JPH02173272A - Silver chemical plating liquid and protection of powder coated by silver - Google Patents
Silver chemical plating liquid and protection of powder coated by silverInfo
- Publication number
- JPH02173272A JPH02173272A JP32774288A JP32774288A JPH02173272A JP H02173272 A JPH02173272 A JP H02173272A JP 32774288 A JP32774288 A JP 32774288A JP 32774288 A JP32774288 A JP 32774288A JP H02173272 A JPH02173272 A JP H02173272A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- powder
- plating solution
- chemical
- silver plating
- 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.)
- Pending
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 128
- 239000004332 silver Substances 0.000 title claims abstract description 128
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000007747 plating Methods 0.000 title claims abstract description 73
- 239000000843 powder Substances 0.000 title claims abstract description 57
- 239000000126 substance Substances 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 title abstract 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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 claims abstract description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims abstract description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract 4
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 4
- 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 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229940100890 silver compound Drugs 0.000 claims description 4
- 150000003379 silver compounds Chemical class 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000003275 alpha amino acid group Chemical group 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 229910002804 graphite Inorganic materials 0.000 abstract description 11
- 239000010439 graphite Substances 0.000 abstract description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 5
- 150000001413 amino acids Chemical class 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 229960001484 edetic acid Drugs 0.000 abstract 1
- 238000007772 electroless plating Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 16
- 229910021382 natural graphite Inorganic materials 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- -1 silver ions Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 235000013922 glutamic acid Nutrition 0.000 description 3
- 239000004220 glutamic acid Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene 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
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 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
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZEWAYSHJQFFWIH-UHFFFAOYSA-N ethane-1,2-diamine;silver Chemical compound [Ag].NCCN ZEWAYSHJQFFWIH-UHFFFAOYSA-N 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- DNHVXYDGZKWYNU-UHFFFAOYSA-N lead;hydrate Chemical compound O.[Pb] DNHVXYDGZKWYNU-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、銀めっき液および銀被覆粉体の製造法に係り
、さらに詳しくは安定剤を含有する化学銀めっき液およ
びこの化学銀メツキ液を用いて粉体に銀皮膜を形成する
方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a silver plating solution and a silver-coated powder, and more specifically to a chemical silver plating solution containing a stabilizer and this chemical silver plating solution. The present invention relates to a method of forming a silver film on powder using.
本発明においては、密着性の優れた均一な銀皮膜を有す
る粉体が得られることから、導電性しゆう助材成形用粉
末、導電性ペースト用フィラー電気接点材料用フィラー
、導電性フィラー等に使用される銀被覆粉体の製造に好
適に採用される。In the present invention, since a powder having a uniform silver film with excellent adhesion can be obtained, it can be used as a powder for molding conductive additives, a filler for conductive paste, a filler for electrical contact materials, a conductive filler, etc. It is suitably adopted for producing the silver-coated powder used.
グラファイト、ガラス、シリカ等の粉体表面に銀化合物
含有水溶液から銀を化学的に析出させ被覆する方法は、
銀鏡反応として古くから行われており、たとえば硝ａｔ
Ｂのアンモニア水溶液にロアセル塩、ブドウ糖、ホルマ
リン等を加えて銀イオンを還元析出させる方法などが採
用されている。The method of chemically precipitating and coating silver from an aqueous solution containing a silver compound on the surface of powder such as graphite, glass, or silica is as follows:
It has been carried out for a long time as a silver mirror reaction, for example,
A method has been adopted in which silver ions are reduced and precipitated by adding Loisel salt, glucose, formalin, etc. to the ammonia aqueous solution of B.
また硝酸銀水溶液にクエン酸二水素アンモニウムを添加
し、ヒドラジンまたはその塩を加えアンモニアでｐＨ９
以上として銀被覆粉体を得る方法（特公昭５９−０４３
５２１号公報参照）などが開示されている。Also, ammonium dihydrogen citrate was added to the silver nitrate aqueous solution, hydrazine or its salt was added, and the pH was adjusted to 9 with ammonia.
Method for obtaining silver-coated powder as described above (Japanese Patent Publication No. 59-043
521), etc. are disclosed.
古くから採用されている銀鏡反応を利用して粉体の銀被
覆を行う方法においては、めっき液が不安定であること
、また得られる銀皮膜の均一性および密着性が不足する
ことから、導電性フィラー等に使用する銀被覆粉体の製
造法としては採用し難い。In the method of coating powder with silver using a silver mirror reaction, which has been used for a long time, the plating solution is unstable and the resulting silver film lacks uniformity and adhesion, so it is difficult to conductive. It is difficult to adopt this method as a method for producing silver-coated powder used in fillers and the like.
