JPS61258868A - Production of inorganic powder containing copper film of coating - Google Patents
Production of inorganic powder containing copper film of coatingInfo
- Publication number
- JPS61258868A JPS61258868A JP60100908A JP10090885A JPS61258868A JP S61258868 A JPS61258868 A JP S61258868A JP 60100908 A JP60100908 A JP 60100908A JP 10090885 A JP10090885 A JP 10090885A JP S61258868 A JPS61258868 A JP S61258868A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating
- inorganic powder
- coating
- powder
- 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.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000843 powder Substances 0.000 title claims abstract description 50
- 239000011248 coating agent Substances 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000007747 plating Methods 0.000 claims abstract description 70
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000010970 precious metal Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 abstract description 8
- 229910052763 palladium Inorganic materials 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 abstract description 2
- QYFRTHZXAGSYGT-UHFFFAOYSA-L hexaaluminum dipotassium dioxosilane oxygen(2-) difluoride hydrate Chemical compound O.[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O QYFRTHZXAGSYGT-UHFFFAOYSA-L 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000012799 electrically-conductive coating Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000010445 mica Substances 0.000 description 16
- 229910052618 mica group Inorganic materials 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- -1 shirasu balloons Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 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 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052628 phlogopite Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は銅被覆を有する無機粉体の製造方法に係り無電
解めっきによる無機粉体に対して均一な、しかも密着性
のある導電性にすぐれた銅被覆を有する粉体の製造方法
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an inorganic powder coated with copper, and relates to a method for producing an inorganic powder coated with copper, which provides uniform and adhesive conductivity to the inorganic powder by electroless plating. The present invention relates to a method for producing powder having an excellent copper coating.
本発明の方法で製造される銅被覆を有する無機粉体は電
磁波シールド材用フィラー、導電性塗料用フィラー、導
電性ペースト用フィラー、粉末冶金用フィラー等に用い
ることができる。The inorganic powder having a copper coating produced by the method of the present invention can be used as a filler for electromagnetic shielding materials, a filler for conductive paints, a filler for conductive pastes, a filler for powder metallurgy, and the like.
めっき浴中の金属イオンを、還元剤の作用によって還元
析出させる無電解めっきは、ニッケル、コバルト、銅等
あるいはこれらの合金のめっきに広く採用されており、
非金属基質上にもめっきできることから、無機粉体への
めっきにも適している。例えば、「実務表面技術Ｊ １
９８０年９月号８〜１２頁には、このような無機粉体へ
の適用例が概説されている。しかしながら、粉体の一粒
一粒に、めっきむらが少なく又密着性の優れためっきを
施すことは、該文献に概説されるような化学めっき法を
もってしても容易なことではな（、特に銅めっきの場合
には困難である。Electroless plating, in which metal ions in a plating bath are reduced and precipitated by the action of a reducing agent, is widely used for plating nickel, cobalt, copper, etc. or their alloys.
Since it can be plated on non-metallic substrates, it is also suitable for plating on inorganic powders. For example, "Practical Surface Technology J 1
Examples of application to such inorganic powders are outlined on pages 8 to 12 of the September 1998 issue. However, it is not easy to plate each particle of powder with less unevenness and excellent adhesion, even with the chemical plating method outlined in this document (in particular, This is difficult in the case of copper plating.
無機粉体の銅めっきに付きむらがある場合、銅めっき量
が多い割合には、それを使用した導電性塗料および電磁
波シールド材の導電性及び電磁波シールド性が悪く、又
樹脂成分との混練の際、剥離する等の不都合がある。無
機粉体へ銅を化学めっきする方法として、特公昭５８−
１７８２５号公報に無機粉体を第１錫塩の酸性溶液に浸
漬し、ついで、パラジウム塩の酸性溶液に浸漬して（い
わゆるセンシタイジングーアクチベーションプロセス）
触媒化処理を行った後、無電解銅めっき液（ロッシェル
塩浴、ＥＤＴＡ塩浴）に浸漬、攪拌してめっきを行うこ
とにより、銅被覆を有する無機粉体を得る方法が記載さ
れている。しかしながら、これらの通常の化学めっき法
では、無機粉体を実質的に完全に被覆しうるような均一
なめっき層を形成させることは困難である上に、無機粉
体とめっき層との結合力即ち密着性が不充分である。If the copper plating of the inorganic powder is uneven, a large amount of copper plating will result in poor conductivity and electromagnetic shielding properties of the conductive paint and electromagnetic shielding material that use it, as well as poor kneading with the resin component. However, there are some inconveniences such as peeling. As a method of chemically plating copper on inorganic powder,
No. 17825 discloses that an inorganic powder is immersed in an acidic solution of a stannous salt, and then immersed in an acidic solution of a palladium salt (so-called sensitizing-activation process).
