて１層目不足分の膜厚調
整）水ガラス２８ｇを、水１リットルに溶解し、前記シ
リカ膜被覆鉄粉１１ｇを加え、超音波により十分に分散
した後、これを９５℃で加熱しながら、１Ｍ硫酸２５ｍ
ｌを１．６ｍｌ／ｍｉｎの速さで添加し、添加後２時間
反応させ、含水シリカ膜を形成した。シリカ膜が形成さ
れた膜被覆粉体を含む溶液に脱イオン水を加え、デカン
テーションを繰り返すことにより電解質を除去した。前
記洗浄後、真空乾燥機で１００℃で８時間乾燥した後、
回転式チューブ炉を用い、１００％水素雰囲気中で、４
００℃で３時間保持した後炉を放冷し還元を行い、シリ
カ被覆鉄粉１０ｇを得た。得られたシリカ被覆鉄粉は、
それぞれの粒子が分離し、１０ｋＯｅでの磁化は１７８
ｅｍｕ／ｇであった。ＸＲＤ（Ｘ線回折装置の略）；Ｐ
ｈｌｉｐｓ社製、ＭＰＤ−１８８０で解析した結果すべ
て鉄に還元されていた。１層目の光学膜厚は目標の７５
ｎｍに対し７５ｎｍで目標の厚さが得られた。(Adjusting the film thickness of the first layer using water glass) 28 g of water glass was dissolved in 1 liter of water, 11 g of the iron powder coated with silica film was added, and the mixture was sufficiently dispersed by ultrasonic waves. While heating this at 95 ° C, 25m of 1M sulfuric acid
1 was added at a rate of 1.6 ml / min, and after the addition, the mixture was reacted for 2 hours to form a hydrous silica film. Deionized water was added to the solution containing the film-coated powder having the silica film formed thereon, and decantation was repeated to remove the electrolyte. After the washing, after drying in a vacuum dryer at 100 ° C. for 8 hours,
Using a rotary tube furnace, in a 100% hydrogen atmosphere, 4
After holding at 00 ° C. for 3 hours, the furnace was allowed to cool and reduction was performed to obtain 10 g of silica-coated iron powder. The obtained silica-coated iron powder,
The particles were separated, and the magnetization at 10 kOe was 178.
It was emu / g. XRD (abbreviation of X-ray diffractometer); P
As a result of analysis with MPD-1880 manufactured by hlipps, all were reduced to iron. The target optical thickness of the first layer is 75
The target thickness was obtained at 75 nm vs. 75 nm.
【００４３】（シリカ膜被覆鉄粉への２層目チタニア膜
コーティング）酢酸０．３Ｍと酢酸ナトリウム０．３Ｍ
緩衝溶液を合計で５００ｍｌになるように調整し、この
緩衝溶液中に前記シリカ膜被覆鉄粉１０ｇを加え、超音
波により十分に分散した後、１Ｍ硫酸チタン水溶液７８
ｍｌと１Ｎ−ＮａＯＨ１３３ｍｌを両者同じく１．６７
ｍｌ／ｍｉｎの速さで添加して、添加後２時間反応させ
チタニア膜を形成した。チタニア膜が形成された膜被覆
粉体を含む溶液に脱イオン水を加え、デカンテーション
を繰り返すことにより電解質を除去した。含水チタニア
／シリカ被覆鉄粉を沈降させ、濾別し、固液分離したの
ち、真空乾燥機で、１００℃で８時間乾燥し、さらに、
回転式チューブ炉を用い、窒素ガス雰囲気で、５００℃
で３時間保持した後炉を放冷し、緑色のチタニア／シリ
カ被覆鉄粉１０ｇを得た。得られたシリカ被覆鉄粉は、
それぞれの粒子が分離し、１０ｋＯｅでの磁化は１６７
ｅｍｕ／ｇであった。(Second layer titania film coating on silica film-coated iron powder) Acetic acid 0.3M and sodium acetate 0.3M
The buffer solution was adjusted to a total volume of 500 ml, 10 g of the silica film-coated iron powder was added to the buffer solution, and the mixture was sufficiently dispersed by ultrasonic waves, and then a 1M titanium sulfate aqueous solution 78 was added.
ml and 1N-NaOH 133 ml are both 1.67.