一方、特公昭５９−０４３５２１号公報に開示された方
法において、空気；囲気下で得られる銀波ｆｆ粉体は導
電性が不足し、十分な導電性を有する銀被覆粉体を製造
するためには、水素または不活性ガス雰囲気下において
、さらに加温することが要求され製造コストが高くなる
。On the other hand, in the method disclosed in Japanese Patent Publication No. 59-043521, the silver wave FF powder obtained under an atmosphere lacks electrical conductivity, and it is difficult to produce silver-coated powder with sufficient electrical conductivity. , further heating is required under a hydrogen or inert gas atmosphere, which increases manufacturing costs.
本発明は、密着性および導電性の優れた銀被覆粉体の工
業的な製造法およびこの方法で用いる安定性の優れた化
学銀めっき液を捉供することをその目的とする。An object of the present invention is to provide an industrial method for producing silver-coated powder with excellent adhesion and conductivity, and a chemical silver plating solution with excellent stability for use in this method.
本発明者等は、前記目的を達成すべく鋭意研究した結果
、ｉＮ錯イオンおよび還元剤を含有する化学銀めっき液
に分子内にカルボキシル基を有するアミノ酸を安定剤と
して添加することにより、めっき液が安定し、この化学
銀めっき液に表面活性化処理を施した粉体を浸漬し、恨
めつき液のｐ Ｈを制御して恨めつき反応を行うことに
より、密着性の優れた均一な銀皮膜が粉体表面に析出す
ることを見出し本発明を完成した。As a result of intensive research to achieve the above object, the present inventors have discovered that by adding an amino acid having a carboxyl group in the molecule as a stabilizer to a chemical silver plating solution containing an iN complex ion and a reducing agent, the plating solution can be improved. By immersing the surface-activated powder in this chemical silver plating solution and performing a plating reaction by controlling the pH of the plating solution, a uniform silver film with excellent adhesion can be created. The present invention was completed based on the discovery that the particles were precipitated on the surface of the powder.
本発明は、銀錯イオン、ｌ！錯イオンに対してｌ〜Ａ−
量の還元剤および銀量に対し１０〜２０重量％の安定剤
を含有することを特徴とする化学銀めっき液、およびｐ
Ｈを１２．５〜１３に調整した前記化学銀めっき液に、
表面活性化処理を施した粉体を浸漬して反応を開始し、
以降銀めっき液の温度を３０〜４０℃、ｐＨを１１．５
〜１２．０に制御し、銀めっき反応をそのまま維持する
か、もしくは銀錯イオンを追加しながら反応を継続する
ことを特徴とする銀被覆粉体の製造法である。The present invention provides a silver complex ion, l! l~A- for complex ions
A chemical silver plating solution characterized by containing an amount of reducing agent and a stabilizer of 10 to 20% by weight based on the amount of silver, and p
The chemical silver plating solution with H adjusted to 12.5 to 13,
The reaction is initiated by immersing the surface-activated powder into the solution.
After that, the temperature of the silver plating solution was set to 30 to 40°C, and the pH was set to 11.5.
This is a method for producing silver-coated powder, which is characterized by controlling the silver plating reaction to 12.0 and maintaining the silver plating reaction as it is, or continuing the reaction while adding silver complex ions.
本発明の化学銀めっき液において、銀錯イオンは、無機
または有機銀化合物と錯化剤とを反応させ錯体化した反
応生成物であり、銀化合物の錯化剤として、銀とキレー
ト環を形成し得る化合物、たとえばエチレンジアミン四
酢酸（ＥＤＴＡ）およびその塩、エチレンジアミン、ジ
エチレントリアミン、トリエチレンテトラミン、アンモ
ニア等が用いられ、特にエチレンジアミンが好ましく使
用される。これらの錯化剤は、銀イオンに対し２当量が
使用される。In the chemical silver plating solution of the present invention, the silver complex ion is a reaction product obtained by reacting an inorganic or organic silver compound with a complexing agent to form a complex, and as a complexing agent for the silver compound, it forms a chelate ring with silver. For example, ethylenediaminetetraacetic acid (EDTA) and its salts, ethylenediamine, diethylenetriamine, triethylenetetramine, ammonia, etc. are used, and ethylenediamine is particularly preferably used. These complexing agents are used in an amount of 2 equivalents relative to silver ions.
還元剤は、銀錯イオンを金属銀に還元するための成分で
あり、たとえばロッシェル塩、ブドウ糖。The reducing agent is a component for reducing silver complex ions to metallic silver, such as Rochelle salt and glucose.