A method is described for obtaining an inorganic powder coated with copper by performing catalytic treatment and plating by dipping and stirring in an electroless copper plating solution (Rochelle salt bath, EDTA salt bath). However, with these ordinary chemical plating methods, it is difficult to form a uniform plating layer that can substantially completely cover the inorganic powder, and the bonding strength between the inorganic powder and the plating layer is low. That is, the adhesion is insufficient.
また、特開昭５９−１５７２６８号公報には、粉体を化
学めっ、き浴中に浸漬し、その表面に金属を被覆する化
学めっき法において、粉体の９０％以上の個数の粒子の
移動速度が５ｃｍ／秒以下となるような浴の流動状態下
で一定時間、初期めっき処理を続ける方法が記載されて
いる。しかし、この方法においても“付きむら”は防止
し得ても密着性についての改良はなされていない。Furthermore, Japanese Patent Application Laid-Open No. 59-157268 discloses that in a chemical plating method in which powder is immersed in a chemical plating bath and the surface thereof is coated with metal, more than 90% of the particles of the powder are coated with a metal. A method is described in which the initial plating process is continued for a certain period of time under a fluidized bath condition such that the moving speed is 5 cm/sec or less. However, although this method can prevent "uneven adhesion", it does not improve adhesion.
本発明者らは“付きむら”がなく、且つ、密着性の優れ
た銅被覆を有する無機粉体の製造方法を提供することを
、その目的とする。It is an object of the present inventors to provide a method for producing an inorganic powder having a copper coating with no "unevenness" and excellent adhesion.
本発明は表面に貴金属を捕捉した無機粉体に銅を化学め
っきするに当たり、化学めっきの開始から少なくとも５
分間の初期銅めっき速度を、０．５■／ ｃｏ！−ｈｒ
以下に保持することを特徴とする銅被覆を有する無機粉
体の製造方法である。In chemically plating copper on an inorganic powder that captures precious metals on the surface, the present invention provides at least 5
The initial copper plating speed per minute is 0.5■/co! -hr
This is a method for producing an inorganic powder having a copper coating, which is characterized in that the following conditions are maintained.
本発明において、銅被覆の対象とする表面に貴金属を捕
捉した無機粉体は、公知の種々の方法に従って作ること
ができる。例えば、塩化第１錫の酸性溶液に浸漬した後
、貴金属の酸性溶液に浸漬する方法、塩化第１錫及び貴
金属の混合酸性溶液に浸漬処理した後、塩酸溶液で処理
する方法、貴金属捕捉性表面処理剤を用いて表面処理し
た粉体を貴金属を含む溶液で処理する方法等が知られて
おり、これらの何れの方法をも採用できる。In the present invention, the inorganic powder in which precious metals are captured on the surface to be coated with copper can be produced according to various known methods. For example, a method in which the surface is immersed in an acidic solution of stannous chloride and then in an acidic solution of a precious metal, a method in which the surface is immersed in a mixed acidic solution of stannous chloride and a precious metal and then treated with a hydrochloric acid solution, and a surface that captures precious metals. A method is known in which powder whose surface has been treated with a treatment agent is treated with a solution containing a noble metal, and any of these methods can be employed.
表面に貴金属を捕捉した無機粉体として、パラジウム、
白金、ロジウム、金などの貴金属が、無機粉体１００重
量部に対して、３Ｘ１０−’〜３ Ｘ １０− ’重量
部捕捉されたものが好ましい。Palladium, as an inorganic powder with precious metals captured on its surface
Preferably, 3 x 10-' to 3 x 10-' parts by weight of noble metals such as platinum, rhodium, gold, etc. are captured per 100 parts by weight of the inorganic powder.
