JPH0258353B2 - - Google Patents
Info
- Publication number
- JPH0258353B2 JPH0258353B2 JP61052045A JP5204586A JPH0258353B2 JP H0258353 B2 JPH0258353 B2 JP H0258353B2 JP 61052045 A JP61052045 A JP 61052045A JP 5204586 A JP5204586 A JP 5204586A JP H0258353 B2 JPH0258353 B2 JP H0258353B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- palladium
- inorganic
- metal
- plated
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 96
- 239000002245 particle Substances 0.000 claims description 62
- 239000010954 inorganic particle Substances 0.000 claims description 51
- 229910052763 palladium Inorganic materials 0.000 claims description 48
- 239000000084 colloidal system Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007863 gel particle Substances 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims 1
- 229910052596 spinel Inorganic materials 0.000 claims 1
- 238000007747 plating Methods 0.000 description 34
- 239000000126 substance Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative 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 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- ZMLDXWLZKKZVSS-UHFFFAOYSA-N palladium tin Chemical compound [Pd].[Sn] ZMLDXWLZKKZVSS-UHFFFAOYSA-N 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 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
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride 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
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Powder Metallurgy (AREA)
- Chemically Coating (AREA)
- Conductive Materials (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
〔産業上の利用分野〕
本発明は、粒子表面が金属めつきされた無機粒
子粉末の製造方法に関するものであり、詳しく
は、無機粒子の粒子表面にパラジウムコロイドを
均一且つ強固に吸着させた後化学めつきをするこ
とにより、粒子表面が均一且つ強固に金属めつき
された無機粒子粉末を得ることを目的とする。
その主な用途は、電磁波シールド用、導電性イ
ンキ用、導電性ポリマー用及び磁気記録用の材料
粒子粉末である。
〔従来の技術〕
近年、各種無機粒子粉末を化学めつきして各種
金属を付与することにより、導電性等の電気的性
質及び磁気的性質等の新しい機能を持たせたり、
また、無機粒子粉末自身が有する特性を向上又は
改良することが行われている。
無機粒子粉末に金属を付与する場合、付与され
た金属を長期に亘り、安定に維持する為には、金
属が無機粒子粉末の粒子表面に出来るだけ均一且
つ強固に付与されることが必要であり、無機粒子
粉末を含む高分子材料等の各種複合材料の製造工
程における機械的な粉砕や混合等によつて容易に
脱落しにくいことが要求される。
従来、無機粒子粉末を化学めつきする方法とし
て最も一般的な方法は、例えば、特開昭56−
25770号公報及び特公昭59−5663号公報に記載さ
れている通り、無機粒子粉末を強酸性塩化第一錫
溶液に浸漬し、次いで、強酸性塩化パラジウム溶
