JP2582034B2 - Powder having multilayer film on surface and method for producing the same - Google Patents
Powder having multilayer film on surface and method for producing the sameInfo
- Publication number
- JP2582034B2 JP2582034B2 JP25217093A JP25217093A JP2582034B2 JP 2582034 B2 JP2582034 B2 JP 2582034B2 JP 25217093 A JP25217093 A JP 25217093A JP 25217093 A JP25217093 A JP 25217093A JP 2582034 B2 JP2582034 B2 JP 2582034B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- powder
- film
- metal oxide
- oxide
- 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 138
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 161
- 239000002184 metal Substances 0.000 claims description 161
- 150000004706 metal oxides Chemical class 0.000 claims description 68
- 229910044991 metal oxide Inorganic materials 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 39
- 150000002736 metal compounds Chemical class 0.000 claims description 29
- 150000004703 alkoxides Chemical class 0.000 claims description 28
- 230000005291 magnetic effect Effects 0.000 claims description 20
- 239000006247 magnetic powder Substances 0.000 claims description 17
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 31
- 239000010410 layer Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 24
- 229910052709 silver Inorganic materials 0.000 description 24
- 239000004332 silver Substances 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- -1 cobalt complex salt Chemical class 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910001337 iron nitride Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- XNRABACJWNCNEQ-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.[Ag+].[O-][N+]([O-])=O XNRABACJWNCNEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 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
- 230000005484 gravity Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Powder Metallurgy (AREA)
- Chemically Coating (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面に多層膜を有し、複
合機能を発揮する金属粉体又は金属化合物粉体に関する
ものであり、特に表面に多層膜を有し、カラー磁性トナ
ーやカラー磁性インキ等のカラー磁性材料原料となる磁
性粉体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal powder or a metal compound powder having a multilayer film on its surface and exhibiting a composite function. The present invention relates to a magnetic powder used as a raw material of a color magnetic material such as a magnetic ink.
【０００２】[0002]
【従来の技術】物品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
られているが、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
膜厚の厚い皮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。2. Description of the Related Art There are many known coating techniques for forming a film on the surface of an article for protection and decoration, such as coating, deposition, sputtering, vacuum deposition, electrodeposition and anodic oxidation. However, it is difficult to make the thickness of the film uniform by the coating method or the deposition method, and it is difficult to obtain a thick film by the sputtering or the vacuum evaporation method. Further, the electrodeposition method and the anodic oxidation method are not suitable for treating powder because the object to be treated is used as an electrode.
【０００３】特開平３−２７１３７６号公報には、非金
属物体である雲母にメタリック光沢を持たせる目的で焼
成還元法により銀皮膜を雲母上に形成することが示され
ているが、高温で熱処理するため本工程は一般の粉末の
処理に適合できない。特開平１−１１９０６２号公報に
は、粉体に導電率を上げることを目的として、粉体に銀
被覆をする技術が開示されている。また、金属表面技術
第１７巻８号２９９頁以降１９６６年には、板状物体を
コバルト錯塩水溶液中に浸漬し、コバルト錯イオンを還
元して、板状物体に金属コバルト膜を設ける無電解メッ
キ法についての技術が開示されている。しかし、これら
技術には複数の層を設けることは全く触れられていな
い。Japanese Patent Application Laid-Open No. 3-271376 discloses that a silver film is formed on mica by a firing reduction method in order to impart a metallic luster to mica which is a non-metallic object. Therefore, this process cannot be adapted to general powder processing. Japanese Patent Application Laid-Open No. 1-119062 discloses a technique of coating a powder with silver for the purpose of increasing the conductivity of the powder. In addition, in Metal Surface Technology, Vol. 17, No. 8, pp. 299 to 1966, electroless plating in which a plate-like object is immersed in an aqueous solution of a cobalt complex salt to reduce cobalt complex ions and provide a metal cobalt film on the plate-like object. Techniques for the law are disclosed. However, there is no mention of providing multiple layers in these techniques.
【０００４】金属粉体又は金属酸化物粉体の表面に金属
の被覆膜を形成する方法については、例えば特開平３−
２７１３７６号公報に金属コバルト、金属ニッケル、金
属鉄などの金属、あるいはフェライト、酸化クロムなど
の金属酸化物の粉体の表面に湿式で水溶性コバルト塩を
還元して金属コバルトの被覆膜を形成する方法が、また
特開平３−２７４２７８号公報に金属コバルト、金属ニ
ッケル、金属鉄などの金属、あるいはフェライト、酸化
クロムなどの金属酸化物の粉体の表面に湿式で水溶性銀
塩を還元して金属銀の被覆膜を形成する方法を提示して
いる。A method of forming a metal coating film on the surface of a metal powder or a metal oxide powder is disclosed in, for example,
No. 271376 discloses a method of forming a metal cobalt coating film on a surface of powder of a metal such as metal cobalt, metal nickel and metal iron, or a metal oxide such as ferrite and chromium oxide by a wet method by reducing a water-soluble cobalt salt. Japanese Unexamined Patent Publication No. 3-274278 discloses a method of reducing a water-soluble silver salt by a wet method on the surface of a powder of a metal such as metal cobalt, metal nickel, or metal iron, or a metal oxide such as ferrite or chromium oxide. A method of forming a coating film of metallic silver by using the method.
【０００５】金属粉体の表面に金属酸化物の被覆膜を形
成する方法については、同種の金属酸化物の皮膜を形成
する場合にはその金属粉体を酸化雰囲気中に置けばよい
が、微細な金属粉体を酸化雰囲気中に置くと急速に酸化
が進み温度が上昇して甚だしい場合は発火におよぶこと
がある等一般に反応が速く、緻密な酸化皮膜が得難い。
また緻密な酸化皮膜を生成させようとするとこの方法で
は膜厚を厚くすることは困難である等、緻密な膜を均一
に希望する膜厚に生成させることは容易ではない。金属
粉体の表面にその金属とは異種の金属酸化物の皮膜を形
成することはより困難である。金属粉体又は金属酸化物
粉体の表面に、その構成金属とは異種の金属酸化物の皮
膜を形成する方法として、例えば金属酸化物となる金属
の塩水溶液中に被覆処理される金属粉体又は金属酸化物
粉体を浸漬して、上記したように該金属塩を還元して金
属を析出させ、これを加熱する等して酸化物に変化させ
る方法では緻密な膜を生成させることはできない。先
に、本発明者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
解するとにより、金属酸化物の皮膜を形成する方法を発
明し特許出願した（特願平５−４０６７８号）。With respect to a method of forming a coating film of a metal oxide on the surface of a metal powder, when a metal oxide film of the same type is formed, the metal powder may be placed in an oxidizing atmosphere. When a fine metal powder is placed in an oxidizing atmosphere, the oxidation proceeds rapidly, and when the temperature rises severely, the reaction may be ignited. In general, the reaction is fast, and it is difficult to obtain a dense oxide film.