無機粉体としては、銅化学めっきに対して、安定性の良
いものであれば制限はなく、マスコバイトマイカ、フロ
ゴパイトマイカ、合成のフッ素系マイカなどの板状マイ
カ、チタン酸カリウムウィスカー、ウオラストナイト、
アスベスト、セピオライトなどの針状鉱物、シリカ、ア
ルミナ、タルク、シラスバルーン、グラファイト、ガラ
スフレーク、ガラスファイバー、カーボンファイバー、
シリコンファイバー、窒化珪素、炭化珪素等が例示でき
る。特に、形状については制限がなく、板状、針状、繊
維状、粒状、など種々の形状のものが使用できる。There are no restrictions on the inorganic powder as long as it is stable for copper chemical plating, such as plate-shaped mica such as muscovite mica, phlogopite mica, synthetic fluorine-based mica, potassium titanate whiskers, Wolastonite,
Acicular minerals such as asbestos and sepiolite, silica, alumina, talc, shirasu balloons, graphite, glass flakes, glass fiber, carbon fiber,
Examples include silicon fiber, silicon nitride, and silicon carbide. In particular, the shape is not limited, and various shapes such as plate, needle, fiber, and granule can be used.
銅化学めっき液としては、通常の化学銅めっき液を用い
ることができる。即、銅源としては、硫酸銅、塩化銅、
硝酸銅等の塩類、又銅イオンの錯化剤としては、ＢＤＴ
Ａ塩、ロッシェル塩類等、還元剤としては、ホルマリン
、パラホルムアルデヒド等およびｐＨｔＪｌ整剤として
は、水酸化ナトリウム、炭酸ナトリウムの水溶液を用い
る。更に液の安定剤として、界面活性剤、シアン塩類等
を微量添加することができる。具体的には、硫酸銅３゜
６％、ＥＤＴＡ塩７．３％、ホルマリン２．６％、苛性
ソーダ０．３％の液が使用できる。As the copper chemical plating solution, a normal chemical copper plating solution can be used. Therefore, copper sources include copper sulfate, copper chloride,
Salts such as copper nitrate, and as a complexing agent for copper ions, BDT
A salt, Rochelle's salts, etc. are used as the reducing agent, such as formalin, paraformaldehyde, etc., and as the pHtJl adjuster, an aqueous solution of sodium hydroxide or sodium carbonate is used. Furthermore, a small amount of a surfactant, cyanide salts, etc. can be added as a liquid stabilizer. Specifically, a solution containing 3.6% copper sulfate, 7.3% EDTA salt, 2.6% formalin, and 0.3% caustic soda can be used.
銅めっき速度を、０．５■／ｃｊ−ｈｒ以下に保持する
ためには種々の方法があるが、銅めっき速度は、各イオ
ン濃度、還元剤濃度、温度およびｐＨに依存するのでイ
オン濃度および還元剤濃度を一定に設定し、温度及びＰ
Ｈをコントロールすることにより、銅めっき速度をコン
トロールすることができる。即、ｐＨを下げることによ
り、また温度を低くすることによりめっき速度を小さく
することができる。通常は、温度を一定に設定してｐＨ
をコントロールする方法が、容易に行いうる方法である
。There are various methods to keep the copper plating rate below 0.5■/cj-hr, but since the copper plating rate depends on each ion concentration, reducing agent concentration, temperature and pH, the ion concentration and The reducing agent concentration is set constant, and the temperature and P
By controlling H, the copper plating speed can be controlled. That is, the plating rate can be reduced by lowering the pH or by lowering the temperature. Normally, the temperature is set constant and the pH is
The easiest method is to control the
本発明において、めっき開始後のｐＨを、開始期のｐＨ
より低く保持することにより、めっき反応の開始から少
なくとも５分間の初期銅めっき速度を、０．５ｍ１ｒ／
−・ｈｒ以下に保持することができる。しかしながら、
余り低くすることは反応が実質的に停止してしまうので
実際的でない。めっき速度は、０．１■／ｃｉ・ｈｒ以
下では実際的でなく、０．６■／ｃｆｆｌ−ｈｒを越え
ると泡の発生が激しくなり、付きむら”を生じ、密着性
が低下する。In the present invention, the pH after the start of plating is
By keeping the initial copper plating rate lower than 0.5 ml/r/min for at least 5 minutes from the start of the plating reaction,
-・hr or less. however,
Setting it too low is not practical because the reaction will substantially stop. If the plating rate is less than 0.1 .mu./ci.hr, it is not practical, and if it exceeds 0.6 .mu./cffl-hr, the generation of bubbles will become more intense, resulting in uneven plating and poor adhesion.