液に浸漬して活性化処理を施した後、化学めつき
する方法である。
〔発明が解決しようとする問題点〕
粒子表面に均一且つ強固に金属が付与された無
機粒子粉末は現在最も要求されているところであ
るが、前述の公知方法による場合には、未だ、こ
れら要求を満たすものではない。
即ち、前出特開昭56−25770号公報及び特公昭
59−5663号公報に記載の方法は、塩化第一錫と塩
化パラジウムの二つの浴を必要とし、お互いの液
が混入するのを防ぐために、各処理毎に水洗をし
なければならないので工程が非常に複雑である。
しかも、化学めつきのための触媒活性が低いの
で、２〜３度同じ処理を繰り返さなければ金属イ
オンの還元反応を惹起させるに充分なパラジウム
を付与することが出来ず、また、強酸により無機
粒子表面が劣化したり、溶解したりする為、化学
めつき処理の際の還元反応が妨げられ金属を均一
且つ強固に付与することが困難である。
殊に、炭酸カルシウム粒子や炭酸バリウム粒子
のように酸性領域で可溶性となる粒子は、金属め
つきすることが不可能であつた。
均一且つ強固に金属を付与する為の改良方法と
して、例えば、米国特許3011920号公報及び特開
昭52−117242号公報に記載の方法が提案されてい
る。米国特許3011920号公報に記載の方法は、被
めつき物を強酸性パラジウム−錫コロイド溶液に
接触させ、化学めつきのための触媒作用を行うパ
ラジウムを付与するものであるが、無機粒子の粒
子表面に均一且つ、強固に金属を付与すること
は、未だ、困難である。
この理由は、化学めつきの触媒として使用する
強酸性パラジウム−錫コロイドが調製後、凝集沈
澱や触媒活性の低下等の経時変化を生起しやすく
不安定なものである為であり、また、無機粒子の
粒子表面に、化学めつきの為の触媒として作用す
るパラジウム以外に触媒作用の妨げとなる錫水酸
化物までが多量に付与され、また、強酸により無
機粒子が劣化したり、溶解したりする為、化学め
つき処理の際の還元反応が妨げられる為である。
無機粒子の粒子表面から、触媒作用の妨げとな
る錫水酸化物等の不純物を除去する為、無機粒子
を強酸性パラジウム−錫コロイド溶液に浸漬した
後、更に、アルカリ溶液中で浸漬処理をしている
が、錫水酸化物等の不純物を完全に除去すること
は困難であり、しかも、工程が一層複雑化する。
特開昭52−117242号公報に記載の方法は、絶縁体
をパラジウム等の貴金属の含水酸化物を含む酸性
溶液で処理することにより、化学めつきのための
触媒作用を行うパラジウム等の貴金属の含水酸化
物を付与するものであるが、その組成に起因し
て、化学めつきのための触媒活性が不十分である
という欠点がある。
上述した通り、無機粒子の粒子表面に極めて容
易に均一且つ強固に金属を付与する方法の確立が
強く要望されている。
〔問題点を解決する為の手段〕
本発明者は、無機粒子の粒子表面に均一且つ強
固に金属を付与する方法について種々検討を重ね
た結果、本発明に到達したのである。
即ち、本発明は、無機粒子を含む水懸濁液と陽
イオン性、陰イオン性及び非イオン性界面活性剤
から選ばれた一種又は二種以上を含むパラジウム
ヒドロゾルとを混合撹拌して前記無機粒子の粒子
表面にパラジウムコロイドを吸着させ、次いで、
水洗、過した後、該パラジウムコロイドが吸着
されている無機粒子を化学めつきすることにより
粒子表面が金属めつきされた無機粒子を得ること
からなる金属めつきされた無機粒子粉末の製造方
法である。
〔作用〕
先ず、本発明において、最も重要な点は、活性
化処理にあたり使用するパラジウムヒドロゾルが
弱アルカリ性であり、且つ化学めつきの為の触媒
作用の妨げとなる錫水酸化物等の不純物を含有し
ておらず、しかも、長期に亘り安定である為、被
めつき物である無機粒子が溶けることなく、粒子
表面にパラジウムコロイドを均一且つ強固に吸着
させることができることに起因して、無機粒子の
粒子表面に均一且つ強固に化学めつきできる点で
ある。
本発明において、弱アルカリ性であり、且つ、
触媒作用の妨げとなるような不純物を含有してお
らず、しかも、長期に亘り安定であるパラジウム
ヒドロゾルは、パラジウムヒドロゾル中に陽イオ
ン性、陰イオン性及び非イオン性界面活性剤の一
種又は二種以上を存在させることにより調製して
いる。
次に、本発明実施にあたつての諸条件について
述べる。
本発明における無機粒子粉末としては、α−酸
化第二鉄、マグネタイト、マグヘマイト等の酸化
鉄粒子、Baフエライト、Srフエライト、Pbフエ
ライト等のマグネトプランバイト型フエライト粒
子、Mn−Znフエライト等のスピネル型フエライ
ト粒子、チタン酸カリウム粒子、炭酸カルシウム
粒子、シリカゲル粒子、酸化チタン粒子、酸化ア
ルミニウム粒子又は酸化アルミニウムゲル粒子、
炭酸バリウム粒子、ゼオライト粒子又はシラスバ
ルーン粒子から選ばれた一種又は二種以上の水不
溶性、難溶性の粒子を使用することができる。粒
子の大きさは0.01μｍ以上のものが適し、また、
針状、球状、粒状等のいかなる粒子形態であつて
も同様の効果を得ることができる。