Further, it is not easy to uniformly form a dense film to a desired film thickness, for example, it is difficult to increase the film thickness by this method in order to form a dense oxide film. It is more difficult to form a film of a metal oxide different from the metal on the surface of the metal powder. As a method for forming a film of a metal oxide different from the constituent metal on the surface of the metal powder or the metal oxide powder, for example, a metal powder coated with an aqueous salt solution of a metal to be a metal oxide Alternatively, a method in which a metal oxide powder is immersed and the metal salt is reduced to precipitate a metal as described above, and this is changed to an oxide by heating or the like cannot produce a dense film. . Previously, the present inventor invented a method of forming a metal oxide film by dispersing a metal powder or a metal oxide powder in a metal alkoxide solution and hydrolyzing the metal alkoxide. Japanese Patent Application No. 5-40678.
【０００６】[0006]
【発明が解決しようとする課題】上記したように、本発
明者は金属粉体又は金属化合物粉体（以下には紛らわし
くない時には金属又は金属化合物粉体とする）の表面に
金属又は金属酸化物の皮膜を形成して、核になる金属又
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。しかしながら、例えばカラー磁性ト
ナーやカラー磁性インキ等のカラー磁性材料原料となる
白色の磁性粉体を得るために上記特開平３−２７１３７
６号公報や特開平３−２７４２７８号公報に記載したよ
うに金属鉄、フェライト、酸化クロムなどの磁性体粉体
の表面に金属コバルトの被覆膜を形成したり、また金属
銀の被覆膜を形成する方法では相当に被覆膜の厚味を厚
くしなければならず、厚くしてもなお十分に白色の磁性
粉体を得るには至らない等、粉体に単層の被覆膜を形成
して良質の機能性粉体を得ることは困難である。As described above, the present inventor has proposed that the surface of metal powder or metal compound powder (hereinafter referred to as metal or metal compound powder when not confused) is coated with metal or metal oxide. In order to develop a highly functional metal or metal compound powder by forming a film and adding other properties to the properties of the core metal or metal compound powder. However, in order to obtain a white magnetic powder which is a raw material of a color magnetic material such as a color magnetic toner or a color magnetic ink, the method disclosed in Japanese Patent Application Laid-Open No. 3-27137 is used.
No. 6, JP-A-3-274278, a metal cobalt coating film on the surface of a magnetic powder such as metallic iron, ferrite, chromium oxide, or a metallic silver coating film. In the method of forming a coating film, the thickness of the coating film must be considerably thickened, and even if the thickness is increased, it is not possible to obtain a sufficiently white magnetic powder. It is difficult to obtain high quality functional powder by forming
【０００７】鋭意研究の結果、十分に白色の磁性粉体を
得ることは、例えば金属鉄、フェライト、酸化クロムな
どの磁性体粉体の表面に先ず金属膜を形成し、その上に
金属酸化物の被覆膜を形成し、その上に金属コバルトや
金属銀の被覆膜を形成する方法など、金属膜及び金属酸
化物膜を交互に形成し、かつこれらの膜を合計して３層
以上設けることにより達成されることを見出した。さら
には、核になる金属粉体に熱伝導性の良い金属銀や金属
銅を使用しその表面に金属膜及び金属酸化物膜を交互に
複数層設けることにより熱伝導性の良い絶縁性粉体が得
られ、しかも電気絶縁層が金属粉体に強固に密着してい
る粉末を提供することができることなど、複合機能を発
揮する粉体が得られることが判明し、本発明に到達し
た。As a result of intensive studies, obtaining a sufficiently white magnetic powder requires, for example, first forming a metal film on the surface of a magnetic powder such as metallic iron, ferrite, and chromium oxide, and then depositing a metal oxide thereon. A metal film and a metal oxide film are alternately formed, such as a method of forming a coating film of metallic cobalt or metallic silver thereon , and a total of three layers of these films.
It has been found that this is achieved by providing the above . Furthermore, insulating powder with good thermal conductivity is obtained by using metallic silver or copper with good thermal conductivity as the core metal powder and providing multiple layers of metal films and metal oxide films alternately on the surface. It has been found that a powder exhibiting a composite function can be obtained, for example, a powder having an electric insulating layer firmly adhered to a metal powder can be provided, and the present invention has been achieved.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明の目的
である複合機能を発揮する粉体は、金属粉体又は金属化
合物粉体の表面に、１層当たり均一な０．０１〜２０μ
ｍの厚みでの金属膜及び金属酸化物膜を交互に形成し、
かつこれらの膜を合計して３層以上形成し、これらの層
によって光学的な性質を有するものであることを特徴と
する表面に多層膜を有する粉体により得られ、特に、カ
ラー磁性トナーやカラー磁性インキ等のカラー磁性材料
原料となる優れた白色の磁性粉体は、前記金属粉体又は
金属化合物粉体を磁性を有するものであるとした前記の
表面に多層膜を有する粉体により得られる。That is, the powder exhibiting the composite function, which is the object of the present invention, is formed on the surface of the metal powder or the metal compound powder at a uniform thickness of 0.01 to 20 μm per layer.
forming a metal film and a metal oxide film alternately with a thickness of m
In addition, these films are formed in total of three or more layers, and these layers are formed.
An excellent white magnetic powder that is obtained as a powder having a multilayer film on the surface, and is a raw material of a color magnetic material such as a color magnetic toner and a color magnetic ink, characterized in that it has optical properties. The body is the metal powder or
The metal compound powder is assumed to be magnetic
It is obtained by a powder having a multilayer film on the surface .
【０００９】上記金属膜及び金属酸化物膜を交互に形成
し、かつこれらの膜を合計して３層以上形成し、これら
の層によって光学的な性質を有するものである粉体は、
金属アルコキシド溶液中に、金属膜を有するあるいは有
しない金属粉体又は金属膜を有する金属化合物粉体を分
散し、該金属アルコキシドを加水分解することにより、
前記金属粉体又は金属化合物粉体の表面に金属酸化物膜
を形成させ、前記金属酸化物膜を形成させた金属粉体又
は金属化合物粉体の表面に金属膜を形成することを特徴
とする表面に金属酸化物膜及び金属皮膜を交互に形成
し、かつこれらの膜を合計して３層以上形成せしめてな
る粉体の製造方法によって得られる。特に上記カラー磁
性材料原料となる優れた白色の磁性粉体は、金属粉体又
は金属化合物粉体の表面に先ず金属膜を形成し、次いで
該金属膜を被覆した磁性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、金属被覆を有する粉体の表面に金属酸化物膜を形成
させ、該金属酸化物膜を形成させた金属粉体又は金属化
合物粉体の表面に金属膜を形成することにより製造する
ことができる。勿論、反射率の大きい金属粉体を核とす
る場合には、最初の金属膜を被覆する工程を省略して
も、金属酸化物膜や最上層の金属膜の種類や層の厚さを
選択し３層以上とすることにより優れた白色の磁性粉体
を製造することができる。The above-mentioned metal film and metal oxide film are alternately formed.
