JPS60243277A - Manufacture of copper powder coated with silver - Google Patents
Manufacture of copper powder coated with silverInfo
- Publication number
- JPS60243277A JPS60243277A JP59096144A JP9614484A JPS60243277A JP S60243277 A JPS60243277 A JP S60243277A JP 59096144 A JP59096144 A JP 59096144A JP 9614484 A JP9614484 A JP 9614484A JP S60243277 A JPS60243277 A JP S60243277A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- copper powder
- salt
- ammonia
- ammonium carbonate
- 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
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 60
- 239000004332 silver Substances 0.000 title claims abstract description 60
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims abstract description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000003973 paint Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- 241001590997 Moolgarda engeli Species 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal cyanide Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- C23C18/42—Coating with noble metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
- H01L23/4827—Materials
- H01L23/4828—Conductive organic material or pastes, e.g. conductive adhesives, inks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Description
【発明の詳細な説明】 本発明は、銀被覆銅粉の製造方法に関するものである。[Detailed description of the invention] The present invention relates to a method for producing silver-coated copper powder.
更に詳しくは、導電性に優れ且つ耐酸化性に極めて優れ
た銀被覆銅粉の安価な製造方法に関するものである。More specifically, the present invention relates to an inexpensive method for producing silver-coated copper powder that has excellent conductivity and extremely high oxidation resistance.
従来より、銀粉、銅粉、ニッケル粉等の導電フィラーを
合成樹脂バインダー中に分散させ導電性塗料とし、塗布
後その塗膜に導電性を付与する事は知られている。It has been known to disperse conductive fillers such as silver powder, copper powder, nickel powder, etc. in a synthetic resin binder to make a conductive paint, and to impart conductivity to the coating film after application.
導電フィラーとして銀粒子を使用した場合、その塗膜は
導電性に優れ、且つ耐酸化性があり、耐久性もあるが、
銀は価格が高（資源的にも問題がある。When silver particles are used as a conductive filler, the coating film has excellent conductivity, oxidation resistance, and durability, but
The price of silver is high (there is also a resource problem).
一方銅粉を使用する場合は、銅は価格が安く初期の導電
性は良好であるが、酸化劣化により導電性が低下し耐久
性に問題がある。On the other hand, when using copper powder, although copper is cheap and has good initial conductivity, the conductivity decreases due to oxidative deterioration and there are problems with durability.
従来よりかかる銅粉の欠点を改良する為、銅粉表面に銀
を被覆し、安価で導電性に優れ、而も耐久性のある導電
フィラーを製造しようとする試みが種々なされて来た。In order to improve the drawbacks of copper powder, various attempts have been made to coat the surface of copper powder with silver to produce a conductive filler that is inexpensive, has excellent conductivity, and is durable.
例えば、特公昭４７−３０１９号公報の如く、銀シアン
化物を使用し銅表面に銀を析出させる方法がある。この
方法では毒性の高いアルカリ金属シアン化物を高濃度で
使用する為、作業環境等に於いて問題が多い。For example, as disclosed in Japanese Patent Publication No. 47-3019, there is a method of depositing silver on the surface of copper using silver cyanide. This method uses a highly toxic alkali metal cyanide at a high concentration, which causes many problems in the working environment.
又、硝酸銀、アンモニア水及びチオ硫酸ナトリウムを使
用し置換メッキ法により銀を銅粉上に析出させる方法、
或いはブドウ糖を還元剤として銀を銅粉上に析出させる
方法等が提案されているが、これらの方法により製造さ
れた銀被覆銅粉の導電性は充分ｉいも。とは言えない。Also, a method of depositing silver on copper powder by displacement plating using silver nitrate, aqueous ammonia and sodium thiosulfate;
Alternatively, methods have been proposed in which silver is deposited on copper powder using glucose as a reducing agent, but the conductivity of silver-coated copper powder produced by these methods is sufficient. It can not be said.