ホルマリン、ヒドラジンおよびその塩などが使用される
。特に銀錯イオンの還元速度が比較的遅いロッシェル塩
、ブドウ糖などが好ましく使用されくは１．６〜２．
Ａ量の範囲である。Formalin, hydrazine and its salts are used. In particular, Rochelle's salt, glucose, etc., which have a relatively slow reduction rate of silver complex ions, are preferably used, preferably 1.6 to 2.
This is the range of A amount.
安定剤は、銀めっき液の安定性を保持するために添加さ
れる成分であり、分子内にカルボキシル基を有するアミ
ノ酸、たとえばグルタミン酸、アミノ酪酸などが用いら
れる。またハロゲン化カルボン酸、チオ硫酸ナトリウム
等の微量を前記安定剤と併用することにより、銀めっき
液の安定性をさらに向上することができる。安定剤は、
銀めっき液中の銀量に対して１０〜２０重量％、好まし
くは１２〜１８重量％添加される。The stabilizer is a component added to maintain the stability of the silver plating solution, and amino acids having a carboxyl group in the molecule, such as glutamic acid and aminobutyric acid, are used. Further, by using a trace amount of halogenated carboxylic acid, sodium thiosulfate, etc. in combination with the above-mentioned stabilizer, the stability of the silver plating solution can be further improved. The stabilizer is
It is added in an amount of 10 to 20% by weight, preferably 12 to 18% by weight, based on the amount of silver in the silver plating solution.
本発明の銀被覆粉体の製造法において、銀被覆の対象と
なる粉体は、銀めっき液に対して安定な物質であり、粉
末状、粒状、フレーク状、繊維状等、通常粉体として取
り扱われるものである。In the method for producing silver-coated powder of the present invention, the powder to be silver-coated is a substance that is stable against a silver plating solution, and is usually in the form of powder, granules, flakes, fibers, etc. It is something that is handled.
これらの粉体として、たとえばマスコバイトマイカ２
フロゴバイトマイカ１合成マイカ、セリサイト等のフレ
ーク状粉体、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、セとオライド等の針状無機粉体、
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、窒化ケイ素、炭化ケイ素等の結
晶質または不定形無機粉体、ガラスファイバー、カーボ
ンファイバー２シリコンフアイバー等の無機繊維状粉体
、木材バルブ、種毛繊維等の天然繊維、ナイロン、ビニ
ロン、ポリエステル、ポリエチレン、ポリプロピレン等
の合成繊維および合成樹脂粉末などが挙げられる。These powders include, for example, muscovite mica 2
Phlogovite Mica 1 Synthetic mica, flake powder such as sericite, potassium titanate whisker, acicular inorganic powder such as wollastonite, asbestos, cetoolide, etc.
Crystalline or amorphous inorganic powder such as silica, alumina, talc, shirasu balloon, graphite, glass flake, silicon nitride, silicon carbide, inorganic fibrous powder such as glass fiber, carbon fiber 2 silicon fiber, wood bulb, seeds Examples include natural fibers such as hair fibers, synthetic fibers such as nylon, vinylon, polyester, polyethylene, and polypropylene, and synthetic resin powders.
これらの粉体は、銀被覆めっきの前処理として表面活性
化処理が施される。粉体の表面活性化処理法には、特に
制限はなく公知の方法が採用される。たとえば塩化第１
Ｇｍの酸性水溶液に粉体を浸漬し、塩化第１錫を粉体に
吸着させた後、水洗する方法などを採用することができ
る。These powders are subjected to surface activation treatment as a pretreatment for silver coating plating. There are no particular restrictions on the surface activation treatment method for the powder, and any known method may be employed. For example, first chloride
A method may be adopted in which the powder is immersed in an acidic aqueous solution of Gm to adsorb stannous chloride to the powder, and then washed with water.
銀被覆粉体は、前記化学銀めつき液に、前記活性化処理
を施した粉体を浸漬し、銀めっき液の温度を３０〜４０
℃、初期ｐＨを１２．５〜１３．０に調整してめっき反
応を開始し、めっき反応の進行に従って低下するめっき
液のｐＨを１１．５〜１２゜０の範囲に制御して銀めっ
き反応を継続することにより製造される。また、必要に
応じて銀錯イオンを添加しながら銀めっき反応を継続す
ることにより、製造される。The silver-coated powder is prepared by immersing the activated powder in the chemical silver plating solution and increasing the temperature of the silver plating solution to 30 to 40℃.