And a total of three or more layers of these films are formed.
Powder that has optical properties due to the layer of
In a metal alkoxide solution, by dispersing a metal powder having or without a metal film or a metal compound powder having a metal film, and hydrolyzing the metal alkoxide,
A metal oxide film is formed on the surface of the metal powder or metal compound powder, and a metal film is formed on the surface of the metal powder or metal compound powder on which the metal oxide film is formed. Metal oxide film and metal film are alternately formed on the surface
And do not form a total of three or more of these films.
Produced by the process of that powder. In particular, the excellent white magnetic powder used as the color magnetic material raw material is formed by first forming a metal film on the surface of a metal powder or a metal compound powder, and then coating the magnetic powder coated with the metal film in a metal alkoxide solution. To form a metal oxide film on the surface of the powder having a metal coating by hydrolyzing the metal alkoxide, and the surface of the metal powder or metal compound powder on which the metal oxide film is formed. It can be manufactured by forming a metal film on the substrate. Of course, in the case of using a metal powder having a high reflectivity as a nucleus, the type and thickness of the metal oxide film and the uppermost metal film can be selected even if the step of coating the first metal film is omitted. By using three or more layers, an excellent white magnetic powder can be produced.
【００１０】また、本発明において上記金属膜及び金属
酸化物膜を交互に形成し、かつこれらの膜を合計して３
層以上形成せしめてなるとは、粒子の表面に金属膜と金
属酸化物膜あるいはその逆の順に膜が少なくとも３層存
在すれば良い。また、本発明の上記金属及び金属化合物
において、金属とは金属合金を含むことを意味する。す
なわち、鉄と記載した場合、鉄・ニッケルや鉄・コバル
ト合金を含み、また鉄窒化物と記載した場合、鉄・ニッ
ケル合金窒化物や鉄・ニッケル・コバルト合金窒化物を
含み、さらに酸化鉄には鉄・ニッケル合金酸化物や鉄・
ニッケル・コバルト合金酸化物を含むことを意味する。
また、金属アルコキシドも混合金属アルコキシドを含
み、例えば、バリウムアルコキシド中にはカルシウムア
ルコキシドを含んでも良い。In the present invention, the metal film and the metal oxide film are alternately formed, and the total of these films is three.
The composed allowed formed over a layer, film in the order of the metal film and the metal oxide film or vice versa on the surface of the particles may be at least three layers presence <br/> standing. In the above-mentioned metals and metal compounds of the present invention, the term “metal” means a metal alloy. That is, when it is described as iron, it contains iron / nickel or iron / cobalt alloy, and when it is described as iron nitride, it contains iron / nickel alloy nitride or iron / nickel / cobalt alloy nitride, Is iron / nickel alloy oxide or iron / nickel
It includes nickel-cobalt alloy oxide.
The metal alkoxide also includes a mixed metal alkoxide, and for example, a barium alkoxide may include a calcium alkoxide.
【００１１】本発明において、金属又は金属化合物粉体
の表面に金属膜を設ける手段としては、上記無電解メッ
キ法による他、接触電気メッキ法によって設けることも
でき、またスパッタリング法によって設けることもでき
る。しかしながら、接触電気メッキ法では粉体が電極に
接触しないときにはメッキされず、スパッタリング法に
おいては、粉体に金属蒸気が均一に当たらず、いずれの
方法も各粉体にごとに被覆される膜厚が異なる。これに
対し無電解メッキによる皮膜形成法では緻密で均一な膜
を形成でき、かつ膜厚の調節がし易いので好ましい。以
下には主として無電解メッキによる皮膜形成法により説
明するが、他の皮膜形成法を制限するものではない。In the present invention, a means for providing a metal film on the surface of a metal or metal compound powder can be provided by a contact electroplating method in addition to the above-mentioned electroless plating method, or can be provided by a sputtering method. . However, in the contact electroplating method, the powder is not plated when the powder does not contact the electrode, and in the sputtering method, the metal vapor is not uniformly applied to the powder. Are different. On the other hand, a film forming method by electroless plating is preferable because a dense and uniform film can be formed and the film thickness can be easily adjusted. In the following, description will be made mainly on a film forming method by electroless plating, but other film forming methods are not limited.
【００１２】本発明において、粉体の核となる金属とし
ては、鉄、ニッケル、クロム、チタン、アルミニウム
等、どのような金属でもよいが、その磁性を利用するも
のにおいては、鉄等磁性を帯びるものが好ましい。これ
らの金属は合金でも良く、前記の磁性を有するものであ
るときには、強磁性合金を使用することが好ましい。本
発明の製造工程は粉体の核が金属の場合、通常はその表
面に先ず金属酸化物膜を生成させ、次いで金属膜を設
け、必要に応じてさらに金属酸化物層を生成させる等と
いう工程となるが、金属酸化物層が粉体構成金属に接着
し難い場合には、上記したように核の金属の表面に先ず
金属膜を設けても良い。In the present invention, any metal such as iron, nickel, chromium, titanium, and aluminum may be used as the metal serving as a core of the powder. Are preferred. These metals may be alloys, and when having the above-mentioned magnetism, it is preferable to use ferromagnetic alloys. In the production process of the present invention, when the core of the powder is a metal, usually, a metal oxide film is first formed on the surface, then a metal film is provided, and a metal oxide layer is further formed as necessary. However, when the metal oxide layer does not easily adhere to the powder constituent metal, a metal film may be first provided on the surface of the core metal as described above.
【００１３】粉体の核が金属化合物の場合はその、表面
に先ず金属膜を生成させ、次いで金属酸化物膜を生成さ
せるという工程となり、次いで金属膜を設け、続いて金
属酸化物膜を設けるという工程となるのが一般的であ
る。本発明において、粉体の核となる金属化合物として
は、金属あるいは金属合金窒化物、金属あるいは金属合
金炭化物及び金属酸化物等を挙げることができ、具体的
には鉄窒化物、鉄とニッケルあるいは鉄とコバルト等の
鉄系合金の窒化物及び金属酸化物等が好ましい。また金
属酸化物としては例えば鉄、ニッケル、クロム、チタ
ン、アルミニウム、ケイ素等の他カルシウム、マグネシ
ウム、バリウム等の酸化物あるいはこれらの複合酸化物
でも良い。これらの粉体の核は、その粒径については特
に限定するものではないが、０．０１μｍ〜数ｍｍの範
囲のものが好ましい。When the core of the powder is a metal compound, a step of first forming a metal film on the surface and then forming a metal oxide film is performed, then a metal film is provided, and then a metal oxide film is provided. Generally, this is the step. In the present invention, examples of the metal compound serving as the core of the powder include a metal or metal alloy nitride, a metal or metal alloy carbide and a metal oxide, and specifically, iron nitride, iron and nickel or Preference is given to nitrides and metal oxides of iron and iron-based alloys such as cobalt. Examples of the metal oxide include iron, nickel, chromium, titanium, aluminum, silicon, and the like, as well as calcium, magnesium, barium, and the like, or a composite oxide thereof. The particle size of the core of these powders is not particularly limited, but is preferably in the range of 0.01 μm to several mm.