It was added at a speed of ml / min, and after the addition, the mixture was reacted for 2 hours to form a titania film. The electrolyte was removed by adding deionized water to the solution containing the film-coated powder on which the titania film was formed and repeating decantation. The hydrous titania / silica-coated iron powder was allowed to settle, separated by filtration, and solid-liquid separated, and then dried at 100 ° C. for 8 hours in a vacuum dryer.
Using a rotary tube furnace, in a nitrogen gas atmosphere, 500 ℃
After holding for 3 hours, the furnace was allowed to cool and 10 g of green titania / silica-coated iron powder was obtained. The obtained silica-coated iron powder,
The particles were separated, and the magnetization at 10 kOe was 167.
It was emu / g.
【００４４】比較例１
水ガラス７５ｇを、水１リットルに溶解し平均粒径０．
５μｍのマグネタイト粉１２ｇを加え、超音波により十
分に分散した後、これを９５℃で加熱しながら、１Ｍ硫
酸７０ｍｌを１．１ｍｌ／ｍｉｎの速さで添加し、添加
後２時間反応させ、含水シリカ膜を形成した。シリカ膜
が形成された膜被覆粉体を含む溶液に脱イオン水を加
え、デカンテーションを繰り返すことにより電解質を除
去した。前記洗浄後、真空乾燥機で１００℃で８時間乾
燥した後、乾燥粉を回転式チューブ炉を用い、１００％
水素雰囲気中で、４００℃で３時間保持した後炉を放冷
し還元を行いシリカ被覆鉄粉１１ｇを得た。得られたシ
リカ被覆鉄粉は、それぞれの粒子が分離し、１０ｋＯｅ
での磁化は１８４ｅｍｕ／ｇであった。ＸＲＤで解析し
た結果、鉄が大部分（９割以上）であったが少量の未還
元マグネタイトが検出された。緑色を目標とした１層目
の光学膜厚は目標の７５ｎｍに対し８０ｎｍであり、厚
さが厚すぎるために、還元反応が不十分であったと考え
られる。Comparative Example 1 75 g of water glass was dissolved in 1 liter of water to obtain an average particle size of 0.
After adding 12 g of magnetite powder of 5 μm and thoroughly dispersing by ultrasonic waves, 70 ml of 1M sulfuric acid was added at a rate of 1.1 ml / min while heating at 95 ° C., and after the addition, the mixture was reacted for 2 hours to obtain water content. A silica film was formed. Deionized water was added to the solution containing the film-coated powder having the silica film formed thereon, and decantation was repeated to remove the electrolyte. After the washing, it was dried in a vacuum dryer at 100 ° C. for 8 hours, and the dried powder was dried in a rotary tube furnace to 100%.
After holding at 400 ° C. for 3 hours in a hydrogen atmosphere, the furnace was allowed to cool and reduction was performed to obtain 11 g of silica-coated iron powder. In the obtained silica-coated iron powder, each particle was separated and 10 kOe
The magnetization at 184 emu / g was 184 emu / g. As a result of XRD analysis, most of iron (90% or more) was detected, but a small amount of unreduced magnetite was detected. The optical thickness of the first layer, which is targeted for green, is 80 nm as compared to the target of 75 nm, and it is considered that the reduction reaction was insufficient because the thickness was too thick.
【００４５】実施例２
比較例１と同様の方法で乾燥粉（シリカ膜被覆マグネタ
イト粉）１１ｇを得、これを還元温度だけを、４５０℃
で３時間、保持した後、炉を放冷し還元を行った。この
場合は、ＸＲＤで解析した結果すべてが鉄であった。Example 2 11 g of dried powder (silica film-coated magnetite powder) was obtained in the same manner as in Comparative Example 1, and the reduction temperature was adjusted to 450 ° C.