この銅めっき速度でのめっきを、少なくとも５分間保持
することがめっきの“付きむら”の防止及び密着性に必
要である。これは粉体の表面に均一に実質的に第１層の
銅皮膜が形成されるのに相当する。It is necessary to maintain plating at this copper plating speed for at least 5 minutes to prevent "unevenness" of plating and to ensure good adhesion. This corresponds to substantially uniformly forming a first layer of copper film on the surface of the powder.
具体的な実施方法として、化学めっき液をあらかじめ所
定の温度に上げ、ＮａＯＨ溶液でその温度に最適な初期
ｐＨ値に調整する。この初期ｐＨ値は、その化学めっき
液でめっきが開始する下限値（粉体を投入して数秒〜数
十秒以内にめっきが開始するｐＨ値）とする。貴金属を
捕捉した無機粉体を、この化学めっき液に投入すると、
反応が開始しｐｏ値は急速に低下するが、ＮａＯＨ溶液
を添加する等の手段により、銅めっき速度を０．５ｗ／
ａｄ・ｈｒ以下で一定に保持することができる。この状
態でのめっきを、５〜２０分、好ましくは１０〜１５分
行う。その後のめっきは、任意のめっき速度で所望のめ
っき量に達するまで行うことができる。As a specific implementation method, the chemical plating solution is raised to a predetermined temperature in advance, and the initial pH value is adjusted to the optimum value for that temperature using a NaOH solution. This initial pH value is the lower limit value at which plating starts with the chemical plating solution (pH value at which plating starts within several seconds to several tens of seconds after the powder is introduced). When inorganic powder that captures precious metals is added to this chemical plating solution,
The reaction starts and the po value decreases rapidly, but the copper plating rate can be reduced to 0.5w/by adding NaOH solution or other means.
It can be kept constant below ad.hr. Plating in this state is performed for 5 to 20 minutes, preferably 10 to 15 minutes. Subsequent plating can be performed at any plating speed until a desired plating amount is reached.
例えば、ｐｉ（を１０〜９程度に調整してめっきを開始
し、５〜１０分間そのｐＨに保持して、初期めっき速度
を調整した後、ｐ）ｌを１１程度に上昇させ、比較的高
速でめっきを終了させることにより、 付きむら”がな
い、かつ、密着性の良好な銅被覆を有する無機粉体が得
られる。また、ｐＨを１０〜９程度に保持して、比較的
低速でめっきを終了させることも可能である。For example, start plating by adjusting pi() to around 10 to 9, hold it at that pH for 5 to 10 minutes, adjust the initial plating speed, then increase p)l to around 11, and then start plating at a relatively high speed. By finishing the plating with , it is possible to obtain an inorganic powder with a copper coating that is free of uneven adhesion and has good adhesion.In addition, the pH is maintained at about 10 to 9 and plating is performed at a relatively low speed. It is also possible to terminate the
本発明者らは、化学めっきによる無機粉体の銅被覆の
付きむら”および密着性に関し鋭意研究した結果、初期
銅めっき速度が大きく影響することを見出し、本発明を
完成した。The present inventors have developed a method for coating copper on inorganic powder by chemical plating.
As a result of intensive research into "unevenness" and adhesion, it was discovered that the initial copper plating speed has a large effect, and the present invention was completed.
無機粉体に対する化学銅めっきの場合、粉体の比表面積
が０，１ｒｒｒ／ｇ以上と大きいため、一旦めっきが開
始されると、めっき速度が加速度的に速くなり、Ｈ２ガ
スが急速に発生して、細かい粉末はＨ２ガスと共に浮上
してしまうとか、又銅が粉体の上に析出せず、単独に析
出する現象が現れ、“付きむら”が発生し、また、密着
性が低下する。In the case of chemical copper plating on inorganic powder, the specific surface area of the powder is as large as 0.1 rrr/g or more, so once plating starts, the plating speed accelerates and H2 gas is rapidly generated. As a result, the fine powder floats up together with the H2 gas, or the copper does not precipitate on the powder, but instead precipitates alone, resulting in "uneven adhesion" and reduced adhesion.