【００１４】粉体の表面に被覆膜を構成する金属酸化物
としては、例えば、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
等の他カルシウム、マグネシウム、バリウム等の酸化物
を用いることができる。この金属酸化物の種類は、その
粉体の表面に付与しようとする性質に応じてそれに適す
るものが選択される。Examples of the metal oxide constituting the coating film on the surface of the powder include iron, nickel, chromium, titanium, zinc, aluminum, cadmium, zirconium, silicon and the like, and oxides of calcium, magnesium, barium and the like. Things can be used. As the kind of the metal oxide, one suitable for the property to be imparted to the surface of the powder is selected.
【００１５】金属被覆膜を生成するに際しては、その金
属の錯塩の水溶液中に、金属粉体や金属化合物粉体を分
散させ、粉体の存在下に金属の錯塩を還元すると金属粉
体の表面に金属被覆膜が生成する。上記金属錯塩は、金
属の水溶性塩に錯化剤を加えて生成する。その例として
は、硝酸銀にアンモニア水を加える場合あるいは硫酸コ
バルトにクエン酸ナトリウムや酒石酸カリウムの水溶液
を加えて生成する場合を挙げることができる。In forming the metal coating film, a metal powder or a metal compound powder is dispersed in an aqueous solution of the metal complex salt, and the metal complex salt is reduced in the presence of the powder to form the metal powder. A metal coating film is formed on the surface. The metal complex salt is formed by adding a complexing agent to a water-soluble salt of a metal. Examples thereof include a case in which aqueous ammonia is added to silver nitrate or a case in which an aqueous solution of sodium citrate or potassium tartrate is added to cobalt sulfate.
【００１６】金属酸化物を生成するに際しては、その金
属酸化物の成分である金属のアルコキシドの溶液中に、
金属、金属化合物または金属の表面にさらに金属被覆膜
を生成させた粉体を分散し、金属アルコキシドを加水分
解することにより、前記粉体の表面上にその金属の酸化
物を生成させる。この加水分解による金属の酸化物を生
成させる方法は、いわゆるゾル−ゲル法と呼ばれ、微細
で均一な組成の酸化物が形成されるが、この方法を粉体
に適用することにより、均一で厚さの厚い膜が得られ
る。金属アルコキシドとしては、亜鉛、アルミニウム、
カドミウム、チタン、ジルコニウム、タンタル、ケイ素
等必要な金属酸化物に対応する金属のアルコキシドが選
択される。磁性トナー用の磁性粉体を作成するには、表
面の金属酸化物として、チタン、ケイ素の酸化物を形成
させる例が多く、この場合はケイ素又はチタンのアルコ
キシドが使用される。In producing a metal oxide, a solution of a metal alkoxide which is a component of the metal oxide is
A metal, a metal compound, or a powder in which a metal coating film is further formed on the surface of the metal is dispersed, and a metal alkoxide is hydrolyzed to generate an oxide of the metal on the surface of the powder. This method of producing a metal oxide by hydrolysis is called a sol-gel method, and an oxide having a fine and uniform composition is formed. By applying this method to powder, a uniform and uniform oxide is obtained. A thick film can be obtained. Metal alkoxides include zinc, aluminum,
An alkoxide of a metal corresponding to a required metal oxide such as cadmium, titanium, zirconium, tantalum, silicon or the like is selected. In many cases, a magnetic powder for a magnetic toner is formed by forming an oxide of titanium or silicon as a metal oxide on the surface. In this case, an alkoxide of silicon or titanium is used.
【００１７】金属アルコキシドは、水により分解するた
め、有機溶媒の溶液として使用される。有機溶媒は、ア
ルコール、例えばエタノール、メタノール等、ケトン類
等が使用される。有機溶媒は脱水したものを使用するこ
とが好ましい。金属アルコキシド溶液の濃度は、溶解す
る金属アルコキシドの種類や有機溶媒の種類によって変
わるが、最適な条件を設定する。金属アルコキシド溶液
の濃度と金属アルコキシド溶液の粉体に対する使用量に
より、粉体上の金属酸化物膜の厚さが決まる。The metal alkoxide is used as a solution in an organic solvent because it is decomposed by water. As the organic solvent, alcohols such as ethanol and methanol, ketones and the like are used. It is preferable to use a dehydrated organic solvent. The concentration of the metal alkoxide solution varies depending on the type of metal alkoxide to be dissolved and the type of organic solvent, but optimal conditions are set. The thickness of the metal oxide film on the powder is determined by the concentration of the metal alkoxide solution and the amount of the metal alkoxide solution used for the powder.
【００１８】この金属アルコキシド溶液に金属又は金属
化合物粉体を分散し、それに水を加えて金属アルコキシ
ドを加水分解して金属酸化物を生成させると共に、それ
を前記粉体上に析出させて、金属酸化物膜を生成させ
る。この金属酸化物膜が生成した粉体は、溶液から取り
出し、乾燥すると、強固な金属酸化物膜が得られる。こ
の金属酸化物膜の生成を具体的に行うに当たっては、前
記粉体を脱水したアルコール中に分散させ、充分攪拌し
ながら金属アルコキシド溶液を加えて混合し、この均一
混合物に徐々にアルコールと水の混合液を添加して、金
属アルコキシドを加水分解し、粉体表面上に金属酸化物
を析出させる。この粉体表面に被覆された金属酸化物膜
を乾燥することにより被覆粉体が得られる。乾燥は真空
乾燥することが好ましい。A metal or metal compound powder is dispersed in the metal alkoxide solution, and water is added to the metal alkoxide to hydrolyze the metal alkoxide to form a metal oxide. An oxide film is generated. The powder on which the metal oxide film is formed is taken out of the solution and dried to obtain a strong metal oxide film. To specifically form the metal oxide film, the powder is dispersed in dehydrated alcohol, a metal alkoxide solution is added and mixed with sufficient stirring, and alcohol and water are gradually added to the uniform mixture. The mixed solution is added to hydrolyze the metal alkoxide to precipitate a metal oxide on the powder surface. The coated powder is obtained by drying the metal oxide film coated on the powder surface. Drying is preferably performed under vacuum.