更に又、特公昭５７−５９２８３号公報の如く、硝酸銀
、炭酸アンモニウム及びエチレンジアミン４酢酸３ナト
リウム塩を使用する方法で製造された銀被覆銅粉の導電
性は良好であるが、耐湿性が十分でなく、従って経時的
な酸化安定性は十分なものと言えない。Furthermore, as disclosed in Japanese Patent Publication No. 57-59283, silver-coated copper powder produced by a method using silver nitrate, ammonium carbonate, and ethylenediaminetetraacetic acid trisodium salt has good conductivity, but moisture resistance is insufficient. Therefore, the oxidation stability over time cannot be said to be sufficient.
本発明者等は上述の問題に鑑み、これらを解決すべく鋭
意検討した結果、銀塩、炭酸アンモニア水及びアンモニ
ア水を主成分とする銀錯塩溶液が、取扱い時の作業環境
に於ける毒性が少なく、価格゛ も安く導電性に優れ、
且つ僅かの銀被覆量でも、耐熱性、耐湿性に優れ、極め
て酸化安定性の高い銀被覆銅粉を与えるという事実を見
出し、本発明を完成するに至った。In view of the above-mentioned problems, the inventors of the present invention have conducted intensive studies to solve these problems, and have found that a silver complex salt solution containing silver salt, aqueous ammonia carbonate, and aqueous ammonia as main components has no toxicity in the working environment during handling. low cost, excellent conductivity,
Furthermore, the present inventors have discovered that even with a small amount of silver coating, a silver-coated copper powder having excellent heat resistance, moisture resistance, and extremely high oxidation stability can be obtained, and the present invention has been completed.
即ち、本発明は銀塩、炭酸アンモニウム塩及びアンモニ
ア水を主成分とする銀錯塩溶液を使用し銅粉の表面に金
属銀を置換析出させる事により導電性に優れ、酸化安定
性に極めて優れる銀被覆銅粉の経済性に優れた製造方法
を提供するものである。That is, the present invention uses a silver complex salt solution mainly composed of silver salt, ammonium carbonate salt, and aqueous ammonia to deposit metallic silver on the surface of copper powder, thereby producing silver that has excellent conductivity and extremely excellent oxidation stability. The present invention provides a method for manufacturing coated copper powder with excellent economic efficiency.
本発明の銀塩は硝酸銀、炭酸銀及び酸化銀の１種又は２
種以上の組合せから選ばれる塩であり、炭酸アンモニウ
ム塩は炭酸アンモニウム及び炭酸水素アンモニウムの１
種又はその組合せから選ばれる塩である。又アンモニア
水は通常２５〜３０Ｗ／Ｖ％の濃度のものが使用される
が、これに限定されるものではない。The silver salt of the present invention is one or two of silver nitrate, silver carbonate, and silver oxide.
It is a salt selected from a combination of more than one species, and ammonium carbonate salt is one of ammonium carbonate and ammonium hydrogen carbonate.
Salts selected from species or combinations thereof. Further, ammonia water having a concentration of 25 to 30 W/V% is usually used, but the concentration is not limited thereto.
炭酸アンモニウム塩とアンモニア水中のアンモニアのモ
ル比は、炭酸アンモニウム塩として炭酸アンモニウムを
使用する場合ゆ０．１〜３が好ましく、更に好ましくは
０．２〜２が良い。The molar ratio of ammonium carbonate salt to ammonia in the ammonia water is preferably 0.1 to 3, more preferably 0.2 to 2 when ammonium carbonate is used as the ammonium carbonate salt.
又、炭酸アンモニウム塩として炭酸水素アンモニウムを
使用する場合は二〇、１〜６が好ましく、更に好ましく
は０．２〜４が良い。Further, when ammonium hydrogen carbonate is used as the ammonium carbonate salt, it is preferably 20, 1 to 6, more preferably 0.2 to 4.
炭酸アンモニウム塩とアンモニア水中のアンモニアのモ
ル比が上記の範囲外の組成に於いて銅粉表面に銀被覆を
行った場合、塗布後の塗膜の導電性が低下する事があり
、炭酸アンモニウム塩とアンモニア水中のアンモニアの
モル比は上記範囲内の組成とする事が望ましい。If the surface of the copper powder is coated with silver in a composition in which the molar ratio of ammonium carbonate salt and ammonia in aqueous ammonia is outside the above range, the conductivity of the coated film may decrease, and ammonium carbonate salt It is desirable that the molar ratio of ammonia and ammonia in the aqueous ammonia be within the above range.