℃, the plating reaction is started by adjusting the initial pH to 12.5 to 13.0, and the pH of the plating solution, which decreases as the plating reaction progresses, is controlled in the range of 11.5 to 12℃ to conduct the silver plating reaction. Manufactured by continuing. Moreover, it is manufactured by continuing the silver plating reaction while adding silver complex ions as necessary.
本発明の化学銀めっき液は、銀錯イオンおよび還元剤を
含有する化学銀めっき液に、安定剤を添加したことを特
徴とする。The chemical silver plating solution of the present invention is characterized in that a stabilizer is added to the chemical silver plating solution containing silver complex ions and a reducing agent.
また銀被覆粉体の製造法は、前記化学銀めっき液を用い
、そのｐ）（を制御して表面活性化処理を施した粉体の
化学銀めっきを行うことを特徴とする。The method for producing a silver-coated powder is characterized in that the chemical silver plating solution described above is used to chemically plate a powder that has been subjected to a surface activation treatment by controlling its p).
本発明の化学銀めつき液において、安定剤の添加は、そ
の機構は明らかではないが、ｐＨ１１程廣までは化学銀
めっき液を安定に存在させる。In the chemical silver plating solution of the present invention, the addition of a stabilizer allows the chemical silver plating solution to exist stably up to a pH of about 11, although the mechanism thereof is not clear.
この安定剤として、分子内にカルボキシル基を存するア
ミノ酸が存効であり、さらにハロゲン化カルボン酸およ
び／またはチオ硫酸ナトリウムを微量添加併用すること
により、化学銀めっき液の安定性はさらに向上する。Amino acids having carboxyl groups in their molecules are effective as stabilizers, and the stability of the chemical silver plating solution is further improved by adding a small amount of halogenated carboxylic acid and/or sodium thiosulfate.
従来の化学銀めっきにおいては、めっき処理の直前に銀
イオンと還元剤とを混合して銀めっき液を調製しなけれ
ばならない程不安定であり、したがって銀めっき反応の
速度を制御することは極めて困難であったが、本発明の
銀被覆粉体の製造法においては、前記安定な化学銀めっ
き液を用いることにより、銀めっき反応の反応速度を、
そのｐＨを制御する簡単な手法で容易に制御できる結果
、密着性の優れた均一な銀皮膜を粉体表面に形成するこ
とができる。Conventional chemical silver plating is so unstable that a silver plating solution must be prepared by mixing silver ions and a reducing agent just before the plating process, and therefore it is extremely difficult to control the speed of the silver plating reaction. Although it was difficult, in the method for producing silver-coated powder of the present invention, by using the stable chemical silver plating solution, the reaction rate of the silver plating reaction can be improved.
Since the pH can be easily controlled by a simple method, a uniform silver film with excellent adhesion can be formed on the powder surface.
本発明の銀被覆粉体の製造法においては、３０〜４０℃
に加温した前記化学銀めっき液に表面活性化処理を施し
た粉体を浸漬し、アルカリ添加して９Ｈを１２．５以上
、好ましくは１２．５〜１３．５に調整することにより
、めっき反応が開始する。In the method for producing silver-coated powder of the present invention, 30 to 40°C
Plating is carried out by immersing the surface-activated powder in the chemical silver plating solution heated at The reaction begins.
反応が進行するにつれて、ｐｉ−＋は低下し１１．０以
下になると反応は停止する。したがって、反応はｐ Ｈ
１１，０以上で行う必要があり、好ましくは、粉体の種
類、形状などによりその最適値は異なるが、ｐ Ｈ１１
，５〜１２．０の範囲の一定値に制御して行われる。As the reaction progresses, pi-+ decreases, and when it becomes 11.0 or less, the reaction stops. Therefore, the reaction is at pH
It is necessary to carry out the process at a pH of 11.0 or higher, and preferably the pH is 11.0 or higher, although the optimum value varies depending on the type and shape of the powder.
, 5 to 12.0.
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 by way of examples.
ただし、本発明の範囲は、下記実施例により何等の制限
を受けるものではない。However, the scope of the present invention is not limited in any way by the following examples.
（１１［ｌ被覆天然黒鉛粉末の製造
（ａｌ 化学銀めっき液の調製
硝酸ＩＩ ２３．６ ｇを純水１，０００ｍｆｆ１に溶
解した中に、エチレンジアミン１６．７ｇ（エチレンジ
アミン／硝酸銀モル比＝−２）およびグルタミン酸２ｇ
を添加して溶解し化学銀めっき液を調製した。(11 [L Preparation of coated natural graphite powder (al) Preparation of chemical silver plating solution 16.7 g of ethylenediamine (ethylenediamine/silver nitrate molar ratio = -2) was dissolved in 1,000 mff1 of pure water with 23.6 g of nitric acid II. and 2g glutamic acid
was added and dissolved to prepare a chemical silver plating solution.