【００１９】金属アルコキシドの加水分解においては、
まず金属酸化物のゾルが生成し、その後ゲル化するが、
加水分解反応後、暫くおくとゲル化が進行し、場合によ
っては乾燥によりゲル化が完了する。その反応におい
て、粉体の表面に前記のゾルが生成するため、連続した
膜が形成され、それにより容易に厚さが均一で、組成も
均一であり、強固な金属酸化物膜が形成されるものと考
えられる。このような性質を有する金属酸化物膜は従来
の沈着法等によっては得られないものである。前記加水
分解反応においては、水の量が多いと、反応速度が早
く、微細な金属酸化物粒子が形成され易いが、反応を緩
やかにするためアルカノールアミン類などを添加するこ
とができる。また、前記反応を促進するため、酸類、ア
ミン類などの触媒を使用することもできる。この粉体の
製造方法においては、単に金属粉体の表面を酸化して得
る金属酸化物膜とは違った優れた性質の金属酸化物膜が
得られる。In the hydrolysis of a metal alkoxide,
First, a metal oxide sol is formed and then gelled,
After the hydrolysis reaction, gelation proceeds after a while, and in some cases, gelation is completed by drying. In the reaction, the sol is generated on the surface of the powder, so that a continuous film is formed, whereby a uniform metal oxide film having a uniform thickness and a uniform composition is easily formed. It is considered something. A metal oxide film having such properties cannot be obtained by a conventional deposition method or the like. In the hydrolysis reaction, when the amount of water is large, the reaction speed is high and fine metal oxide particles are easily formed, but alkanolamines and the like can be added to slow the reaction. In order to accelerate the reaction, a catalyst such as an acid or an amine can be used. In the method for producing a powder, a metal oxide film having excellent properties different from a metal oxide film obtained by simply oxidizing the surface of the metal powder can be obtained.
【００２０】このようにして製造した、表面に金属酸化
物膜を有する金属又は金属化合物粉体は、それを構成す
べく選択した粉体の金属又は金属化合物の材質、及び表
面の膜の金属酸化物の材質により、種々の性質を合わせ
持つので、それぞれの用途に用いることができる。例え
ば、粉体として磁性体の金属鉄、窒化鉄、四三酸化鉄な
どを用い、その上の膜として金属に比べて屈折率のより
低い酸化ケイ素や酸化チタン等を用い、その外膜として
より屈折率の高い金属銀の層を用いれば、白色度の高い
磁性粉が得られる。また、粉体の核として銀、銅あるい
はアルミニウムを核として金、白金、銀等の金属層を設
け、該金属層の上に金属酸化物として酸化アルミニウム
を用いれば、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 metal or metal compound powder having a metal oxide film on the surface manufactured as described above is made of the metal or metal compound of the powder selected to constitute the powder and the metal oxide of the surface film. It has various properties depending on the material of the object, and can be used for each purpose. For example, using magnetic iron, iron nitride, triiron tetroxide, etc. as a powder, and using silicon oxide or titanium oxide having a lower refractive index than metal as a film thereon, as an outer film, If a metal silver layer having a high refractive index is used, a magnetic powder having a high whiteness can be obtained. Further, if a metal layer of gold, platinum, silver or the like is provided with silver, copper or aluminum as a core of powder and aluminum oxide is used as a metal oxide on the metal layer, an electrically insulating surface layer can be formed. Is obtained.
【００２１】例えば、物体の表面に、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に相当する厚さだけ設けると、干渉により光は大
部分反射（フレネル反射）され、この作用を利用し、例
えば鉄、コバルト、ニッケルなどの金属粉末あるいは合
金粉末、あるいは窒化鉄の粉末などの磁性体を芯とし、
この表面に膜の物質の屈折率と膜の厚さとの積が可視光
の４分の１波長の厚さの銀あるいはコバルト等の高い反
射率の金属層を設け、さらに外側に金属より屈折率の低
い酸化ケイ素や酸化チタンのような酸化物層を、同じく
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
長の厚さ設け、さらにその上に厚さが物質の屈折率と膜
の厚さとの積が可視光の４分の１波長の厚さの銀あるい
はコバルト等の高い反射率の金属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１００℃〜５００℃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波長の厚さになる条件が満たされなけれ
ばならない。For example, a coating having a different refractive index is provided on the surface of an object, and the product of the refractive index of the material of the film and the thickness of the film is 4 times of the electromagnetic wave.
If a thickness corresponding to one-half is provided, light is mostly reflected (Fresnel reflection) by interference, and utilizing this effect, for example, metal powder or alloy powder of iron, cobalt, nickel, etc., or iron nitride powder With a magnetic material such as a core,
On this surface, there is provided a metal layer having a high reflectance such as silver or cobalt having a thickness of a quarter wavelength of visible light, the product of the refractive index of the material of the film and the thickness of the film, and further having a refractive index outside the metal. An oxide layer such as silicon oxide or titanium oxide having a low thickness is provided with a thickness of a quarter wavelength of visible light in which the product of the refractive index of the oxide and the thickness of the film is the same. The product of the refractive index of the film and the thickness of the film is a quarter-wave thickness of visible light. By coating a metal layer with a high reflectivity such as silver or cobalt, the light is reflected, and the magnet shines white. A magnetic powder for a toner can be manufactured. Further, by subjecting the produced powder to a heat treatment at a temperature of 100 ° C. to 500 ° C. in an inert gas atmosphere, it is possible to obtain a stronger and higher whiteness powder. In the case where the powder is heat-treated, the condition that the product of the refractive index of the substance and the thickness of the film in each layer of the heat-treated powder must be a quarter wavelength of visible light must be satisfied.
【００２２】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粒子の酸化物と金属の各層の
厚さは、物質の屈折率と膜の厚さとの積が可視光の４分
の１波長の厚さに近い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。図１は、そのような粉体粒
子を断面図により説明するものであって、磁性粒子１を
芯とし、その表面上に２の金属膜Ａと３の金属酸化物膜
Ｂがそれぞれ交互に複数設けられ、その最外殻は金属膜
になっている。Further, if a colored layer is 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 wide range, the thickness of each of the oxide and metal layers of the particles constituting the magnetic toner is determined by the product of the refractive index of the substance and the thickness of the film is a quarter wavelength of visible light. May be alternately provided in a plurality of portions slightly different from each other within a range close to the thickness. FIG. 1 is a cross-sectional view illustrating such a powder particle. The magnetic particle 1 is used as a core, and two metal films A and three metal oxide films B are alternately formed on the surface thereof. The outermost shell is a metal film.