After holding for 3 hours, the furnace was left to cool and reduction was performed. In this case, all of the results of XRD analysis were iron.
【００４６】実施例３
比較例１と同様の方法で乾燥粉（シリカ膜被覆マグネタ
イト粉）１１ｇを得、これを還元温度だけを、４００℃
で６時間、保持した後、炉を放冷し還元を行った。この
場合は、ＸＲＤで解析した結果すべてが鉄であった。Example 3 In the same manner as in Comparative Example 1, 11 g of dry powder (silica film-coated magnetite powder) was obtained, which was reduced at 400 ° C.
After holding for 6 hours, the furnace was left to cool and reduction was performed. In this case, all of the results of XRD analysis were iron.
【００４７】実施例４
（緩衝溶液と水ガラスを用いて酸化防止膜を形成する方
法：水系４層被膜）ｐＨ８．５の緩衝溶液（０．４Ｍほ
う酸、０．４Ｍ塩化カリウムおよび０．４Ｍほう酸ナト
リウムの水溶液）１リットルに、平均粒径０．５μｍの
マグネタイト粉１２ｇを加え、超音波により十分に分散
した。この混合溶液にＳｉＯ2換算で１０ｗｔ％の水ガ
ラス溶液６０ｍｌを滴下し、含水シリカ膜を形成した。
形成された膜被覆粉体を含む溶液に脱イオン水を加え、
デカンテーションを繰り返すことにより電解質を除去し
た。前記水溶液中の含水シリカ膜被覆マグネタイト粉を
沈降させ、濾別し、固液分離したのち、真空乾燥機で、
１００℃で８時間乾燥し、還元用原料シリカ被覆マグネ
タイト粉とした。還元は回転式チューブ炉を用い、水素
ガス雰囲気で、４００℃で、２時間、次いで５００℃で
３時間保持した後、炉を放冷し還元を行いシリカ被覆鉄
粉１０ｇを得た。得られたシリカ被覆鉄粉は、それぞれ
の粒子が分離し、１０ｋＯｅでの磁化は１７７ｅｍｕ／
ｇであった。ＸＲＤで解析した結果すべて鉄に還元され
ていた。この光学膜厚は６７ｎｍであり、青色の原料の
目標に合致した。Example 4 (Method of forming an antioxidant film using a buffer solution and water glass: four-layer water-based film) pH 8.5 buffer solution (0.4 M boric acid, 0.4 M potassium chloride and 0.4 M boric acid) To 1 liter of an aqueous solution of sodium), 12 g of magnetite powder having an average particle size of 0.5 μm was added and sufficiently dispersed by ultrasonic waves. To this mixed solution, 60 ml of a 10 wt% water glass solution in terms of SiO 2 was added dropwise to form a hydrous silica film.
Deionized water was added to the solution containing the formed film-coated powder,
The electrolyte was removed by repeating decantation. The hydrous silica film-coated magnetite powder in the aqueous solution is allowed to settle, filtered, and after solid-liquid separation, with a vacuum dryer,
It was dried at 100 ° C. for 8 hours to obtain a reducing raw material silica-coated magnetite powder. The reduction was carried out by using a rotary tube furnace in a hydrogen gas atmosphere at 400 ° C. for 2 hours and then at 500 ° C. for 3 hours, and then the furnace was allowed to cool and reduction was performed to obtain 10 g of silica-coated iron powder. In the obtained silica-coated iron powder, the particles were separated, and the magnetization at 10 kOe was 177 emu /
It was g. As a result of analysis by XRD, all were reduced to iron. This optical film thickness was 67 nm, which met the target of the blue raw material.