本発明において、初期めっき速度を低く保持し、一定量
の銅を低速でめっきすることにより・その後のめっき速
度にかかわりなく、Ｈ２ガスの急激な発生を防止でき、
粉末がＨ２ガスに包含されて表面に浮上することが防止
されると同時に、銅めっきの“付きむら”が防止され、
緻密で均一な密着性の強い銅被覆が無機粉体の表面に形
成させる。In the present invention, by keeping the initial plating speed low and plating a certain amount of copper at a low speed, it is possible to prevent rapid generation of H2 gas regardless of the subsequent plating speed.
Powder is prevented from being included in H2 gas and floating to the surface, and at the same time, "unevenness" of copper plating is prevented.
A dense, uniform, and highly adhesive copper coating is formed on the surface of the inorganic powder.
本発明を実施例により、さらに詳細に説明する。 The present invention will be explained in more detail with reference to Examples.
ただし本発明の範囲は、下記実施例により同等限定され
るものではない。However, the scope of the present invention is not limited to the same extent by the following examples.
実施例１
平均粒径１５０ｍｅｓｈのフロゴパイトマイカ（比表面
積； ０．２ ｒｒｆ／ｇ） ７５０ｇを、エポキシ樹
脂（エポキシ４ｇ 、ポリアミド４ｇ ）を溶解したエ
タノール−アセトン混合溶液中に３０分間浸漬し、次い
で濾過し、溶媒を揮散させた後、１００℃で１時間硬化
した。次にこのようにして表面処理されたマイカ７５０
ｇを、塩化パラジウムの塩酸酸性水溶液（ＰｄＣ１ｚ
ｆａ度ｌＸｌ０−’ｇ ／ｍｌ） １５００ｍｌに室
温で１時間浸漬したのち、濾過して下地処理を行い、表
面にパラジウムを捕捉したマイカを得た。Example 1 750 g of phlogopite mica (specific surface area: 0.2 rrf/g) with an average particle size of 150 mesh was immersed for 30 minutes in an ethanol-acetone mixed solution in which an epoxy resin (4 g of epoxy, 4 g of polyamide) was dissolved. After filtering and volatilizing the solvent, the mixture was cured at 100° C. for 1 hour. Next, the mica 750 surface-treated in this way
g in an acidic aqueous solution of palladium chloride in hydrochloric acid (PdC1z
After being immersed in 1500 ml of fa degree lXl0-'g/ml) at room temperature for 1 hour, it was filtered and a surface treatment was performed to obtain mica with palladium captured on its surface.
次に、この表面にパラジウムを捕捉したマイカを、次の
組成を有する銅無電解めっき液３０ Ｎに投入しめっき
反応を行った。反応温度６５℃、初期ｐＨ１１，５で反
応を開始し、その後、ＮａＯＨ液を滴下してｐＨを９．
５に保持し、銅の析出速度０．３６ｔｒｙ ／ ｃｒＡ
−ｈｒで反応を行った。反応時間は３０分であった。Next, the mica with palladium trapped on its surface was put into a 30 N copper electroless plating solution having the following composition to perform a plating reaction. The reaction was started at a reaction temperature of 65°C and an initial pH of 11.5, and then NaOH solution was added dropwise to adjust the pH to 9.5.
5, copper precipitation rate 0.36try/crA
The reaction was carried out for -hr. Reaction time was 30 minutes.
その結果、銅含有率２７．１％、体積充填率（ｖｆ）１
８％における粉体の体積固有抵抗値３．０Ｘ１０弓Ω・
ｃｒｎ、色調が輝銅色の銅被覆ををするマイカが得られ
た。又、得られた銅被覆を有するマイカは、均一なめっ
き被覆が得られていることが、走査型電子顕微鏡による
観察により確認された。As a result, the copper content was 27.1% and the volume filling factor (vf) was 1.
Volume specific resistance value of powder at 8% 3.0 x 10 bow Ω・
crn, a copper-coated mica with bright copper color was obtained. Further, it was confirmed by observation using a scanning electron microscope that the obtained mica having a copper coating had a uniform plating coating.