【００２３】上記のようにして得られた磁性トナーの利
用方法について概略説明する。例えば、ポリエステルフ
イルムの上に金属蒸着層を設けて導電層とし、その上に
アクリル樹脂などのバインダー中に例えば酸化亜鉛のよ
うな光導電性半導体の微粒子、光増感色素、色増感剤や
分散助剤などを分散し、塗布して形成した光導電層を設
けた感光体を用意する。上記感光体上に均一にコロナ帯
電を与え、複写すべき画像からの反射光を上記帯電感光
体に照射すると、感光体上に原画像のポジ荷電像が形成
される。このポジ荷電像に磁気ブラシから、上記ポジ荷
電像と反対に帯電した本発明の磁気粉体からなる磁気ト
ナーを、感光体に付着させ、付着しない部分の磁気トナ
ーを除くと、感光体上に原画像に対応する磁気トナー像
が得られる。この磁気トナー像を紙等に転写し、定着さ
せると紙上に複写画像が得られる。紙が白色であって、
本発明の粉体を原料として着色された磁性トナーがカラ
ーであった場合には従来にない新規な複写画像となる。The method of using the magnetic toner obtained as described above will be described briefly. For example, a metal deposition layer is provided on a polyester film to form a conductive layer, and a fine particle of a photoconductive semiconductor such as zinc oxide in a binder such as an acrylic resin, a photosensitizing dye, a color sensitizer, A photoreceptor having a photoconductive layer formed by dispersing and applying a dispersing agent or the like is prepared. When a corona charge is uniformly applied to the photosensitive member and reflected light from an image to be copied is irradiated on the charged photosensitive member, a positive charged image of an original image is formed on the photosensitive member. The magnetic brush composed of the magnetic powder of the present invention charged in the opposite direction to the above positively charged image is adhered to the photoreceptor from the magnetic brush on the positively charged image. A magnetic toner image corresponding to the original image is obtained. When this magnetic toner image is transferred to paper and fixed, a copied image is obtained on paper. The paper is white,
When the magnetic toner colored by using the powder of the present invention as a raw material is a color, a new copy image which has never existed before is obtained.
【００２４】[0024]
【実施例】上記、本発明の金属粉体の表面に、金属膜及
び金属酸化物膜を交互に複数層有する粉体を製造する例
を以下に実施例を示して説明する。しかし本発明は以下
の実施例によって制限されるものではない。EXAMPLE An example of producing a powder having a plurality of metal films and metal oxide films alternately formed on the surface of the metal powder of the present invention will be described below with reference to examples. However, the present invention is not limited by the following examples.
【００２５】実施例１ 金属膜の形成：先ず銀液と還元液を調整する。銀液は以
下に示す組成である。 硝酸銀 ３．７５ｇ アンモニア水 沈澱が再溶解するまで 水 ６５ミリリットル 水酸化ナトリウム ２．７ｇ／６５ミリリットル 銀液の調整法：硝酸銀３．７５ｇを水３０ミリリットル
に溶解し、比重０．８８のアンモニア溶液を加えると、
黒褐色の酸化銀が沈澱する。この沈澱にアンモニア水を
追加すると、銀とアンモニアの錯体を形成し溶解する。
これを銀液とする。 還元液組成： ブドウ糖 ４．５ｇ 酒石酸 ４ｇ アルコール １００ミリリットル 水 １０００ミリリットル 還元液は水１０００ミリリットルにブドウ糖および酒石
酸を順次溶解した後、１０分間煮沸し、常温まで冷却し
た後、アルコールを加える。還元液の還元能力は調製後
１週間位が最も良く、予め用意して置くのが良い。Example 1 Formation of Metal Film: First, a silver solution and a reducing solution are prepared. The silver liquid has the composition shown below. 3.75 g of silver nitrate Ammonia water 65 ml of water until the precipitate is redissolved Water 2.7 ml of sodium hydroxide 2.7 g / 65 ml Adjustment of silver solution: 3.75 g of silver nitrate is dissolved in 30 ml of water, and an ammonia solution having a specific gravity of 0.88 is dissolved. In addition,
Black-brown silver oxide precipitates. When aqueous ammonia is added to the precipitate, a complex of silver and ammonia is formed and dissolved.
This is used as a silver liquid. Reducing solution composition: glucose 4.5 g tartaric acid 4 g alcohol 100 ml water 1000 ml The reducing solution is prepared by dissolving glucose and tartaric acid sequentially in 1000 ml of water, boiling for 10 minutes, cooling to room temperature, and adding alcohol. The reducing ability of the reducing solution is best about one week after preparation, and it is better to prepare in advance.
【００２６】この銀液１３０ミリリットルにカルボニル
鉄粉７５ｇを入れ、十分に攪拌し分散させた後、還元液
１３０ミリリットルを加え攪拌を行う。得られた金属被
覆粉体Ａを蒸留水で洗浄し、濾過した後、室温で８時間
真空乾燥する。この金属被覆粉体Ａの全銀（Ａｇ）量は
２．３ｇであり、それから予想される膜厚は０．０１５
μｍであった。To 130 ml of the silver solution, 75 g of carbonyl iron powder is added, sufficiently stirred and dispersed, and then 130 ml of a reducing solution is added and stirred. The obtained metal-coated powder A is washed with distilled water, filtered, and dried under vacuum at room temperature for 8 hours. The total silver (Ag) amount of the metal-coated powder A was 2.3 g, and the expected film thickness was 0.015 g.
μm.
【００２７】次に、乾燥した金属被覆粉体Ａに酸化物皮
膜を施す。 膜形成方法：チタンエトキシド７２ｇをエタノール３０
０ミリリットルに溶解した溶液中に金属被覆粉体Ａ７５
ｇを加え十分攪拌する。なお、使用するエタノールは１
昼夜以上モレキュラーシーブ３Ａ１／８で十分脱水す
る。次に、この溶液を攪拌しながら、予め用意して置い
たエタノール３００ｇに対し蒸留水３６ｇを混合した含
水アルコール溶液を徐々に滴下する。滴下終了後、５時
間攪拌し、アルコール溶液を濾別し真空乾燥機で室温で
８時間真空乾燥する。乾燥して被覆粉体Ｂを得る。被覆
粉体Ｂの全ＴｉＯ2 量は２５ｇであり、それから予想さ
れる膜厚は０．５μｍである。Next, an oxide film is applied to the dried metal-coated powder A. Film formation method: 72 g of titanium ethoxide and 30 g of ethanol
Metal-coated powder A75 in a solution dissolved in 0 ml
g and stirred well. The ethanol used is 1
Fully dehydrate with molecular sieve 3A1 / 8 day and night. Next, while stirring the solution, a hydroalcoholic solution obtained by mixing 36 g of distilled water with 300 g of ethanol prepared in advance is gradually dropped. After completion of the dropwise addition, the mixture is stirred for 5 hours, the alcohol solution is separated by filtration, and dried in a vacuum dryer at room temperature for 8 hours. Dry to obtain coated powder B. The total TiO 2 content of the coated powder B is 25 g, and the expected film thickness is 0.5 μm.