本発明におけるパラジウムヒドロゾルは、陽イ
オン性、陰イオン性及び非イオン性界面活性剤の
一種又は二種以上の存在下、パラジム（）塩水
溶液、好ましくは塩化パラジウム（）水溶液を
水素化ホウ素ナトリウム、ジメチルアミンボラ
ン、ヒドラジンなどの還元剤で還元処理して得ら
れる（特開昭59−120249号公報）。ここで、界面
活性剤は、パラジウムヒドロゾルの凝集沈澱を防
ぐ安定剤として働くが、これには、ステアリルト
リメチルアンモニウムクロライドなどの陽イオン
性界面活性剤、ドデシルベンゼンスルホン酸ナト
リウム等の陰イオン性界面活性剤、およびポリエ
チレングリコール−ｐ−ノニルフエニルエーテル
などの非イオン性界面活性剤を用いることができ
る。ヒドロゾル中のパラジウム濃度は0.01〜10mg
−atom／の範囲がよい。
0.01mg−atom／以下の場合には、安定なパ
ラジウムヒドロゾルの調製はできるが、パラジウ
ムコロイドの濃度が薄いので、無機粒子表面にパ
ラジウムコロイドを吸着させる為に長時間を要
し、実用的ではない。
10mg−atom／以上の場合には、安定なパラ
ジウムヒドロゾルを得ることが出来ない。
界面活性剤の濃度は、0.002〜１％の範囲が望
ましい。
0.002％以下の場合には、安定なパラジウムヒ
ドロゾルを得ることが出来ない。
１％以上の場合には、界面活性剤の安定作用が
強い為、パラジウムコロイドの無機粒子表面への
吸着が遅く実用的ではない。
本発明におけるパラジウムコロイドの吸着量
は、無機粒子の種類に応じて化学めつきの為に必
要且つ充分な量を付与することが必要である。
均一且つ強固な化学めつきをする為には、例え
ば、シリカゲル粒子の場合には、１m2当たりの表
面に2μｇ以上、酸化チタン粒子の場合には、１
m2当たりの表面に86μｇ以上のパラジウムコロイ
ドが吸着されていることが必要である。
本発明におけるパラジウムコロイドの吸着速度
は、パラジウムヒドロゾルの温度、濃度及び界面
活性剤の種類等により異なる為、目的に応じて適
当な条件を設定すればよい。
温度は、０℃〜100℃の範囲で目的に応じて自
由に選択すればよく、温度が高くなる程パラジウ
ムコロイドの吸着速度は速くなる傾向にある。
本発明においては、無機粒子表面への吸着に関
与しない余分のパラジウムコロイドが付着してい
る場合には、その後の化学めつきに際して、余分
のパラジウムコロイドが化学めつき液中に単独分
離して、その部分で無機粒子表面とは別に化学め
つきが生起するので、無機粒子表面にパラジウム
コロイドを吸着させた後水洗し、過し、必要に
より更に乾燥することにより余分のパラジウムコ
ロイドを除去しておくことが好ましい。
本発明における化学めつきは常法により行うこ
とができる。即ち、パラジウムコロイドが吸着さ
れた無機粒子を含む水懸濁液と金属イオン及び還
元剤を含む化学めつき液とを混合撹拌することに
より、無機粒子に吸着されているパラジウムコロ
イド部分で金属イオンが還元されて金属が析出す
るものである。
本発明における化学めつきの為の金属イオン溶
液としては、電気的、磁気的性質を付与する為に
通常使用される中性又はアルカリ性のニツケル、
コバルト、銅、銀等の一種又は二種以上を使用す
ることができる。
本発明における化学めつきの為の還元剤として
は、次亜リン酸ナトリウム、ホルムアルデヒド、
ぶどう糖等を使用することができる。
〔実施例〕
次に実施例並びに比較例により本発明を説明す
る。
尚、実施例におけるパラジウム量は、試料を王
水（体積比で濃硝酸：濃塩酸＝１：１）に溶解
し、過することにより得られた液を、ICAP
−575型発光プラズマ分光分析（Nippon Jarrell
−Ash社製）を用いて測定した発光プラズマ分光
分析値を試料重量当たりに換算して示したもので
ある。
また、飽和磁束密度及び保磁力は、5KOeの磁
場において測定したものである。
導電率はTR6142電流発生器（タケダ理研(株)
製）及びME−540電圧計（SOAR(株)製）を用い
て、四端子法により測定したものである。
＜パラジウムヒドロゾルの調製＞試料Ａ〜Ｃ；
試料：Ａ
塩化パラジウム（）50μmolを塩化ナトリウ
ム250μmolを含む水溶液2.5mlに溶解し、次いで
純水で94mlに希釈した。この溶液を激しく撹拌し
ながら、ステアリルトリメチルアンモニウムクロ
ライド10mgを含む水溶液１mlを加え、次いで、水
素化ホウ素ナトリウム200μmolを含む水溶液５ml
を滴下すると、溶液の色が急変し、PH9.0の黒褐
色透明なパラジウムヒドロゾルを得た。
試料：Ｂ
界面活性剤としてポリエチレングリコール−ｐ
−ノニルフエニルエーテル（ポリエチレングリコ
ールの重合度10）を使用した以外は、試料Ａと同
様にしてPH8.5のパラジウムヒドロゾルを得た。
試料：Ｃ
界面活性剤としてドデシルベンゼンスルホン酸
ナトリウムを使用した以外は、試料Ａと同様にし
てPH8.7のパラジウムヒドロゾルを得た。
＜化学めつき液の調製＞試料〜；
試料：（ニツケルめつき液の調製）
無水塩化ニツケル（）0.1molを4mol／の