山） 天然黒鉛粉末の表面活性化処理
平均粒径１００ｍμ、比表面積１ ｒｄ ／ ｇの天然
黒鉛１５ｇを、塩化第１錫含有塩酸酸性水溶液（塩化第
１錫濃度−１，５ｇ／ｊ） １，０００ｍｌに３０分間
浸漬した後、濾過、水洗して表面活性化処理を施した天
然黒鉛粉末を調製した。Surface activation treatment of natural graphite powder 15 g of natural graphite with an average particle diameter of 100 mμ and a specific surface area of 1 rd/g was added to an acidic aqueous solution of hydrochloric acid containing tinn chloride (concentration of tin chloride - 1.5 g/j) 1. 000 ml for 30 minutes, filtered and washed with water to prepare a surface activated natural graphite powder.
（Ｃ） 化学銀めっき処理
前記＋８１項で調製した化学銀めつき液に、前記（至）
）項で調製した表面活性化処理を施した天然黒鉛粉末１
５ｇを浸漬して撹拌下に４０℃に加温した。(C) Chemical silver plating treatment Add the chemical silver plating solution prepared in item +81 above to
Natural graphite powder 1 subjected to surface activation treatment prepared in section )
5 g was immersed and heated to 40° C. while stirring.
さらに、ロッセル塩７８．４ ｇを添加溶解した後、水
酸化ナトリウム水溶液を添加してｐＨを１２．８に調整
した結果、反応が開始した。４分後にｐ Ｈが１２．０
まで低下したので、水酸化ナトリウム水溶液を添加して
ｐＨを１２．０に制？■して保持し、３０分間攪拌保持
して反応を継続し、銀被覆天然黒鉛粉末を得た。Furthermore, after adding and dissolving 78.4 g of Rosselle's salt, an aqueous sodium hydroxide solution was added to adjust the pH to 12.8, and the reaction started. After 4 minutes pH is 12.0
The pH dropped to 12.0 by adding sodium hydroxide aqueous solution. The reaction was continued by stirring and holding for 30 minutes to obtain silver-coated natural graphite powder.
得られた銀被覆天然黒鉛粉末は、真比重３．６０、金属
化率５０．１重量％、色調は銀白色であった。The obtained silver-coated natural graphite powder had a true specific gravity of 3.60, a metallization rate of 50.1% by weight, and a silvery white color tone.
また、得られた銀被覆天然黒鉛粉末を圧縮成形した体積
充填率（Ｖｆ）８５％の成形体は、体積固有抵抗値が４
０μΩ・１と優れた導電性を示した。In addition, a compact with a volume filling factor (Vf) of 85% obtained by compression molding the obtained silver-coated natural graphite powder has a volume resistivity value of 4.
It showed excellent conductivity of 0 μΩ·1.
さらに、得られた銀被覆天然黒鉛粉末を、走査型電子ｇ
徽鏡を用いて観察した結果、天然湯鉛粉末が均一な銀め
っき皮膜で被覆されていた。Furthermore, the obtained silver-coated natural graphite powder was transferred to a scanning electronic g
Observation using a mirror revealed that the natural hot water lead powder was covered with a uniform silver plating film.
（２） 銀被覆黒鉛微粉末
（ａｌ 黒鉛微粉末の表面活性化処理平均粒径１０ｍ
μ、比表面積１６ｎ（／ｇの黒鉛粉末１５ｇを、塩化第
１ｖＡ含有塩酸酸性水溶液（塩化第ｉｍｉ＊度−１，５
ｇ／ ｊ） １．０００ｍｊに３０分間浸漬した後、濾
過、水洗して表面活性化処理を施した天然黒鉛粉末を調
製した。(2) Surface activation treatment of silver-coated graphite fine powder (al) graphite fine powder average particle size 10 m
μ, 15 g of graphite powder with a specific surface area of 16 n (/g) was added to an acidic aqueous solution of hydrochloric acid containing 1 vA of chloride (1 vA of chloride - 1,5 degrees of chloride).
g/j) Natural graphite powder was prepared by immersing it in 1.000 mJ for 30 minutes, filtering and washing with water to perform surface activation treatment.