本発明の銅粉を銀被覆する方法には、銅粉を水に懸濁さ
せ銀錯塩溶液を滴下する方法、銅粉をアンモニア水に懸
濁させ銀錯塩溶液を滴下する方法、銅粉を炭酸アンモニ
ウム塩水溶液に懸濁させ銀錯塩溶液を滴下する方法等が
あり、その何れをも使用出来る。但し銀塩はアンモニア
水に均一に溶解した状態で使用する事が望ましい。The method of coating copper powder with silver according to the present invention includes a method of suspending copper powder in water and dropping a silver complex salt solution, a method of suspending copper powder in aqueous ammonia and dropping a silver complex salt solution, and a method of suspending copper powder in water and dropping a silver complex salt solution. There are methods such as suspending it in an aqueous ammonium salt solution and dropping a silver complex salt solution, and any of these methods can be used. However, it is desirable to use the silver salt in a state in which it is uniformly dissolved in aqueous ammonia.
銀塩の種類が異なれば、アンモニア水に対する銀塩の溶
解性は異なって来る。従って、銀塩の量が炭酸アンモニ
ウム塩とアンモニア水の量に比べて比較的少ない場合は
容易に均一溶液になるが、銀塩の量が多くなるにつれて
銀塩はアンモニア水に溶解し難くなる。Different types of silver salt have different solubility in aqueous ammonia. Therefore, when the amount of silver salt is relatively small compared to the amounts of ammonium carbonate salt and aqueous ammonia, a homogeneous solution is easily obtained, but as the amount of silver salt increases, it becomes difficult to dissolve the silver salt in aqueous ammonia.
それ故、炭酸アンモニウム塩とアンモニア水は銀塩に対
して過剰に用いる事が望ましい。Therefore, it is desirable to use ammonium carbonate salt and aqueous ammonia in excess of the silver salt.
銅粉は電解銅粉、噴霧銅粉、還元銅粉、搗砕銅粉等何れ
でも良く、又銅粉の形状も球状、偏平状、樹枝状、針状
等何れでも良い。The copper powder may be any electrolytic copper powder, sprayed copper powder, reduced copper powder, crushed copper powder, etc., and the shape of the copper powder may be spherical, flat, dendritic, acicular, etc.
更に、銅粉の大きさも特に限定されるものではない。Furthermore, the size of the copper powder is not particularly limited either.
銀被覆銅粉の銅と銀の比は特に制限はないが、銀被覆量
が多くなると価格が高くなるので好ましくない。Although there is no particular restriction on the ratio of copper to silver in the silver-coated copper powder, an increase in the amount of silver coating increases the price, which is not preferable.
本発明で製造した銀被覆銅粉はその銀被覆量が約１ｗｔ
％と僅かであつても、塗料化後の塗膜は良好な導電性を
有し、且つ極めて優れた耐久性を有する等その工業的価
値は高いものである。The silver-coated copper powder produced according to the present invention has a silver coating amount of about 1wt.
Even if the amount is as small as %, the coated film after being made into a paint has good conductivity and extremely excellent durability, so its industrial value is high.
以下、本発明の実施例並びに比較例を示して、更に本発
明の詳細な説明する。EXAMPLES Hereinafter, the present invention will be further explained in detail by showing examples and comparative examples of the present invention.
実施例１
銅粉（福田金属箔製、ＣＥＩＩＩＯ）６０ｇをアルカリ
水溶液による脱脂処理及び希硫酸による酸化被膜除去処
理後、蒸溜水（以下水と略称する）１５０ｍＪ！を加え
て４００ｒｐｍで攪拌しながら室温で、下記組成の銀錯
塩溶液を５分間で滴下し、更に１時間攪拌を続は銀被覆
銅粉を得た。Example 1 After degreasing 60 g of copper powder (manufactured by Fukuda Metal Foil Co., Ltd., CEIIIO) with an alkaline aqueous solution and removing an oxide film with dilute sulfuric acid, 150 mJ of distilled water (hereinafter abbreviated as water) was applied! was added, and while stirring at 400 rpm, a silver complex salt solution having the following composition was added dropwise over 5 minutes at room temperature, and the mixture was further stirred for 1 hour to obtain silver-coated copper powder.