アンモニア水溶液に溶解し、該溶液に0.2mol／
の次亜リン酸ナトリウム500mlを加えた後、濃
塩酸により溶液のPHを8.9に調整した。
試料：（コバルトめつき液の調製）
0.05molの硫酸コバルト（）・７水塩、
0.2molの次亜リン酸ナトリウム、0.2molのクエ
ン酸ナトリウム・２水塩および0.5molの硫酸ア
ンモニウムを純水に溶解して全容１とし、該溶
液に7.4mol／のアンモニア水溶液を加えてPH
を10に調整した。
試料：（銅めつき液の調製）
0.8mol／のロツセル塩と、0.8mol／の水
酸化ナトリウムおよび0.5mol／の硫酸銅（）
５水塩を純水に溶解して100mlとし、さらに35％
ホルムアルデヒド溶液100mlを混合した。
＜無機粒子粉末の化学めつき＞ 実施例１〜15
比較例１〜15；
実施例 １
平均粒子径0.25μｍの粒状マグネタイト粒子粉
末（戸田工業(株)製）（導電率5.0×10-9s／cm）7.5
ｇを試料Ａのパラジウムヒドロゾル282mlに室温
下60分間浸漬した後、水洗、別した。
得られたパラジウムコロイドが吸着されたマグ
ネタイト粒子粉末は、原子吸光法により測定した
結果、140μｇのパラジウムコロイド（マグネタ
イト粒子粉末に対し0.2重量％に該当する）が吸
着されていた。
上記パラジウムコロイドが吸着されたマグネタ
イト粒子粉末を試料のニツケル化学めつき液に
室温下浸漬した後、水洗、乾燥した。
得られたマグネタイト粒子粉末の導電率は1.5
×102s／cmであり、電子顕微鏡観察の結果、粒子
表面に均一且つ強固にめつきがされていることが
確認された。
実施例 ２〜15
被めつき物である無機粒子粉末の種類、パラジ
ウムヒドロゾルの種類及び化学めつき液の種類を
種々変えた以外は実施例１と同様にして金属めつ
きされた無機粒子粉末を得た。この時の主要製造
条件及び金属めつきされた無機粒子粉末の諸特性
を表１に示す。
また、実施例２〜15の各実施例で得られた金属
めつきされた無機粒子粉末は、いずれも電子顕微
鏡観察の結果、粒子表面が均一且つ強固にめつき
されていことが確認された。
比較例 １
実施例１と同一のマグネタイト粒子粉末５ｇを
塩化第一錫1.7ｇ、濃塩酸3.0ml及び水150mlから
なる溶液に分散混合し、60分間放置した後、別
した。得られた粒子粉末を塩化パラジウム0.13
ｇ、濃塩酸3.0ml及び水150mlからなる溶液に分散
混合し、60分間放置した後、別して活性化処理
をおこなつた。
活性化処理がされたマグネタイト粒子粉末を試
料のニツケルめつき液を用いて実施例１と同一
の手順でニツケルめつきを行つた。
得られたマグネタイト粒子粉末は、電子顕微鏡
観察の結果、粒子表面が凸凹状態で不均一なもの
であつた。
比較例 ２〜15
実施例２〜15の各実施例の無機粒子粉末を用
い、比較例１と同様に活性化処理をした。比較例
９〜11で用いた炭酸カルシウム粒子は、強酸性塩
化第一錫溶液中に溶解した。
比較例２〜８及び比較例12〜15の活性化処理後
の無機粒子粉末を用いて実施例２〜８及び実施例
12〜15のそれぞれと同様にして金属めつきされた
無機粒子粉末を得た。
比較例２〜８及び比較例12〜15の各比較例で得
られた金属めつきされた無機粒子粉末は、いずれ
も、電子顕微鏡観察の結果、粒子表面が凸凹状態
で不均一なものであつた。
[Industrial Application Field] The present invention relates to a method for producing inorganic particle powder whose particle surface is metal-plated, and more specifically, after palladium colloid is uniformly and firmly adsorbed on the particle surface of inorganic particles. The purpose is to obtain inorganic particle powder whose particle surface is uniformly and strongly metal-plated by chemical plating. Its main uses are material particles for electromagnetic shielding, conductive inks, conductive polymers, and magnetic recording. [Prior art] In recent years, by chemically plating various inorganic particles and adding various metals to them, new functions such as electrical properties such as conductivity and magnetic properties can be imparted.