銅無電解めっき液の組成
Ｃｕ５Ｏｎ ・５ Ｈｚｏ ４０ ｇ ／ ｊ！
ＥＤＴＡ ・４ Ｎａ ８０ ｇ／Ｉｔ１（
ＣＨＯ（３５％） ７３ ｍｌ実施例２
平均粒径３２５ｍｅｓｈのフロゴバイトマイカ３００
ｇを、実施例１と同一の方法で表面処理を行い、更に塩
化パラジウム溶液で下地処理を行い、表面にパラジウム
を捕捉したマイカを得た。このマイカを、実施例１と同
一仕様の銅無電解めっき液３０１に投入し、めっき反応
を行った。反応温度は６５℃、初期ｐＨ１０，５で反応
を開始し、ＮａＯＨ溶液を滴下してｐＨを９．０に保持
して、銅の析出速度を０．２０ ｍｇ／ ｃｎ！ ・ｈ
ｒに調整し、１０分間反応を行い、次いで、ｐｔｔを１
０．０に調整して、銅の析出速度を０．５２ ｔｒｉ；
ｚ ／ ｃ＋Ａ−ｈｒとして、さらに１０分間反応を継
続し全反応を終了した。Composition of copper electroless plating solution Cu5On ・5 Hz 40 g/j!
EDTA ・4 Na 80 g/It1 (
CHO (35%) 73 ml Example 2 Phlogovite mica 300 with average particle size of 325 mesh
g was surface-treated in the same manner as in Example 1, and further treated with a palladium chloride solution to obtain mica with palladium trapped on its surface. This mica was put into a copper electroless plating solution 301 having the same specifications as in Example 1, and a plating reaction was performed. The reaction temperature was 65°C, the reaction was started at an initial pH of 10.5, and the pH was maintained at 9.0 by dropping NaOH solution to increase the copper precipitation rate to 0.20 mg/cn!・h
The reaction was carried out for 10 minutes, and then PTT was adjusted to 1
Adjust the copper precipitation rate to 0.52 tri;
The reaction was continued for an additional 10 minutes at z/c+A-hr to complete the entire reaction.
その結果、銅含有率４８％、・体積充填率（ｖｆ）１８
％における粉体の体積固有抵抗値２ Ｘ １０−３Ω・
ｃｍ、色調が銅色の銅被覆を有するマイカが得られた。As a result, the copper content was 48%, and the volume filling factor (vf) was 18.
Volume resistivity value of powder in %2 x 10-3Ω・
cm, a mica with a copper coating of copper color was obtained.
実施例１の場合と同様に均一なめっき被覆が得られた。As in Example 1, a uniform plating coating was obtained.
実施例３
平均粒径１５０ｍｅｓｈのガラスフレーク４５０ｇをＴ
−グリシドキシプロピルトリメトキシシランのアルコー
ル溶液で表面処理した後、実施例１と同一の方法でエポ
キシ樹脂（エポキシ＋ポリアミド）による表面処理及び
塩化パラジウム溶液で下地処理を行い、表面にパラジウ
ムを捕捉したガラスフレークを得た。このガラスフレー
クを、実施例１と同一仕様の無電解めっき液３０ βに
投入し、めっき反応を行った。反応温度７０℃、初期ｐ
Ｈ１１゜０で反応を開始し、その後、ＮａＯＨ溶液を滴
下してｐｉ（を９．５に保持し、銅の析出速度０．４２
■／ｃ１１！・ｈｒで５分間反応を行い、引続きいてｐ
Ｈを９゜０に保持して、０．３２■／−・ｈｒの銅の析
出速度で全反応を終了した。反応時間は５０分であった
。Example 3 450g of glass flakes with an average particle size of 150mesh were
- After surface treatment with an alcoholic solution of glycidoxypropyltrimethoxysilane, surface treatment with epoxy resin (epoxy + polyamide) and base treatment with palladium chloride solution are performed in the same manner as in Example 1 to capture palladium on the surface. obtained glass flakes. This glass flake was placed in an electroless plating solution 30β having the same specifications as in Example 1, and a plating reaction was performed. Reaction temperature 70℃, initial p
The reaction was started at H11°0, and then NaOH solution was added dropwise to maintain pi at 9.5, and the copper precipitation rate was 0.42.