銀錯塩溶液の組成
硝酸銀 １２．５ｇ
炭酸アンモニウム ２０．０ｇ
アンモニア水（濃度２Ｈ／Ｖ％）〜２０．０ｇ水 １０
０ ｍｊ！
この銀被覆銅粉を洗浄水のＰＨが７になるまで洗浄した
後、５０℃で真空乾燥した。銀被覆銅粉の収量は６３．
５ｇで、銀含有量は１２．５ｗｔ％であった。Composition of silver complex salt solution Silver nitrate 12.5g Ammonium carbonate 20.0g Ammonia water (concentration 2H/V%) ~ 20.0g Water 10
0 mj! This silver-coated copper powder was washed until the pH of the washing water became 7, and then vacuum-dried at 50°C. The yield of silver-coated copper powder is 63.
At 5 g, the silver content was 12.5 wt%.
この銀被覆銅粉３０ｇと下記組成のポリメチルメタクリ
レート溶液７５ｇを、ホモジナイダーを使用して３００
０ｒｐｍで３０分間混合して塗料を製造し、ＡＢＳ板に
５０μｍの膜厚に塗布した。Using a homogenizer, 30 g of this silver-coated copper powder and 75 g of a polymethyl methacrylate solution having the following composition were heated to 300 g.
A paint was prepared by mixing at 0 rpm for 30 minutes and applied to an ABS board to a film thickness of 50 μm.
ポリメチルメタクリレート溶液組成
ポリメチルメタクリレート １０ ％
トルエン ４０ ％
メチルエチルケトン １８．８％
酢酸ブチル ３１．２％
得られた塗膜の表面抵抗は５０μｍの厚さで０゜０５Ω
／口であり、良好な導電性を示した。Polymethyl methacrylate solution composition Polymethyl methacrylate 10% Toluene 40% Methyl ethyl ketone 18.8% Butyl acetate 31.2% The surface resistance of the resulting coating film was 0°05Ω at a thickness of 50 μm.
/ mouth, and showed good conductivity.
更に、この塗膜の耐久性を調べる為、７０℃、相対湿度
９３％の恒温恒湿槽中に試料を２０日間放置後、塗膜の
表面抵抗を測定したところ、全く変化がなかった。Furthermore, in order to investigate the durability of this coating film, the surface resistance of the coating film was measured after leaving the sample in a constant temperature and humidity bath at 70° C. and 93% relative humidity for 20 days, and no change was found.
又、８５℃の恒温槽中に２０日間放置後の表面抵抗は全
く変化しておらず、優れた耐久性を示した。Further, the surface resistance after being left in a constant temperature bath at 85° C. for 20 days did not change at all, indicating excellent durability.
実施例２〜１１
実施例１と同様にして処理した銅粉４０ｇに、水１００
ｍ７！を加え４００ｒｐｍで攪拌しながら室温で、銀塩
、炭酸アンモニウム塩及びアンモニア水（濃度２９Ｗ／
Ｖ％）を水１００ｍｊ＋に溶解した表１及び表２の銀錯
塩溶液を５分間で滴下し、更に１時間攪拌後実施例１と
同様にして銀被覆銅粉を得た。Examples 2 to 11 To 40 g of copper powder treated in the same manner as in Example 1, 100 g of water was added.
m7! silver salt, ammonium carbonate salt and aqueous ammonia (concentration 29W/
The silver complex salt solutions shown in Tables 1 and 2 in which V%) was dissolved in 100 mj+ of water were added dropwise over 5 minutes, and after further stirring for 1 hour, silver-coated copper powder was obtained in the same manner as in Example 1.
得られた銀被覆銅粉を実施例１と同様にして塗料化し、
塗膜の表面抵抗及び耐久性を測定した。The obtained silver-coated copper powder was made into a paint in the same manner as in Example 1,
The surface resistance and durability of the coating film were measured.