Further, efforts are being made to improve or improve the properties of the inorganic particles themselves. When adding metal to inorganic particles, in order to maintain the applied metal stably over a long period of time, it is necessary to apply the metal as uniformly and firmly as possible to the particle surface of the inorganic particles. It is required that the material is not easily fallen off during mechanical crushing, mixing, etc. in the manufacturing process of various composite materials such as polymeric materials containing inorganic particle powder. Conventionally, the most common method for chemically plating inorganic particles is, for example, the method disclosed in Japanese Patent Application Laid-open No. 1983-
As described in Publication No. 25770 and Japanese Patent Publication No. 59-5663, inorganic particles were immersed in a strongly acidic stannous chloride solution, and then immersed in a strongly acidic palladium chloride solution for activation treatment. This is followed by chemical plating. [Problems to be Solved by the Invention] Currently, inorganic particle powder in which metal is uniformly and firmly applied to the particle surface is most in demand, but the above-mentioned known methods have not yet met these demands. It's not fulfilling. That is, the aforementioned Japanese Patent Application Publication No. 56-25770 and
The method described in Publication No. 59-5663 requires two baths of stannous chloride and palladium chloride, and in order to prevent the two baths from mixing, the process must be washed with water after each treatment. It's very complicated.
Moreover, since the catalytic activity for chemical plating is low, sufficient palladium cannot be applied to the metal ion reduction reaction unless the same treatment is repeated two or three times. Because the metal deteriorates or dissolves, the reduction reaction during chemical plating is hindered, making it difficult to uniformly and firmly apply the metal. In particular, it has been impossible to metal plate particles such as calcium carbonate particles and barium carbonate particles that are soluble in acidic regions. As an improved method for applying metal uniformly and firmly, methods described in, for example, US Pat. The method described in U.S. Pat. No. 3,011,920 involves bringing the object to be plated into contact with a strongly acidic palladium-tin colloidal solution to impart palladium that acts as a catalyst for chemical plating. It is still difficult to apply metal uniformly and firmly to the substrate. The reason for this is that the strongly acidic palladium-tin colloid used as a catalyst for chemical plating is unstable and tends to undergo changes over time such as agglomeration and precipitation and a decrease in catalytic activity after preparation. In addition to palladium, which acts as a catalyst for chemical plating, a large amount of tin hydroxide, which obstructs the catalytic action, is added to the surface of the particles, and strong acids degrade or dissolve inorganic particles. This is because the reduction reaction during chemical plating treatment is hindered. In order to remove impurities such as tin hydroxide that impede catalytic action from the particle surface of the inorganic particles, the inorganic particles are immersed in a strongly acidic palladium-tin colloidal solution and then further immersed in an alkaline solution. However, it is difficult to completely remove impurities such as tin hydroxide, and the process becomes even more complicated.
The method described in JP-A No. 52-117242 involves treating an insulator with an acidic solution containing a hydrated oxide of a noble metal such as palladium, which acts as a catalyst for chemical plating. Although it imparts oxides, it has the drawback of insufficient catalytic activity for chemical plating due to its composition. As mentioned above, there is a strong desire to establish a method for extremely easily, uniformly and strongly applying metal to the particle surface of inorganic particles. [Means for Solving the Problems] The present inventor has arrived at the present invention as a result of various studies on methods for uniformly and firmly applying metal to the particle surfaces of inorganic particles. That is, the present invention involves mixing and stirring an aqueous suspension containing inorganic particles and a palladium hydrosol containing one or more selected from cationic, anionic, and nonionic surfactants. Palladium colloid is adsorbed onto the particle surface of inorganic particles, and then
A method for producing metal-plated inorganic particle powder, which comprises obtaining inorganic particles with metal-plated particle surfaces by chemically plating the inorganic particles on which the palladium colloid has been adsorbed after washing with water and filtering. be. [Function] First of all, the most important point in the present invention is that the palladium hydrosol used in the activation treatment is weakly alkaline and free of impurities such as tin hydroxide that interfere with the catalytic action for chemical plating. Palladium colloid is not contained and is stable over a long period of time, so palladium colloid can be uniformly and strongly adsorbed onto the surface of the particles without dissolving the inorganic particles on which they are coated. The point is that chemical plating can be uniformly and firmly applied to the particle surface of the particles. In the present invention, it is weakly alkaline, and