■/c11!・Run for 5 minutes at hr, followed by p
H was maintained at 9°0 and the entire reaction was completed at a copper deposition rate of 0.32 ./-.hr. The reaction time was 50 minutes.
その結果、銅含有率３７％、体積充填率（ｖｆ）１８％
における粉体の体積固有抵抗値３．５ Ｘ １０−３Ω
・ｃｍ、色調輝銅色の、均一な銅被覆を有するガラスフ
レークを得た。As a result, the copper content was 37% and the volume filling factor (vf) was 18%.
Volume resistivity value of powder at 3.5 x 10-3Ω
.cm, glass flakes with a uniform copper coating of bright copper color were obtained.
応用例１ 電磁波シールド材への応用
実施例１で得た平均粒径１５０ｍｅｓｈの銅被覆マイカ
（Ｃｕ含有率２７．１％、粉体の体積固有抵抗値（ｖｆ
＝ １８％における） ３．０Ｘ１０−３Ω・Ｃｌ
１１）を、次の組成のニッケルめっき液を用いて、温度
４５℃、陰極電流密度１４／ｄｍの条件で、内側に隔膜
を設けたバレル（１９０ｍｍφＸ ２５０ ｍｍ ）中
において電気めっきを行った。その結果、銅含有率２０
゜５％、ニッケル含有率２１．０％、金属化率４１．５
％、粉体の体積固有抵抗値（ｖｆ ＝ １８％における
） ７．５Ｘ１０−３Ω’ｃｍ、真比重３．７７のＣ
ｕ −Ｎｉ２層コートマイカが得られた。この２層コー
トマイカを、ポリプロピレンに体積充填率１２．５％に
なるようにニーグーを用いて混練し、圧縮成形して複合
材（６０Ｘ ３０ Ｘ ２ ｍｍ ）を製造した。製造
した複合材の体積固有抵抗値は、６．５Ｘ１０−’Ω・
口であった。また、矩形導波管を用いた４０００ＭＨｚ
における電磁波透過損失率は、装置の測定限界である４
０ ｄＢ以上であった。Application example 1 Application to electromagnetic shielding material Copper-coated mica with an average particle size of 150 mesh obtained in Example 1 (Cu content 27.1%, powder volume resistivity (vf)
= at 18%) 3.0X10-3Ω・Cl
11) was electroplated using a nickel plating solution having the following composition at a temperature of 45° C. and a cathode current density of 14/dm in a barrel (190 mmφ×250 mm) provided with a diaphragm inside. As a result, the copper content was 20
゜5%, nickel content 21.0%, metallization rate 41.5
%, volume resistivity value of powder (at vf = 18%) 7.5X10-3 Ω'cm, true specific gravity 3.77 C
Mica coated with two u-Ni layers was obtained. This two-layer coated mica was kneaded in polypropylene using a Neegoo so that the volume filling rate was 12.5%, and the mixture was compression molded to produce a composite material (60 x 30 x 2 mm). The volume resistivity value of the manufactured composite material is 6.5X10-'Ω・
It was the mouth. In addition, 4000MHz using a rectangular waveguide
The electromagnetic wave transmission loss rate at 4 is the measurement limit of the device.
It was more than 0 dB.