【００４８】（シリカ膜被覆鉄粉への２層目チタニア膜
コーティング）酢酸０．３Ｍと酢酸ナトリウム０．３Ｍ
の緩衝溶液を合計で５００ｍｌになるように調整し、こ
の緩衝溶液中に前記シリカ膜被覆鉄粉１０ｇを加え、超
音波により十分に分散した。１Ｍ塩化チタン水溶液８０
ｍｌと１Ｎ−ＮａＯＨ ８０ｍｌを両者同じく１．６７
ｍｌ／ｍｉｎの速さで添加して、添加後２時間反応させ
チタニアを形成した。形成された膜被覆粉体を含む溶液
に脱イオン水を加え、デカンテーションを繰り返すこと
により電解質を除去した。含水チタニアシリカ被覆鉄粉
を沈降させ、濾別し、固液分離したのち、真空乾燥機
で、１００℃で８時間乾燥し、さらに、回転式チューブ
炉を用い、窒素ガス雰囲気で、５００℃で３時間保持し
た後炉を放冷し、チタニアシリカ被覆鉄粉１０ｇを得
た。(Second layer titania film coating on silica powder coated iron powder) 0.3M acetic acid and 0.3M sodium acetate
The buffer solution prepared in (1) was adjusted to a total volume of 500 ml, and 10 g of the above-mentioned iron powder coated with silica film was added to this buffer solution and sufficiently dispersed by ultrasonic waves. 1M Titanium Chloride Aqueous Solution 80
ml and 1N-NaOH 80 ml both 1.67
The titania was added at a rate of ml / min and reacted for 2 hours after the addition to form titania. Deionized water was added to the solution containing the formed film-coated powder, and the decantation was repeated to remove the electrolyte. The hydrous titania-silica-coated iron powder is allowed to settle, filtered, and solid-liquid separated, and then dried in a vacuum dryer at 100 ° C for 8 hours, and further, using a rotary tube furnace in a nitrogen gas atmosphere at 500 ° C. After holding for 3 hours, the furnace was allowed to cool to obtain 10 g of titania-silica-coated iron powder.
【００４９】（チタニアシリカ膜被覆鉄粉への３層目シ
リカ膜コーティング）１層目と同様の緩衝溶液（０．４
Ｍほう酸、０．４Ｍ塩化カリウムおよび０．４Ｍほう酸
ナトリウムの水溶液）１リットルに、チタニアシリカ被
覆鉄粉１０ｇを加え、超音波により十分に分散した。こ
の混合溶液にＳｉＯ2換算で１０ｗｔ％の水ガラス溶液
５８ｍｌを滴下し、含水シリカ膜を形成した。形成され
た３層目含水シリカ膜被覆粉体を含む溶液に脱イオン水
を加え、デカンテーションを繰り返すことにより電解質
を除去した。前記水溶液中の含水シリカ膜被覆鉄粉を沈
降させ、濾別し、固液分離したのち、真空乾燥機で、１
００℃で８時間乾燥し、還元用原料３層目シリカ被覆鉄
粉９ｇを得た。(Third layer silica film coating on titania silica film-coated iron powder) The same buffer solution as the first layer (0.4
1 g of an aqueous solution of M boric acid, 0.4 M potassium chloride and 0.4 M sodium borate) was added with 10 g of titania-silica-coated iron powder and sufficiently dispersed by ultrasonic waves. To this mixed solution, 58 ml of a 10 wt% water glass solution in terms of SiO 2 was dropped to form a hydrous silica film. Deionized water was added to the formed solution containing the third layer hydrous silica film-coated powder, and decantation was repeated to remove the electrolyte. The hydrous silica film-coated iron powder in the aqueous solution is allowed to settle, separated by filtration, and solid-liquid separated.
It was dried at 00 ° C. for 8 hours to obtain 9 g of a third raw material for reduction, silica-coated iron powder.