結果を表１及び表２に示す。The results are shown in Tables 1 and 2.
比較例１〜２
実施例２と同様にして、表１の銀錯塩溶液を使用して銀
被覆銅粉を製造した。Comparative Examples 1 to 2 Silver-coated copper powder was produced in the same manner as in Example 2 using the silver complex salt solution shown in Table 1.
塗膜の表面抵抗は実）Ｎ例２〜１１に比し表１の如く高
い値を示した。As shown in Table 1, the surface resistance of the coating film was higher than that of Examples 2 to 11.
比較例３
硝酸銀３．５ｇを水６０ｍｊｉに溶解し、アンモニア水
（濃度２９Ｗ／Ｖ％）を３ ｍ ｊ２加えた。Comparative Example 3 3.5 g of silver nitrate was dissolved in 60 mj2 of water, and 3 mj2 of aqueous ammonia (concentration 29 W/V%) was added.
この溶液に水酸化ナトリウム２．５４ｇを水６０ｍＩ２
に溶解した溶液を加えた後、更にアンモニア水（濃度２
９Ｗ／Ｖ％）３．５ｍＪを加え無色透明な均一溶液を得
た。この溶液をＡ液とする。Add 2.54 g of sodium hydroxide to this solution and 60 mI2 of water.
After adding the solution dissolved in
9W/V%) 3.5 mJ was added to obtain a colorless and transparent homogeneous solution. This solution will be referred to as Solution A.
又、ブドウ［２２，５ｇ及び酒石酸２ｇを水５００ ｍ
Ａに溶かした溶液を加熱し１０分間煮沸した後室温に
戻した。この溶液をＢ液とする。Also, add 22.5 g of grapes and 2 g of tartaric acid to 500 m of water.
The solution dissolved in A was heated and boiled for 10 minutes, then returned to room temperature. This solution will be referred to as Solution B.
実施例１と同様にして処理した銅粉５０ｇに水１００ｒ
ｒ＋ｌを加え攪拌しながら室温で、Ａ液とＢ液それぞれ
１２５ｍ１を混合後直ちに１分間以内で添加した。更に
１時間攪拌後、実施例１と同様にして銀被覆銅粉を得た
。この銀被覆銅粉の銀含有量は４．３ｗｔ％であった。Add 100 r of water to 50 g of copper powder treated in the same manner as in Example 1.
Immediately after mixing, 125 ml each of liquids A and B were added within 1 minute at room temperature while stirring. After further stirring for 1 hour, silver-coated copper powder was obtained in the same manner as in Example 1. The silver content of this silver-coated copper powder was 4.3 wt%.
実施例１と同様にして塗料化し、塗膜の表面抵抗を測定
したところ、５０μｍの膜厚で０．３７Ω／口であった
。本発明に比し銀含有量が多いにもかかわらず導電性は
劣っている。A paint was prepared in the same manner as in Example 1, and the surface resistance of the paint film was measured, and it was found to be 0.37 Ω/mouth at a film thickness of 50 μm. Although the silver content is higher than that of the present invention, the conductivity is inferior.
比較例４（特公昭５７−５９２８３号公報の追試）実施
例１と同様にして処理した銅粉４０ｇに水１００ｍｊ２
を加えて４０Ｏｒｐｍで攪拌しながら室温で、硝酸銀０
．７５ｇ、炭酸アンモニラ云３゜１ｇ及びエチレンジア
ミン４酢酸３ナトリウム塩３．５ｇを水５ Ｑｍｊ！に
溶解した溶液を５分間で滴下し、更に１時間攪拌後、実
施例１と同様にして銀被覆銅粉を得た。銀含有量は１．
２９ｗｔ％であった。Comparative Example 4 (Additional test of Japanese Patent Publication No. 57-59283) 40 g of copper powder treated in the same manner as in Example 1 and 100 mj2 of water
of silver nitrate at room temperature while stirring at 40 rpm.