ニッケルめっき液組成
ＮｉＳＯ４・ ６ Ｈ２Ｏ２５０ｇ／ＡＮｉＣ１ｚ・
６ ）１２０ ５０ ｇ／ ’８３Ｂ０３
５０ ｇ／ＡｐＨ３，０
応用例２ 電磁波シールド塗料への応用実施例２で得た
平均粒径３２５ｍｅｓｈの銅被覆マイカ（Ｃｕ含有率４
８％、粉体の体積固有抵抗値（ｖｆ＝ １８％における
） ２．０Ｘ１０−３Ω・ｃｆｆＩ）を、酸化防止剤
（ＣＢブライト 菱江化学株式会社製）１０％水溶液に
５分間浸漬し、濾過した後１００”Ｃで２時間乾燥し酸
化防止処理を行った。。この結果、体積固有抵抗値（ｖ
ｆ ＝ １８％における）は、３．５Ｘ１０−’Ω・ｃ
ｍとなった。次に、樹脂バインダーとして、アクリル系
塗料のアクリツクＩｌｈ ２０２６Ｇクリヤー及びシン
ナーに、乾燥塗膜中の体積充填率が３０％となる量のこ
のフィラーを混合し、塗料を作成した。次に、得られた
塗料をＡＢＳ樹脂にスプレーで塗装し、厚さが５０ μ
の塗膜を得た。乾燥後、塗膜の厚さ、表面抵抗および電
磁波シールド性能（電界シールド特性）を測定した。Nickel plating solution composition NiSO4・6 H2O250g/ANiC1z・
6) 120 50 g/'83B03
50 g/ApH3,0 Application example 2 Application to electromagnetic shielding paint Copper-coated mica with an average particle size of 325 mesh obtained in Example 2 (Cu content: 4
8%, powder volume resistivity value (at vf = 18%) 2.0 x 10-3 Ω/cffI) was immersed in a 10% aqueous solution of antioxidant (CB Bright, manufactured by Ryoe Chemical Co., Ltd.) for 5 minutes and filtered. After that, it was dried at 100"C for 2 hours to perform oxidation prevention treatment. As a result, the volume resistivity value (v
) at f = 18% is 3.5X10-'Ω・c
It became m. Next, as a resin binder, this filler was mixed with the acrylic paint Acryk Ilh 2026G clear and thinner in an amount such that the volume filling rate in the dry coating film was 30% to prepare a paint. The resulting paint was then sprayed onto ABS resin to a thickness of 50 μm.
A coating film was obtained. After drying, the thickness, surface resistance, and electromagnetic shielding performance (electric field shielding properties) of the coating film were measured.
その結果は次表の通り。The results are shown in the table below.
本発明の方法で製造した銅被覆を有する無機粉体は、実
施例及び応用例にも示したごとく、優れた体積固有抵抗
値を有し、また、該粉体を使用した電磁波シールド材（
塗膜）も、優れた電磁波シールド性能を示す。これらの
緒特性は、緻密で均一な、かつ、密着性に優れた銅被覆
を有する無機粉体であることを示している。As shown in the Examples and Application Examples, the inorganic powder coated with copper produced by the method of the present invention has an excellent volume resistivity value, and an electromagnetic shielding material using the powder (
coating film) also exhibits excellent electromagnetic shielding performance. These properties indicate that the powder is dense, uniform, and has a copper coating with excellent adhesion.
本発明は、緻密で均一な、かつ、密着性に優れた銅被覆
を有する無機粉体の、工業的規模での生産を可能とする
製造方法を提供するものである。The present invention provides a manufacturing method that enables production on an industrial scale of an inorganic powder having a copper coating that is dense, uniform, and has excellent adhesion.
Claims (1)
に当たり、化学めっきの開始から少なくとも５分間の初
期銅めっき速度を、０．５ｍｇ／ｃｍ＾２・ｈｒ以下に
保持することを特徴とする銅被覆を有する無機粉体の製
造方法When chemically plating copper on inorganic powder with precious metals captured on its surface, the initial copper plating rate for at least 5 minutes from the start of chemical plating is maintained at 0.5 mg/cm^2・hr or less. Method for producing inorganic powder with copper coating
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60100908A JPS61258868A (en) | 1985-05-13 | 1985-05-13 | Production of inorganic powder containing copper film of coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60100908A JPS61258868A (en) | 1985-05-13 | 1985-05-13 | Production of inorganic powder containing copper film of coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61258868A true JPS61258868A (en) | 1986-11-17 |
| JPH0453949B2 JPH0453949B2 (en) | 1992-08-28 |
Family
ID=14286437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60100908A Granted JPS61258868A (en) | 1985-05-13 | 1985-05-13 | Production of inorganic powder containing copper film of coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61258868A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219724A (en) * | 2005-02-10 | 2006-08-24 | Alps Electric Co Ltd | Electroless plating process |
-
1985
- 1985-05-13 JP JP60100908A patent/JPS61258868A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219724A (en) * | 2005-02-10 | 2006-08-24 | Alps Electric Co Ltd | Electroless plating process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0453949B2 (en) | 1992-08-28 |
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