伽） 化学銀めっき処理
前記第（１） ＋８１項と同一の条件で調製した化学銀
めっき液に、前記中）項で調製した表面活性化処理を施
した黒鉛微粉末１５ｇを浸漬して攪拌下に４０℃に加温
した。さらに、ロッセル塩７００ｇを添加溶解した後、
水酸化ナトリウム水溶液を添加してｐＨを１２．５に調
整した結果、反応が開始した。５分後にｐＨが１１．８
まで低下した後、水酸化ナトリウム水溶液を添加してｐ
Ｈを１１．８に制御して保持しながら、銀濃度１２０ｇ
／ｌ、エチレンジアミン濃度８５ｇ／ｊの銀−エチレン
ジアミン諸イオン溶液１，０００ｍＮを３０分にわたり
攪拌したに添加して反応を継続し、銀被覆黒鉛微粉末を
得た。佽) Chemical silver plating treatment 15 g of graphite fine powder subjected to the surface activation treatment prepared in item (middle) above was immersed in a chemical silver plating solution prepared under the same conditions as in item (1) +81 above, and the mixture was stirred. It was heated to 40°C. Furthermore, after adding and dissolving 700g of Rossel salt,
As a result of adjusting the pH to 12.5 by adding an aqueous sodium hydroxide solution, the reaction started. After 5 minutes pH is 11.8
After the p
While controlling and maintaining H at 11.8, the silver concentration was 120g.
The reaction was continued by adding 1,000 mN of a solution of silver-ethylenediamine various ions with a concentration of 85 g/l and an ethylenediamine concentration of 85 g/j for 30 minutes to obtain a silver-coated graphite fine powder.
得られた銀被覆黒鉛微粉末は、真比重７．３５、金属化
率８９．０重量％、色調は銀白色であった。The obtained silver-coated fine graphite powder had a true specific gravity of 7.35, a metallization rate of 89.0% by weight, and a silvery white color tone.
また、得られた銀被覆黒鉛微粉末を圧縮成形した体積充
填率（Ｖｆ）６７％の成形体は、体積固を抵抗値が１２
μΩ・個と優れた導電性を示した。In addition, a compact with a volume filling factor (Vf) of 67% obtained by compression molding the obtained silver-coated fine graphite powder has a volumetric solidity of 12% in resistance value.
It showed excellent conductivity of μΩ.
さらに、得られた銀被覆黒鉛微粉末を、走査型電子顕微
鏡を用いて観察した結果、黒鉛微粉末が均一な恨めつき
皮膜で被覆されていた。Furthermore, as a result of observing the obtained silver-coated graphite fine powder using a scanning electron microscope, it was found that the graphite fine powder was coated with a uniform grating film.
＋３＋ １１被覆ガラス繊維
（＋１） 化学銀めっき液の調製
硝酸銀５．９ｇを純水１．ＯＯＯｍｊ！に溶解した中に
、エチレンジアミン４．２ｇ（エチレンジアミン／硝酸
銀モル比−２）およびグルタミン酸０．６ｇを添加して
溶解し化学銀めっき液を調製した。+3+ 11 Coated glass fiber (+1) Preparation of chemical silver plating solution Add 5.9 g of silver nitrate to 1.0 g of pure water. OOOmj! A chemical silver plating solution was prepared by adding and dissolving 4.2 g of ethylenediamine (ethylenediamine/silver nitrate molar ratio -2) and 0.6 g of glutamic acid.
（ｂｌ ガラス繊維の表面活性化処理直径１１ｍμφ
、長さ０．１ｍｍのガラス繊維１５ｇを、塩化第１錫含
有塩酸酸性水溶液（塩化第１！ｆｉ度＝１．５ｇ／ｌ）
１．ＯＯＯｍｊ！に３０分間浸漬した後、濾過、水洗し
て表面活性化処理を施した天然黒鉛粉末を調製した。(bl Surface activation treatment of glass fiber diameter 11 mμφ
, 15 g of glass fiber with a length of 0.1 mm was added to an acidic aqueous solution of hydrochloric acid containing tin chloride (1!fi degree of chloride = 1.5 g/l).
1. OOOmj! Natural graphite powder was prepared by immersing it in water for 30 minutes, filtering it, and washing it with water to perform a surface activation treatment.
（Ｃ） 化学銀めっき処理
前記ｆａ１項で調製した化学銀めつき液に、前記（ｂ１
項で調製した表面活性化処理を施したガラス繊維１５ｇ
を浸漬して攪拌下に３０℃に加温した。(C) Chemical silver plating treatment The above (b1) is added to the chemical silver plating solution prepared in the above fa1
15 g of surface-activated glass fiber prepared in Section 1.
was immersed and heated to 30°C while stirring.