Palladium hydrosol, which does not contain impurities that would interfere with catalytic activity and is stable over a long period of time, is a type of cationic, anionic, and nonionic surfactant in palladium hydrosol. Or, it is prepared by having two or more types present. Next, various conditions for implementing the present invention will be described. Inorganic particles in the present invention include iron oxide particles such as α-ferric oxide, magnetite, and maghemite, magnetoplumbite-type ferrite particles such as Ba ferrite, Sr ferrite, and Pb ferrite, and spinel-type ferrite particles such as Mn-Zn ferrite. ferrite particles, potassium titanate particles, calcium carbonate particles, silica gel particles, titanium oxide particles, aluminum oxide particles or aluminum oxide gel particles,
One or more types of water-insoluble or sparingly soluble particles selected from barium carbonate particles, zeolite particles, and shirasu balloon particles can be used. Suitable particle size is 0.01 μm or more, and
The same effect can be obtained regardless of the shape of the particles, such as acicular, spherical, or granular. The palladium hydrosol in the present invention is prepared by mixing a palladium salt aqueous solution, preferably a palladium chloride salt aqueous solution, with sodium borohydride in the presence of one or more of cationic, anionic and nonionic surfactants. , dimethylamine borane, hydrazine, or the like (Japanese Patent Application Laid-open No. 120249/1983). Here, the surfactant acts as a stabilizer to prevent coagulation and precipitation of palladium hydrosol, and this includes cationic surfactants such as stearyltrimethylammonium chloride, anionic surfactants such as sodium dodecylbenzenesulfonate, etc. Active agents and nonionic surfactants such as polyethylene glycol-p-nonylphenyl ether can be used. Palladium concentration in hydrosol is 0.01-10mg
-atom/ range is good. At 0.01 mg-atom/or less, a stable palladium hydrosol can be prepared, but since the concentration of palladium colloid is low, it takes a long time to adsorb the palladium colloid on the surface of the inorganic particles, making it impractical. do not have. If the amount is 10 mg-atom/or more, a stable palladium hydrosol cannot be obtained. The concentration of the surfactant is preferably in the range of 0.002 to 1%. If it is less than 0.002%, a stable palladium hydrosol cannot be obtained. If it is 1% or more, the stabilizing effect of the surfactant is strong, so that the adsorption of palladium colloid to the surface of the inorganic particles is slow, making it impractical. The adsorption amount of palladium colloid in the present invention needs to be a necessary and sufficient amount for chemical plating depending on the type of inorganic particles. In order to achieve uniform and strong chemical plating, for example, in the case of silica gel particles, 2 μg or more is applied to the surface per square meter, and in the case of titanium oxide particles, 1 μg or more is applied to the surface per square meter.
It is necessary that at least 86 μg of palladium colloid is adsorbed on the surface per m 2 . Since the adsorption rate of palladium colloid in the present invention varies depending on the temperature, concentration, type of surfactant, etc. of palladium hydrosol, appropriate conditions may be set depending on the purpose. The temperature may be freely selected in the range of 0°C to 100°C depending on the purpose, and the higher the temperature, the faster the palladium colloid adsorption rate tends to be. In the present invention, if extra palladium colloid that does not participate in adsorption onto the inorganic particle surface is attached, the extra palladium colloid is separated into the chemical plating solution during subsequent chemical plating. Chemical plating occurs on that part separately from the surface of the inorganic particles, so after adsorbing palladium colloid on the surface of the inorganic particles, remove excess palladium colloid by washing with water, filtering, and further drying if necessary. It is preferable. Chemical plating in the present invention can be performed by a conventional method. That is, by mixing and stirring an aqueous suspension containing inorganic particles on which palladium colloid has been adsorbed and a chemical plating solution containing metal ions and a reducing agent, metal ions are absorbed in the palladium colloid portion adsorbed on the inorganic particles. It is reduced and metal is precipitated. The metal ion solution for chemical plating in the present invention includes neutral or alkaline nickel, which is commonly used to impart electrical and magnetic properties.
One or more of cobalt, copper, silver, etc. can be used. Reducing agents for chemical plating in the present invention include sodium hypophosphite, formaldehyde,
Glucose etc. can be used. [Example] Next, the present invention will be explained with reference to Examples and Comparative Examples. In addition, the amount of palladium in the examples is determined by dissolving the sample in aqua regia (concentrated nitric acid: concentrated hydrochloric acid = 1:1 by volume) and filtering the solution obtained by ICAP.
−575 type luminescence plasma spectrometry (Nippon Jarrell)
-Ash Co., Ltd.)) is calculated based on the weight of the sample. Moreover, the saturation magnetic flux density and coercive force were measured in a magnetic field of 5 KOe. Conductivity was measured using TR6142 current generator (Takeda Riken Co., Ltd.)
(manufactured by SOAR Co., Ltd.) and ME-540 voltmeter (manufactured by SOAR Co., Ltd.) using the four-terminal method. <Preparation of palladium hydrosol> Samples A to C; Sample: A 50 μmol of palladium chloride () was dissolved in 2.5 ml of an aqueous solution containing 250 μmol of sodium chloride, and then diluted to 94 ml with pure water. While vigorously stirring this solution, 1 ml of an aqueous solution containing 10 mg of stearyltrimethylammonium chloride was added, followed by 5 ml of an aqueous solution containing 200 μmol of sodium borohydride.