【００２８】再度銀液と還元液を調整する。銀液の調整
量は下記の通りである。調整方法は前記の通りである。
また還元液の組成および調整方法は前記の通りである。 硝酸銀 ４．７５ｇ アンモニア水 沈殿が再溶解するまで 水 ８３ミリリットル 水酸化ナトリウム水溶液 ３．４１ｇ／８３ミリリッ
トル この銀液１６６ミリリットルに被覆粉体Ｂ７５ｇを入
れ、十分に攪拌し分散させた後、還元液１６６ミリリッ
トルを加え攪拌を行う。５分間程経つと銀が析出し、１
５分間程で析出が完全に終了する。得られた金属被覆粉
体Ｃを蒸留水で洗浄し、濾過した後、室温で８時間真空
乾燥する。この金属被覆粉体Ｃの全Ａｇ量は５．２ｇで
あり、前回のＡｇ被覆量を減じた量、すなわち最外殻の
Ａｇ量は２．９ｇであり、それから予想される膜厚は
０．０１５μｍであった。かくして得られた金属被覆粉
体Ｃについて、白度計を用いて測定した反射率は７８で
あった。比較のため、原料のカルボニル鉄粉について測
定した反射率は４３であり、被覆を施すことにより、反
射率が大幅に向上した。The silver solution and the reducing solution are adjusted again. The adjustment amount of the silver solution is as follows. The adjustment method is as described above.
The composition of the reducing solution and the adjusting method are as described above. 4.75 g of silver nitrate ammonia water until the precipitate is redissolved 83 ml of water 3.41 g / 83 ml of aqueous sodium hydroxide solution 75 g of the coated powder B was added to 166 ml of this silver solution, and the mixture was sufficiently stirred and dispersed. Add milliliter and stir. After about 5 minutes, silver precipitates and 1
The precipitation is completely completed in about 5 minutes. The obtained metal-coated powder C is washed with distilled water, filtered, and dried under vacuum at room temperature for 8 hours. The total Ag amount of the metal-coated powder C was 5.2 g, and the amount obtained by subtracting the previous Ag coating amount, that is, the Ag amount of the outermost shell was 2.9 g. It was 015 μm. The reflectance of the metal-coated powder C thus obtained was 78 using a whiteness meter. For comparison, the reflectance measured for the raw material carbonyl iron powder was 43, and the coating significantly improved the reflectance.
【００２９】比較例１ （最終膜の膜厚を非常に薄くし
た場合） 実施例１と同様にして得られた被覆粉体Ｂ７５ｇを、予
め用意しておいた銀液３０ミリリットルと水１３６ミリ
リットルの混合溶液に分散させた後、還元液１６６ミリ
リットルを加え、銀膜の析出が終わるまで１時間放置し
た。結果、この被覆粉体の全Ａｇ量は２．８ｇであり、
前回のＡｇ被覆量を減じた量、すなわち最外殻のＡｇ量
は２．９ｇであり、それから予想される膜厚は０．００
３μｍであった。しかし、金属被覆粉体Ｃは、暗い青灰
色の粉末となり、目的の白色にはならなかった。これ
は、金属被覆粉体Ｃの最外殻が非常に薄いため、吸収が
起こり、光が反射されなかったためと考えられる。Comparative Example 1 (When the final film thickness was extremely thin) 75 g of the coated powder B obtained in the same manner as in Example 1 was prepared by mixing 30 ml of a silver liquid and 136 ml of water prepared in advance. After dispersing in the mixed solution, 166 ml of the reducing solution was added, and the solution was left for 1 hour until the deposition of the silver film was completed. As a result, the total Ag amount of this coated powder was 2.8 g,
The amount obtained by subtracting the previous Ag coating amount, that is, the outermost shell Ag amount is 2.9 g, and the expected film thickness is 0.00.
It was 3 μm. However, the metal-coated powder C was a dark blue-gray powder and did not have the desired white color. This is probably because the outermost shell of the metal-coated powder C was very thin, so that absorption occurred and light was not reflected.
【００３０】[0030]
【発明の効果】本発明により、複数の性質を合わせ持
ち、複合した機能を果たし得る金属又は金属化合物粉体
を得ることができる。そして、この粉体は従来得られて
いない金属膜及び金属酸化物膜を交互に複数層を設ける
ことにより、特異な性質を与えることができ、例えば白
色の粉体を得ることができる。また、その金属膜及び金
属酸化物膜は、厚さが均一でかつ結合が強固であるの
で、剥離しがたく、有用な表面層を構成することができ
る。具体的用途として、白色の磁性トナー用磁性粉体
や、電気絶縁性を備えた熱伝導性粉体などが得られ、後
者は半導体の封止材用樹脂に用いられる充填材料あるい
は電子部品の絶縁放熱を目的とした放熱シートなどに用
いられる。According to the present invention, it is possible to obtain a metal or metal compound powder having a plurality of properties and capable of performing a composite function. This powder can be given a unique property by alternately providing a plurality of layers of a metal film and a metal oxide film which have not been obtained conventionally, and for example, a white powder can be obtained. Further, since the metal film and the metal oxide film have a uniform thickness and a strong bond, they are hard to peel off and can form a useful surface layer. Specific applications include magnetic powders for white magnetic toners and thermally conductive powders with electrical insulation. The latter is used for filling materials used in resin for semiconductor encapsulants or for insulating electronic components. It is used as a heat dissipation sheet for heat dissipation.
【図１】本発明のカラー磁性トナーの断面図FIG. 1 is a cross-sectional view of a color magnetic toner of the present invention.
１ 磁性粉体 ２ 金属膜Ａ ３ 金属酸化膜Ｂ ４ 金属膜Ｃ DESCRIPTION OF SYMBOLS 1 Magnetic powder 2 Metal film A 3 Metal oxide film B 4 Metal film C
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｇ 9/083 Ｇ０３Ｇ 9/08 ３０１ 9/087 ３８１ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location G03G 9/083 G03G 9/08 301 9/087 381
Claims (4)
１層当たり均一な０．０１〜２０μｍの厚みでの金属膜
及び金属酸化物膜を交互に形成し、かつこれらの膜を合
計して３層以上形成し、これらの層によって光学的な性
質を有するものであることを特徴とする表面に多層膜を
有する粉体。1. The method according to claim 1, wherein the surface of the metal powder or the metal compound powder is
A metal film and a metal oxide film having a uniform thickness of 0.01 to 20 μm per layer are alternately formed, and these films are combined.