さらに、ロフセル塩１９．６ ｇを添加溶解した後、水
酸化ナトリウム水溶液を添加してｐＨを１２．８に調整
した結果、反応が開始した。その後水酸化ナトリウム水
溶液を添加してｐＨを１１．６に制御して保持し、２０
分間撹拌保持して反応をｍ続し、銀被覆ガラス繊維を得
た。Furthermore, after adding and dissolving 19.6 g of Lofcel's salt, an aqueous sodium hydroxide solution was added to adjust the pH to 12.8, and as a result, the reaction started. Thereafter, an aqueous sodium hydroxide solution was added to control and maintain the pH at 11.6, and the pH was maintained at 11.6.
The reaction was continued with stirring for several minutes to obtain silver-coated glass fibers.
得られた銀被覆ガラス繊維は、真比重２．９６、金属化
率１９．８重量％、色調は銀白色であった。The obtained silver-coated glass fiber had a true specific gravity of 2.96, a metallization rate of 19.8% by weight, and a silvery white color tone.
また、得られた銀被覆ガラス繊維を圧縮した体積充填率
（Ｖｆ） ２４％における体積固有抵抗値はｌ×１０−
３μΩ・備であった。Moreover, the volume resistivity value at a volume filling factor (Vf) of 24% when the obtained silver-coated glass fiber is compressed is l×10−
The resistance was 3 μΩ.
さらに、得られた銀被覆ガラス繊維を、走査型電子顕微
鏡を用いて観察した結果、ガラス繊維が均一な銀めっき
皮膜で被覆されていた。Furthermore, as a result of observing the obtained silver-coated glass fiber using a scanning electron microscope, it was found that the glass fiber was coated with a uniform silver plating film.
本発明の化学銀めっき液は、前記実施例に示したように
、急激な反応が起きずｐＨ調整により反応速度の制御が
可能である。したがって、本発明の化学銀めつき液を用
いることにより、緻密で均一な恨めつき皮膜の形成が可
能となる。As shown in the above examples, the chemical silver plating solution of the present invention does not cause a rapid reaction, and the reaction rate can be controlled by adjusting the pH. Therefore, by using the chemical silver plating solution of the present invention, it is possible to form a dense and uniform scratched film.
また、本発明の銀被覆粉体の製造法においては、前記化
学銀めっき液を用い、ｐＨ制御により反応速度を制御し
て粉体の銀被覆めっきを行うことから、緻密で均一な銀
皮膜の形成された粉末が製造される。In addition, in the method for producing silver-coated powder of the present invention, the chemical silver plating solution is used and the reaction rate is controlled by pH control to perform silver-coating of the powder, so that a dense and uniform silver coating can be obtained. A formed powder is produced.
この方法で製造される銀被覆粉体は、銀粉では得られな
い形状、たとえばフレーク状、繊維状等の複合化された
機能をも持たせることができ、また銀粉に代わる材料と
して、導電性しゆう助材成形用材料、導電性ペースト用
フィラー、電気接点材料用フィラー、導電性フィラー等
として利用できる。The silver-coated powder produced by this method can have shapes that cannot be obtained with silver powder, such as flakes, fibers, etc., and can have complex functions, and can also be used as a material to replace silver powder. It can be used as a material for forming support materials, a filler for conductive paste, a filler for electrical contact materials, a conductive filler, etc.
本発明は、密着性に優れた、緻密で均一な銀皮膜を有す
る粉体の製造法およびこの方法で使用する反応速度の制
御が容易な化学銀めつき液を提供するものであり、その
産業上の意義は極めて大きい。The present invention provides a method for producing powder having a dense and uniform silver film with excellent adhesion, and a chemical silver plating solution used in this method that allows easy control of the reaction rate. The above is extremely significant.
特許出願人 （４３０）日本曹達株式会社代 理
人 （７１２５） 横 山 吉 美（９６
４８）東 海裕作Patent applicant (430) Representative of Nippon Soda Co., Ltd.
People (7125) Yoshimi Yokoyama (96)
48) Yusaku Tokai
Claims (7)
還元剤および銀量に対し１０〜２０重量％の安定剤を含
有することを特徴とする化学銀めっき液(1) A chemical silver plating solution containing a silver complex ion, a reducing agent in an amount of 1 to 3 equivalents to the silver complex ion, and a stabilizer in an amount of 10 to 20% by weight based on the amount of silver.
合物と銀イオンとキレート環を形成し得る錯化剤との反
応生成物であることを特徴とする化学銀めっき液(2) The chemical silver plating solution according to claim (1), wherein the silver complex ion is a reaction product of a silver compound, a silver ion, and a complexing agent capable of forming a chelate ring.