【００５０】（３層目シリカ膜被覆鉄粉への４層目チタ
ニア膜コーティング）酢酸０．３Ｍと酢酸ナトリウム
０．３Ｍ緩衝溶液を合計で５００ｍｌとなるように調整
し、この緩衝溶液中に前記３層目シリカ膜被覆鉄粉９ｇ
を加え、超音波により十分分散し、１Ｍ塩化チタン水溶
液８０ｍｌと１Ｎ−ＮａＯＨ ８５ｍｌを両者同じく
１．６７ｍｌ／ｍｉｎの速さで添加して、添加後２時間
反応させ４層目チタニア膜を形成した。チタニア膜が形
成された膜被覆粉体を含む溶液に脱イオン水を加え、デ
カンテーションを繰り返すことにより電解質を除去し
た。４層目含水チタニア膜被覆鉄粉を沈降させ、濾別
し、固液分離したのち、真空乾燥機で、１００℃で８時
間乾燥し、４層目チタニア膜被覆鉄粉８ｇを得た。得ら
れた４層目チタニア膜被覆鉄粉は、４３０ｎｍの反射ピ
ーク反射率が３５％の鮮やかな青色であった。また平均
粒径０．８５μｍで、それぞれの粒子が分離し、１０ｋ
Ｏｅでの磁化は１４４ｅｍｕ／ｇであった。(4th layer titania film coating on 3rd layer silica film coated iron powder) 0.3M acetic acid and 0.3M sodium acetate buffer solution were adjusted to a total volume of 500 ml, and the above solution was added to this buffer solution. Third layer silica film coated iron powder 9g
Was added, and the mixture was sufficiently dispersed by ultrasonic waves, and 80 ml of a 1M titanium chloride aqueous solution and 85 ml of 1N-NaOH were added at the same rate of 1.67 ml / min, and the mixture was reacted for 2 hours after the addition to form a fourth layer titania film. . The electrolyte was removed by adding deionized water to the solution containing the film-coated powder on which the titania film was formed and repeating decantation. The fourth layer hydrous titania film-covered iron powder was precipitated, separated by filtration, and solid-liquid separated, and then dried at 100 ° C. for 8 hours in a vacuum dryer to obtain a fourth-layer titania film-covered iron powder 8 g. The obtained iron powder coated with a fourth-layer titania film was a vivid blue color having a reflectance of 35% at 430 nm. Also, each particle has an average particle size of 0.85 μm and is separated by 10 k.
The magnetization at Oe was 144 emu / g.
【００５１】[0051]
【発明の効果】以上説明したように、本発明は、多層膜
被覆粉体の製造において、基体粒子の原料として、大気
中で劣化・反応し易く危険物である金属粒子を用いず
に、取扱いの容易な金属化合物を用い、この金属化合物
粒子の表面に酸化物膜を形成した粒子を還元する方法を
用い、製膜法としては、低コスト化が達成できる水系溶
媒および水溶性原料を用いる金属塩水溶液からの沈殿法
を用いるにも係わらず、厚さが均一で、所望の膜厚を有
し、干渉により着色されたカラー磁性粉体などの多層膜
被覆粉体を容易に製造することを可能とすることができ
る。また、高価な化合物である金属アルコキシドや引火
性の高い有機溶媒を用いることなく、水を溶媒として用
い、製造施設も防爆設備を必要とせず、温度、湿度の管
理も容易であり、総合的に製品の価格も安価に得られ、
かつ基体粒子の原料として金属粒子を用いることなく、
機能性の高い、多層膜被覆粉体およびその製造方法を提
供できるという効果を奏する。Industrial Applicability As described above, according to the present invention, in the production of multi-layer film-coated powder, as a raw material of the base particles, handling is performed without using metal particles which are dangerous substances which easily deteriorate and react in the atmosphere. Of a metal compound using an aqueous solvent and a water-soluble raw material, which can achieve cost reduction, by using a method of reducing a particle having an oxide film formed on the surface of the metal compound particle using an easy metal compound of Despite the use of a precipitation method from an aqueous salt solution, it is possible to easily produce a multilayer film-coated powder such as a color magnetic powder having a uniform thickness, a desired film thickness and colored by interference. It can be possible. In addition, without using expensive compounds such as metal alkoxides and highly flammable organic solvents, water is used as a solvent, explosion-proof equipment is not required at manufacturing facilities, and temperature and humidity can be easily controlled. The price of the product can be obtained cheaply,
And without using metal particles as a raw material of the base particles,
It is possible to provide a multilayer film-coated powder having a high functionality and a method for producing the same.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平７−11310（ＪＰ，Ａ) 特開 平10−68002（ＪＰ，Ａ) 特開 昭59−213626（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B22F 1/02 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-11310 (JP, A) JP-A-10-68002 (JP, A) JP-A-59-213626 (JP, A) (58) Field (Int.Cl. 7 , DB name) B22F 1/02
Claims (6)
たは金属水酸化物膜を有する粉体の製造方法において、Or in a method for producing a powder having a metal hydroxide film,
金属化合物粒子の表面上に酸化物膜を形成し、この酸化An oxide film is formed on the surface of the metal compound particles and this oxidation
物膜を形成した金属化合物粒子を還元して酸化防止膜被The metal compound particles that have formed a physical film are reduced to cover the antioxidant film.