．． 75g, 3゜1g of ammonia carbonate, and 3.5g of ethylenediaminetetraacetic acid trisodium salt were added to 5Qmj of water. A solution dissolved in was added dropwise over 5 minutes, and after further stirring for 1 hour, silver-coated copper powder was obtained in the same manner as in Example 1. The silver content is 1.
It was 29wt%.
実施例１と同様にして塗料化し、塗膜の゛表面抵抗を測
定したところ、５０μｍの膜厚で表面抵抗は０．２４Ω
／口であった。A paint was prepared in the same manner as in Example 1, and the surface resistance of the paint film was measured, and the surface resistance was 0.24Ω at a film thickness of 50 μm.
/It was a mouth.
各耐湿性を調べる為、７０℃゛、相対湿度９３％の恒温
恒湿槽に放置したところ、塗膜の表面抵抗は６日後には
既に５０％増加していた。In order to examine the humidity resistance of each coating, it was left in a constant temperature and humidity chamber at 70°C and relative humidity of 93%, and the surface resistance of the coating film had already increased by 50% after 6 days.
比較例５
実施例１と同様にして処理した銅粉５０ｇに水１００ｍ
ｆを加えて４ｏｏｒｐｍで攪拌しながら室温で、硝酸銀
２．４６ｇ、アンモニア水（濃度２９Ｗ／Ｖ％）２５ｍ
ｊ！及びチオ硫酸ナトリウム３５ｇを水２００ｍ７！に
溶解した溶液を５分間で滴下し、更に１時間攪拌後、実
施例１と同様にして銀被覆銅粉を得た。銀含有量は３．
０ｗｔ％であった。Comparative Example 5 50g of copper powder treated in the same manner as in Example 1 and 100ml of water
Add 2.46 g of silver nitrate and 25 m of ammonia water (concentration 29 W/V%) at room temperature while stirring at 4 oorpm.
j! And 35g of sodium thiosulfate and 200m7 of water! A solution dissolved in was added dropwise over 5 minutes, and after further stirring for 1 hour, silver-coated copper powder was obtained in the same manner as in Example 1. The silver content is 3.
It was 0wt%.
実施例１と同様にして塗料化し、塗膜の表面抵抗を測定
したところ５０μｍの塗膜で表面抵抗は１．５Ω／口と
極めて導電性の悪い値であった。A paint was prepared in the same manner as in Example 1, and the surface resistance of the paint film was measured. The surface resistance was 1.5 Ω/mouth for a 50 μm film, which was a value with extremely poor conductivity.
手続補正書（自発）
昭和５９年６月 ７９日
１ 事件の表示
昭和５９年特許願第９６１４４号
２ 発明の名称
銀被覆銅粉の製造方法
３ 補正をする者
事件との関係 特許出願人
住所■１０１東京都千代田区神田錦町３丁目７番地１４
補正の対象
明細書の発明の詳細な説明の欄
ｌ）明細書の第４頁７行目の「−・炭酸銀−」の後に「
硫酸銀」を加入する。Procedural amendment (voluntary) June 79, 1980 1 Indication of the case 1982 Patent Application No. 96144 2 Name of the invention Method for producing silver-coated copper powder 3 Person making the amendment Relationship to the case Patent applicant address ■ 101 3-7-14 Kanda Nishikicho, Chiyoda-ku, Tokyo
Column for detailed description of the invention in the specification subject to amendment l) After “-・Silver carbonate-” on page 4, line 7 of the specification, “
Add silver sulfate.
２）明細書の第５頁３行目の「−場合−」の後に「得ら
れた銀被覆銅粉を使用して塗料化し」を加入する。2) In the third line of page 5 of the specification, after "-case-", add "the obtained silver-coated copper powder is used to make a paint".
３）明細書の第５頁１２行目、同１４行目の「−アンモ
ニア水・・・」とあるのを「−・アンモニア性溶液−」
と訂正する。3) "-Ammonia water..." on page 5, line 12 and line 14 of the specification has been replaced with "--ammonia solution-"
I am corrected.
４）明細書の第７頁１３行目の「−ホモジナイザー・・
−」とあるのを置−ホモジナイザー−−−」と訂正する
。4) "-Homogenizer..." on page 7, line 13 of the specification.