ジアミン四酢酸またはその塩、エチレンジアミン、ジエ
チレントリアミン、トリエチレンテトラアミン、アンモ
ニアよりなる群から選ばれた少なくとも１種であること
を特徴とする化学銀めっき液(3) Claim (2) is characterized in that the complexing agent is at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt, ethylenediamine, diethylenetriamine, triethylenetetraamine, and ammonia. chemical silver plating solution
ル塩、ブドウ糖、ホルマリンおよびヒドラジンならびに
その塩よりなる群から選ばれた少なくとも１種であるこ
とを特徴とする化学銀めっき液(4) The chemical silver plating solution according to claim (1), wherein the reducing agent is at least one selected from the group consisting of Rochelle's salt, glucose, formalin, hydrazine, and salts thereof.
カルボキシル基を有するアミノ酸であることを特徴とす
る化学銀めっき液(5) The chemical silver plating solution according to claim (1), wherein the stabilizer is an amino acid having a carboxyl group in the molecule.
（５）項に記載の安定剤とハロゲン化カルボン酸および
／またはチオ硫酸ナトリウムとの混合物であることを特
徴とする化学銀めっき液(6) A chemical according to claim (1), characterized in that the stabilizer is a mixture of the stabilizer according to claim (5) and a halogenated carboxylic acid and/or sodium thiosulfate. silver plating solution
整した請求項第（１）項に記載の銀めっき液に、表面活
性化処理を施した粉体を浸漬して反応を開始し、以降銀
めっき液のｐＨを１１．５〜１２．０に制御し、銀めっ
き反応をそのまま維持するか、もしくは銀錯イオンを追
加しながら反応を継続することを特徴とする銀被覆粉体
の製造法(7) The surface-activated powder is immersed in the silver plating solution according to claim (1), the temperature of which is adjusted to 30 to 40°C and the pH of 12.5 to 13. A silver-coated powder characterized in that the pH of the silver plating solution is controlled at 11.5 to 12.0, and the silver plating reaction is maintained as it is, or the reaction is continued while adding silver complex ions. body manufacturing method
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32774288A JPH02173272A (en) | 1988-12-27 | 1988-12-27 | Silver chemical plating liquid and protection of powder coated by silver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32774288A JPH02173272A (en) | 1988-12-27 | 1988-12-27 | Silver chemical plating liquid and protection of powder coated by silver |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02173272A true JPH02173272A (en) | 1990-07-04 |
Family
ID=18202472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32774288A Pending JPH02173272A (en) | 1988-12-27 | 1988-12-27 | Silver chemical plating liquid and protection of powder coated by silver |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02173272A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016659A (en) * | 2004-07-01 | 2006-01-19 | Okuno Chem Ind Co Ltd | Two-pack electroless silver plating solution |
| WO2010079884A3 (en) * | 2009-01-08 | 2010-08-26 | Ls Cable Ltd. | Method for producing conductive ink |
| CN102560451A (en) * | 2012-02-22 | 2012-07-11 | 江苏大学 | Chemical nano-silver plating solution and preparation method thereof, and silver plating method for copper part |
| JP2015503032A (en) * | 2011-12-15 | 2015-01-29 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Electroless plating of silver on graphite |
| JP2019186206A (en) * | 2018-04-10 | 2019-10-24 | タク・マテリアル株式会社 | Conductive paste and its production method |
-
1988
- 1988-12-27 JP JP32774288A patent/JPH02173272A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016659A (en) * | 2004-07-01 | 2006-01-19 | Okuno Chem Ind Co Ltd | Two-pack electroless silver plating solution |
| WO2010079884A3 (en) * | 2009-01-08 | 2010-08-26 | Ls Cable Ltd. | Method for producing conductive ink |
| KR101012986B1 (en) * | 2009-01-08 | 2011-02-10 | 엘에스전선 주식회사 | Method for Producing Conductive Ink |
| JP2015503032A (en) * | 2011-12-15 | 2015-01-29 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Electroless plating of silver on graphite |
| US10361016B2 (en) | 2011-12-15 | 2019-07-23 | Henkel IP & Holding GmbH | Electroless plating of silver onto graphite |
| US10923249B2 (en) | 2011-12-15 | 2021-02-16 | Henkel IP & Holding GmbH | Electroless plating of silver onto graphite |
| CN102560451A (en) * | 2012-02-22 | 2012-07-11 | 江苏大学 | Chemical nano-silver plating solution and preparation method thereof, and silver plating method for copper part |
| JP2019186206A (en) * | 2018-04-10 | 2019-10-24 | タク・マテリアル株式会社 | Conductive paste and its production method |
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