A total of three or more layers are formed.
Powder having a multilayer film on the surface, characterized in that the powder has high quality .
を有するものであることを特徴とする請求項１記載の表
面に多層膜を有する粉体。2. The method according to claim 1, wherein said metal powder or metal compound powder is magnetic.
2. The table according to claim 1, wherein the table has
Powder having a multilayer film on the surface .
するあるいは有しない金属粉体又は金属膜を有する金属
化合物粉体を分散し、該金属アルコキシドを加水分解す
ることにより、前記金属粉体又は金属化合物粉体の表面
に金属酸化物膜を形成させ、前記金属酸化物膜を形成さ
せた金属粉体又は金属化合物粉体の表面に金属膜を形成
することを特徴とする表面に金属酸化物膜及び金属膜を
交互に形成し、かつこれらの膜を合計して３層以上形成
してなる粉体の製造方法。3. A method of dispersing a metal powder having or without a metal film or a metal compound powder having a metal film in a metal alkoxide solution and hydrolyzing the metal alkoxide, thereby obtaining the metal powder or metal. Forming a metal oxide film on the surface of the compound powder; forming a metal film on the surface of the metal powder or the metal compound powder on which the metal oxide film is formed; And metal films are alternately formed, and these films are formed in total of three or more layers.
A method for producing a powder.
属膜を有するあるいは有しない磁性を有する金属粉体又
は金属膜を有する金属化合物粉体を分散し、該金属アル
コキシドを加水分解することにより前記金属粉体又は金
属化合物粉体の表面に金属酸化物膜を形成させ、前記金
属酸化物膜を形成させた金属粉体又は金属化合物粉体の
表面に金属膜を形成することを特徴とする表面に金属酸
化物膜及び金属膜を交互に形成し、かつこれらの膜を合
計して３層以上形成してなる磁性粉体の製造方法。4. A metal powder having a magnetic property or a metal compound powder having a metal film, both having or not having a metal film, dispersed in a metal alkoxide solution, and the metal alkoxide is hydrolyzed to form the metal. Forming a metal oxide film on the surface of the powder or the metal compound powder, and forming a metal film on the surface of the metal powder or the metal compound powder on which the metal oxide film has been formed; A metal oxide film and a metal film are alternately formed, and these films are combined.
A method for producing a magnetic powder comprising a total of three or more layers .
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25217093A JP2582034B2 (en) | 1993-09-16 | 1993-09-16 | Powder having multilayer film on surface and method for producing the same |
| CA002114913A CA2114913C (en) | 1993-02-05 | 1994-02-03 | Powder having at least one layer and process for preparing the same |
| EP94101727A EP0609897B2 (en) | 1993-02-05 | 1994-02-04 | Powder having at least one layer and process for preparing the same |
| DE69413083T DE69413083T3 (en) | 1993-02-05 | 1994-02-04 | Powder with one layer and manufacturing process |
| US08/532,994 US5763085A (en) | 1993-02-05 | 1995-09-25 | Powder having at least one layer and process for preparing the same |
| US08/976,715 US6048574A (en) | 1993-02-05 | 1997-11-24 | Powder having at least one layer and process for preparing the same |
| HK98110742A HK1009976A1 (en) | 1993-02-05 | 1998-09-18 | Powder having at least one layer and process for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25217093A JP2582034B2 (en) | 1993-09-16 | 1993-09-16 | Powder having multilayer film on surface and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0790310A JPH0790310A (en) | 1995-04-04 |
| JP2582034B2 true JP2582034B2 (en) | 1997-02-19 |
Family
ID=17233470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25217093A Expired - Lifetime JP2582034B2 (en) | 1993-02-05 | 1993-09-16 | Powder having multilayer film on surface and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2582034B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3686167B2 (en) * | 1996-06-10 | 2005-08-24 | 日鉄鉱業株式会社 | Multi-layer coating powder |
| KR100493873B1 (en) * | 1996-06-10 | 2006-01-12 | 닛데츠 고교 가부시키가이샤 | Color magnetic toner and its manufacturing method |
| JP3670395B2 (en) * | 1996-06-10 | 2005-07-13 | 日鉄鉱業株式会社 | Multilayer coating powder and method for producing the same |
| JPH09329915A (en) * | 1996-06-10 | 1997-12-22 | Nittetsu Mining Co Ltd | Color magnetic tower and its production |
| CN1137220C (en) | 1996-06-10 | 2004-02-04 | 日铁矿业株式会社 | Multilayer coated powder |
| JP3742153B2 (en) * | 1996-08-29 | 2006-02-01 | 日鉄鉱業株式会社 | Coated powder consolidated product and method for producing the same |
| JP2000222615A (en) | 1998-11-27 | 2000-08-11 | Nittetsu Mining Co Ltd | Authenticity discriminating method, object of authenticity discrimination and autheticity discrimination device |
| US6325847B1 (en) * | 1999-11-30 | 2001-12-04 | Engelhard Corporation | Precious metal color effect materials and production thereof |
| KR100877115B1 (en) * | 2001-04-27 | 2009-01-07 | 도와 홀딩스 가부시끼가이샤 | Copper powder for electroconductive paste excellent in resistance to oxidation and method for preparation thereof |
| EP1484365B1 (en) | 2002-03-14 | 2020-04-29 | Nittetsu Mining Co., Ltd. | Coated powder, coating composition and coated article |
| JP2010529237A (en) | 2007-06-05 | 2010-08-26 | バンク オブ カナダ | Ink or toner composition, method of use and product obtained from the method |
| KR101341150B1 (en) * | 2011-12-22 | 2013-12-11 | 한국조폐공사 | Magnetic Particle Having High reflection protected layer and the Fabrication Method Thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54797A (en) * | 1977-06-03 | 1979-01-06 | Koujiyundo Kagaku Kenkiyuushiy | Method of making sendust magnetic body |
| JPS58212104A (en) * | 1982-06-03 | 1983-12-09 | Chisso Corp | Magnetic metal fine grain |
| JPS5931003A (en) * | 1982-08-14 | 1984-02-18 | Hitachi Maxell Ltd | Metal magnetic powder and manufacture thereof |
-
1993
- 1993-09-16 JP JP25217093A patent/JP2582034B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54797A (en) * | 1977-06-03 | 1979-01-06 | Koujiyundo Kagaku Kenkiyuushiy | Method of making sendust magnetic body |
| JPS58212104A (en) * | 1982-06-03 | 1983-12-09 | Chisso Corp | Magnetic metal fine grain |
| JPS5931003A (en) * | 1982-08-14 | 1984-02-18 | Hitachi Maxell Ltd | Metal magnetic powder and manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0790310A (en) | 1995-04-04 |
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