-” should be corrected to “Homogenizer---”.
５）明細書の第７頁１６行目の「−溶液組成−・−」と
あるのを「−溶液組成（重量比）・−」と訂正する。5) On page 7, line 16 of the specification, "-solution composition--" is corrected to "-solution composition (weight ratio)--".
６）明細書の第１０頁８行目の「−・−１００ｍ１−・
−」とあるのを「・−１５０ｍ Ｌ−・」と訂正する。6) Page 10, line 8 of the specification “-・-100m1-・
-” should be corrected to “・-150m L-・”.
７）明細書の第１２頁表１最上欄の「−実誌例一」とあ
るのを「・・・実施例・−」と訂正する。7) In the top column of Table 1 on page 12 of the specification, the phrase "-Example 1 of Journal" is corrected to "...Example--".
Claims (1)
分とする銀錯塩溶液を用いて゛金属銅粉の表面に金属銀
を置換析出させる事を特徴とする銀被覆銅粉の製造方法
。 ２、銀塩が硝酸銀、炭酸銀、硫酸銀及び酸化銀からなる
群より選ばれる事を特徴とする特許言ｎ求の範囲第１項
記載の製造方法。 ３、炭酸アンモニウム塩が炭酸アンモニウム及び炭酸水
素アンモニウムからなる群より選ばれる事を特徴とする
特許請求の範囲第１項記載の製造方法。[Claims] 1. Silver-coated copper powder characterized in that metallic silver is precipitated by substitution on the surface of metallic copper powder using a silver complex salt solution containing silver salt, ammonium carbonate salt and aqueous ammonia as main components. Production method. 2. The manufacturing method according to item 1 of the patent claim, wherein the silver salt is selected from the group consisting of silver nitrate, silver carbonate, silver sulfate, and silver oxide. 3. The manufacturing method according to claim 1, wherein the ammonium carbonate salt is selected from the group consisting of ammonium carbonate and ammonium hydrogen carbonate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59096144A JPS60243277A (en) | 1984-05-14 | 1984-05-14 | Manufacture of copper powder coated with silver |
| US06/731,402 US4652465A (en) | 1984-05-14 | 1985-05-07 | Process for the production of a silver coated copper powder and conductive coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59096144A JPS60243277A (en) | 1984-05-14 | 1984-05-14 | Manufacture of copper powder coated with silver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60243277A true JPS60243277A (en) | 1985-12-03 |
| JPH0250992B2 JPH0250992B2 (en) | 1990-11-06 |
Family
ID=14157184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59096144A Granted JPS60243277A (en) | 1984-05-14 | 1984-05-14 | Manufacture of copper powder coated with silver |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60243277A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100438408B1 (en) * | 2001-08-16 | 2004-07-02 | 한국과학기술원 | Method for Synthesis of Core-Shell type and Solid Solution type Metallic Alloy Nanoparticles via Transmetalation Reactions and Their Applications |
| KR100727483B1 (en) * | 2006-04-29 | 2007-06-13 | 주식회사 잉크테크 | Compositions for forming reflecting layer having organic silver complexes, and method for preparing reflecting layer using same |
| KR100791231B1 (en) * | 2000-12-20 | 2008-01-03 | 도와 홀딩스 가부시끼가이샤 | Silver-dispersed copper powder, process for producing the powder, and conductive paste and a conductor for a printed electronic circuit utilizing the powder |
| JP2008530001A (en) * | 2005-02-07 | 2008-08-07 | インクテック カンパニー リミテッド | Organic silver complex compound and thin film forming method using the same |
| JP2009530270A (en) * | 2006-03-14 | 2009-08-27 | インクテック カンパニー リミテッド | Antibacterial composition containing organic silver complex compound, antibacterial treatment method using the same, and antibacterial molded article |
| JP2010500476A (en) * | 2006-08-07 | 2010-01-07 | インクテック カンパニー リミテッド | Method for producing metal laminate |
| CN102260864A (en) * | 2011-07-20 | 2011-11-30 | 淮阴工学院 | Preparation method of attapulgite/copper-core shell structure one-dimensional rod-like superfine copper powder |
| WO2012056952A1 (en) * | 2010-10-26 | 2012-05-03 | コニカミノルタオプト株式会社 | Film mirror, process for manufacture of film mirror, and mirror for reflection of solar light |