When added dropwise, the color of the solution suddenly changed, and a transparent palladium hydrosol with a pH of 9.0 was obtained. Sample: B Polyethylene glycol-p as surfactant
- A palladium hydrosol with a pH of 8.5 was obtained in the same manner as Sample A except that nonylphenyl ether (polymerization degree of polyethylene glycol: 10) was used. Sample: C A palladium hydrosol with a pH of 8.7 was obtained in the same manner as Sample A except that sodium dodecylbenzenesulfonate was used as a surfactant. <Preparation of chemical plating solution>Sample~; Sample: (Preparation of nickel plating solution) Dissolve 0.1 mol of anhydrous nickel chloride () in 4 mol/aqueous ammonia solution, and add 0.2 mol//
After adding 500 ml of sodium hypophosphite, the pH of the solution was adjusted to 8.9 with concentrated hydrochloric acid. Sample: (Preparation of cobalt plating solution) 0.05 mol of cobalt sulfate () heptahydrate,
Dissolve 0.2 mol of sodium hypophosphite, 0.2 mol of sodium citrate dihydrate, and 0.5 mol of ammonium sulfate in pure water to make a total volume of 1, and add 7.4 mol/aqueous ammonia solution to the solution to adjust the pH.
was adjusted to 10. Sample: (Preparation of copper plating solution) 0.8mol/Rotussel salt, 0.8mol/ sodium hydroxide, and 0.5mol/copper sulfate ()
Dissolve pentahydrate salt in pure water to make 100ml, and then add 35%
100ml of formaldehyde solution was mixed. <Chemical plating of inorganic particles> Examples 1 to 15
Comparative Examples 1 to 15; Example 1 Granular magnetite particle powder with an average particle diameter of 0.25 μm (manufactured by Toda Kogyo Co., Ltd.) (electrical conductivity 5.0 × 10 -9 s/cm) 7.5
g was immersed in 282 ml of palladium hydrosol of sample A for 60 minutes at room temperature, washed with water, and separated. The resulting magnetite particles adsorbed with palladium colloid were measured by atomic absorption spectrometry, and as a result, 140 μg of palladium colloid (corresponding to 0.2% by weight relative to the magnetite particles) was adsorbed. The magnetite particle powder on which palladium colloid was adsorbed was immersed in a sample nickel chemical plating solution at room temperature, then washed with water and dried. The conductivity of the obtained magnetite particle powder is 1.5
×10 2 s/cm, and as a result of electron microscopic observation, it was confirmed that the particle surfaces were uniformly and strongly plated. Examples 2 to 15 Inorganic particle powder plated with metal in the same manner as in Example 1 except that the type of inorganic particle powder to be plated, the type of palladium hydrosol, and the type of chemical plating solution were varied. I got it. Table 1 shows the main manufacturing conditions and the properties of the metal-plated inorganic particles. Moreover, as a result of electron microscopic observation, it was confirmed that the metal-plated inorganic particle powders obtained in each of Examples 2 to 15 were uniformly and firmly plated on the particle surface. Comparative Example 1 5 g of the same magnetite particle powder as in Example 1 was dispersed and mixed in a solution consisting of 1.7 g of stannous chloride, 3.0 ml of concentrated hydrochloric acid, and 150 ml of water, left for 60 minutes, and then separated. The obtained particle powder was mixed with palladium chloride 0.13
g, dispersed and mixed in a solution consisting of 3.0 ml of concentrated hydrochloric acid and 150 ml of water, left for 60 minutes, and then separately subjected to activation treatment. The activated magnetite particles were nickel-plated in the same manner as in Example 1 using a sample nickel-plating solution. As a result of electron microscopy observation of the obtained magnetite particles, the particle surface was uneven and nonuniform. Comparative Examples 2 to 15 The inorganic particles of Examples 2 to 15 were activated in the same manner as in Comparative Example 1. The calcium carbonate particles used in Comparative Examples 9-11 were dissolved in a strongly acidic stannous chloride solution. Examples 2 to 8 and Examples using the activated inorganic particle powders of Comparative Examples 2 to 8 and Comparative Examples 12 to 15
Metal-plated inorganic particle powders were obtained in the same manner as in Examples 12 to 15. As a result of electron microscopic observation, the metal-plated inorganic particle powders obtained in Comparative Examples 2 to 8 and Comparative Examples 12 to 15 were found to have uneven and uneven particle surfaces. Ta.