覆金属粒子とし、該酸化防止膜被覆金属粒子の表面に、As the metal particles covered, on the surface of the metal particles coated with the antioxidant film,
水溶液中での金属塩の反応により、厚さが１０ｎｍ〜１Due to the reaction of the metal salt in the aqueous solution, the thickness is 10 nm to 1
０μｍの金属水酸化物膜または金属酸化物膜を形成し、Forming a metal hydroxide film or a metal oxide film of 0 μm,
干渉色により着色することを特徴とする多層膜被覆粉体Multilayer film-coated powder characterized by being colored with an interference color
の製造方法。Manufacturing method.
μｍであることを特徴とする請求項１に記載の多層膜被The multi-layer film coating according to claim 1, wherein
覆粉体の製造方法。A method for manufacturing a covering powder.
とを特徴とする請求項１に記載の多層膜被覆粉体の製造The production of the multilayer film-coated powder according to claim 1, characterized in that
方法。Method.
あることを特徴とする請求項１に記載の多層膜被覆粉体The multilayer film-coated powder according to claim 1, wherein
の製造方法。Manufacturing method.
ることを特徴とする請求項１に記載の多層膜被覆粉体のThe multilayer film-coated powder according to claim 1, characterized in that
製造方法。Production method.
成された金属水酸化物膜または金属酸化物膜が、その形The formed metal hydroxide film or metal oxide film is
成後に加熱処理してなる被覆膜であることを特徴とするCharacterized by a coating film formed by heat treatment after formation
請求項１に記載の多層膜被覆粉体の製造方法。The method for producing a multilayer film-coated powder according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20818498A JP3532417B2 (en) | 1998-07-23 | 1998-07-23 | Method for producing multilayer film-coated powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20818498A JP3532417B2 (en) | 1998-07-23 | 1998-07-23 | Method for producing multilayer film-coated powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000038602A JP2000038602A (en) | 2000-02-08 |
| JP3532417B2 true JP3532417B2 (en) | 2004-05-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP20818498A Expired - Lifetime JP3532417B2 (en) | 1998-07-23 | 1998-07-23 | Method for producing multilayer film-coated powder |
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| JP (1) | JP3532417B2 (en) |
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| JP3772967B2 (en) | 2001-05-30 | 2006-05-10 | Ｔｄｋ株式会社 | Method for producing magnetic metal powder |
| JP2004077048A (en) * | 2002-08-20 | 2004-03-11 | Kuraray Co Ltd | Heat ray low radiation outer jacket |
| US10894907B2 (en) | 2016-05-17 | 2021-01-19 | National University Corporation Hokkaido University | Latent-heat storage body microcapsules and process for producing latent-heat storage body microcapsules |
| JP6913798B1 (en) * | 2020-05-18 | 2021-08-04 | 松山鋼材株式会社 | Steel material connection mechanism and steel material connection method |
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| JP2000038602A (en) | 2000-02-08 |
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