| CN103752842A (en) * | 2013-11-11 | 2014-04-30 | 南京工业大学 | Substitution and chemistry deposition compound preparation method for nano silver coated copper powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5759283A (en) * | 1980-09-25 | 1982-04-09 | Sharp Corp | Card reader |
-
1984
- 1984-05-14 JP JP59096144A patent/JPS60243277A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5759283A (en) * | 1980-09-25 | 1982-04-09 | Sharp Corp | Card reader |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100791231B1 (en) * | 2000-12-20 | 2008-01-03 | 도와 홀딩스 가부시끼가이샤 | Silver-dispersed copper powder, process for producing the powder, and conductive paste and a conductor for a printed electronic circuit utilizing the powder |
| KR100438408B1 (en) * | 2001-08-16 | 2004-07-02 | 한국과학기술원 | Method for Synthesis of Core-Shell type and Solid Solution type Metallic Alloy Nanoparticles via Transmetalation Reactions and Their Applications |
| US8226755B2 (en) | 2005-02-07 | 2012-07-24 | Inktec Co., Ltd. | Organic silver complexes, their preparation methods and their methods for forming thin layers |
| US9914743B2 (en) | 2005-02-07 | 2018-03-13 | Inktec Co., Ltd. | Organic silver complexes, their preparation methods and their methods for forming thin layers |
| US8679242B2 (en) | 2005-02-07 | 2014-03-25 | Inktec Co., Ltd. | Organic silver complexes, their preparation methods and their methods for forming thin layers |
| JP2008530001A (en) * | 2005-02-07 | 2008-08-07 | インクテック カンパニー リミテッド | Organic silver complex compound and thin film forming method using the same |
| JP2009530270A (en) * | 2006-03-14 | 2009-08-27 | インクテック カンパニー リミテッド | Antibacterial composition containing organic silver complex compound, antibacterial treatment method using the same, and antibacterial molded article |
| US8445578B2 (en) | 2006-04-29 | 2013-05-21 | Inktec Co., Ltd. | Compositions for forming reflecting layer having organic silver complexes, and method for preparing reflecting layer using same |
| TWI382029B (en) * | 2006-04-29 | 2013-01-11 | 英泰股份有限公司 | Compositions for forming reflecting layer having organic silver complexes, and method for preparing reflecting layer using the same |
| JP2009535661A (en) * | 2006-04-29 | 2009-10-01 | インクテック カンパニー リミテッド | Reflective film coating liquid composition containing organic silver complex compound and method for producing reflective film using the same |
| WO2007126276A1 (en) * | 2006-04-29 | 2007-11-08 | Inktec Co., Ltd. | Compositions for forming reflecting layer having organic silver complexes,and method for preparing reflecting layer using same |
| KR100727483B1 (en) * | 2006-04-29 | 2007-06-13 | 주식회사 잉크테크 | Compositions for forming reflecting layer having organic silver complexes, and method for preparing reflecting layer using same |
| JP2010500476A (en) * | 2006-08-07 | 2010-01-07 | インクテック カンパニー リミテッド | Method for producing metal laminate |
| US8764960B2 (en) | 2006-08-07 | 2014-07-01 | Inktec Co., Ltd. | Manufacturing methods for metal clad laminates |
| WO2012056952A1 (en) * | 2010-10-26 | 2012-05-03 | コニカミノルタオプト株式会社 | Film mirror, process for manufacture of film mirror, and mirror for reflection of solar light |
| CN102260864A (en) * | 2011-07-20 | 2011-11-30 | 淮阴工学院 | Preparation method of attapulgite/copper-core shell structure one-dimensional rod-like superfine copper powder |
| CN103752842A (en) * | 2013-11-11 | 2014-04-30 | 南京工业大学 | Substitution and chemistry deposition compound preparation method for nano silver coated copper powder |
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| Publication number | Publication date |
|---|---|
| JPH0250992B2 (en) | 1990-11-06 |
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