【表】【table】
本発明に係る金属めつきされた無機粒子粉末
は、前出実施例に示された通り、本発明において
用いられるパラジウムヒドロゾルが弱アルカリ性
であり、且つ、錫水酸化物等の化学めつきの触媒
作用を妨げる不純物を含有しておらず、しかも、
長期に亘り安定である為、被めつき物である無機
粒子が溶けることなく、粒子表面にパラジウムコ
ロイドを均一且つ強固に吸着させることができる
ことに起因して均一且つ強固な化学めつきがされ
たものであり、従つて、長期に亘り安定な金属め
つきされた無機粒子粉末が得られるので、電磁波
シールド用、導電性インキ用、導電性ポリマー用
及び磁気記録用の材料粒子粉末として好適であ
る。
In the metal-plated inorganic particle powder according to the present invention, the palladium hydrosol used in the present invention is weakly alkaline, and a chemical plating catalyst such as tin hydroxide is used, as shown in the above example. It does not contain impurities that interfere with its action, and
Because it is stable over a long period of time, it is possible to uniformly and firmly adsorb palladium colloid on the particle surface without dissolving the inorganic particles that are coated, resulting in uniform and strong chemical plating. Therefore, it is possible to obtain metal-plated inorganic particles that are stable over a long period of time, and are suitable as material particles for electromagnetic shielding, conductive ink, conductive polymers, and magnetic recording. .
Claims (1)
オン性及び非イオン性界面活性剤から選ばれた一
種又は二種以上を含むパラジウムヒドロゾルとを
混合撹拌して前記無機粒子の粒子表面にパラジウ
ムコロイドを吸着させ、次いで、水洗、過した
後、該パラジウムコロイドが吸着されている無機
粒子を化学めつきすることにより粒子表面が金属
めつきされた無機粒子を得ることを特徴とする金
属めつきされた無機粒子粉末の製造方法。 ２ 無機粒子が酸化鉄粒子、マグネトプランバイ
ト型フエライト粒子、スピネル型フエライト粒
子、チタン酸カリウム粒子、炭酸カルシウム粒
子、シリカゲル粒子、酸化チタン粒子、酸化アル
ミニウム粒子、酸化アルミニウムゲル粒子、ゼオ
ライト粒子又はシラスバルーン粒子から選ばれた
一種又は二種以上である特許請求の範囲第１項記
載の金属めつきされた無機粒子粉末の製造方法。[Claims] 1. An aqueous suspension containing inorganic particles and a palladium hydrosol containing one or more selected from cationic, anionic and nonionic surfactants are mixed and stirred. Palladium colloid is adsorbed on the particle surface of the inorganic particles, and then, after washing with water and filtering, the inorganic particles on which the palladium colloid is adsorbed are chemically plated to obtain inorganic particles whose particle surfaces are metal-plated. A method for producing metal-plated inorganic particle powder, characterized by: 2 The inorganic particles are iron oxide particles, magnetoplumbite type ferrite particles, spinel type ferrite particles, potassium titanate particles, calcium carbonate particles, silica gel particles, titanium oxide particles, aluminum oxide particles, aluminum oxide gel particles, zeolite particles or shirasu balloons. The method for producing a metal-plated inorganic particle powder according to claim 1, wherein the metal-plated inorganic particle powder is one or more selected from particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61052045A JPS62207875A (en) | 1986-03-10 | 1986-03-10 | Production of metal plated inorganic particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61052045A JPS62207875A (en) | 1986-03-10 | 1986-03-10 | Production of metal plated inorganic particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62207875A JPS62207875A (en) | 1987-09-12 |
| JPH0258353B2 true JPH0258353B2 (en) | 1990-12-07 |
Family
ID=12903846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61052045A Granted JPS62207875A (en) | 1986-03-10 | 1986-03-10 | Production of metal plated inorganic particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62207875A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2670796B2 (en) * | 1988-02-29 | 1997-10-29 | 戸田工業株式会社 | Method for producing metal-plated ceramic molded body |
| JP2619266B2 (en) * | 1988-07-04 | 1997-06-11 | 日本化学工業 株式会社 | Colored electroless plating powder and method for producing the same |
| JP2808639B2 (en) * | 1989-03-15 | 1998-10-08 | 松下電器産業株式会社 | Conductive particles for electrodes of ceramic electronic components |
| DE4141416A1 (en) * | 1991-12-11 | 1993-06-17 | Schering Ag | METHOD FOR COATING SURFACES WITH FINE-PARTICLE SOLID PARTICLES |
| EP0518422B1 (en) * | 1991-06-12 | 1995-09-06 | Koninklijke Philips Electronics N.V. | Method of selectively metallizing a pattern of a material other than glass on a glass substrate by electroless metallization |
| RU2420459C1 (en) * | 2009-10-14 | 2011-06-10 | Общество С Ограниченной Ответственностью "Нанокомпозит" | Potassium titanate powder |
| JP6675626B1 (en) * | 2019-07-12 | 2020-04-01 | 奥野製薬工業株式会社 | Composition for pretreatment of electroless plating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117242A (en) * | 1976-03-25 | 1977-10-01 | Western Electric Co | Metal attaching method |
-
1986
- 1986-03-10 JP JP61052045A patent/JPS62207875A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52117242A (en) * | 1976-03-25 | 1977-10-01 | Western Electric Co | Metal attaching method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62207875A (en) | 1987-09-12 |
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