JPS61163975A - Electrically conductive paint composition - Google Patents
Electrically conductive paint compositionInfo
- Publication number
- JPS61163975A JPS61163975A JP559185A JP559185A JPS61163975A JP S61163975 A JPS61163975 A JP S61163975A JP 559185 A JP559185 A JP 559185A JP 559185 A JP559185 A JP 559185A JP S61163975 A JPS61163975 A JP S61163975A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- copper powder
- metallic
- complex salt
- coated copper
- 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
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、導電性及び耐酸化性に優れた銀被覆銅粉を主
成分とする導電性塗料組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a conductive coating composition containing silver-coated copper powder as a main component, which has excellent conductivity and oxidation resistance.
（ロ）従来の技術
金属粉末を導電フィラーとして含む導電性塗料組成物は
、電子機器類から発生する電磁波をシールドする目的で
電子機器筐体に塗られる電磁波シールド用塗料、プリン
ト回路基板上の抵抗体等の素子と回路とを電気的に接続
する等の目的で使用される導電性ペースト及びプリント
回路基板上の各種電子部品の接続、リード線取出口への
接着等導電性を必要とする部分の接着を目的とする導電
性接着剤として実用に供されている。(b) Conventional technology Conductive paint compositions containing metal powder as a conductive filler are electromagnetic shielding paints applied to electronic equipment housings for the purpose of shielding electromagnetic waves generated by electronic equipment, and resistors on printed circuit boards. Conductive paste used for the purpose of electrically connecting circuits with elements such as bodies, and parts that require conductivity such as connecting various electronic components on printed circuit boards and adhering to lead wire outlets. It is put into practical use as a conductive adhesive for the purpose of adhesion.
（ハ）発明が解決しようとする問題点
導電性塗料組成物の導電フィラーとしての金属粉末とし
ては、金、銀、銅、ニッケル、パラジウム等が使用され
ているが、金、銀等の貴金属は導電性に優れ、且つ耐酸
化性はあるがこれら貴金属は価格が高価でコスト的に不
利である。(c) Problems to be solved by the invention Gold, silver, copper, nickel, palladium, etc. are used as metal powders as conductive fillers in conductive paint compositions, but noble metals such as gold and silver Although these noble metals have excellent conductivity and oxidation resistance, they are expensive and disadvantageous in terms of cost.
一方、銅は価格が安く、初期の導電性は良好であるが、
耐酸化性が劣り長期間安定した高い導電性を示さない。On the other hand, copper is cheap and has good initial conductivity, but
It has poor oxidation resistance and does not exhibit stable high conductivity over a long period of time.
本発明者らは、比較的安価で導電性及び耐酸化性に優れ
る金属粉の製造方法を鋭意検討した結果、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
液を使用して金属銅粉の表面に銀被覆を施した銀被覆銅
粉が、導電性が高く且つ耐酸化性に優れている事を見出
し先に特許出願（特願昭５９−９６１４４号）を行った
。As a result of intensive research into a method for producing metal powder that is relatively inexpensive and has excellent conductivity and oxidation resistance, the inventors of the present invention discovered a method for producing metal powder that is relatively inexpensive and has excellent conductivity and oxidation resistance. A patent application (Japanese Patent Application No. 59-96144) was filed based on the discovery that silver-coated copper powder, which is produced by coating the surface of metallic copper powder with silver, has high conductivity and excellent oxidation resistance.
この方法により製造された銀被覆銅粉よりなる導電性塗
料組成物が優れた性能を有する事を見出し本発明を完成
した。The present invention was completed by discovering that a conductive coating composition made of silver-coated copper powder produced by this method has excellent performance.
（ニ）問題点を解決するための手段
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て金属銅粉の表面に
金属銀を置換析出させて得られる銀被覆銅粉、バインダ
ー及び有機溶剤を主構成成分とする導電性塗料組成物に
関するものである。(d) Means for Solving the Problems The present invention provides metallic silver obtained by displacing and depositing metallic silver 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. The present invention relates to a conductive coating composition whose main components are silver-coated copper powder, a binder, and an organic solvent.
本発明の銀塩は硝酸銀、炭酸銀、硫酸銀及び酸化銀の１
種又は２種以上の組合せから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。The silver salt of the present invention is one of silver nitrate, silver carbonate, silver sulfate and silver oxide.
The ammonium carbonate salt is a salt selected from one or a combination of ammonium carbonate and ammonium bicarbonate.
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.
バインダーとしては、メチルメタクリレート樹脂、ウレ
タン樹脂、塩化ビニール樹脂、エポキシ樹脂、フェノー
ル樹脂、キシレン樹脂、アルキッド樹脂及びポリエステ
ル等が使用される。As the binder, methyl methacrylate resin, urethane resin, vinyl chloride resin, epoxy resin, phenol resin, xylene resin, alkyd resin, polyester, etc. are used.
有機溶剤としては、芳香族化合物、エステル類、ケトン
類、アルコール類或いはこれらの混合物が使用される。As the organic solvent, aromatic compounds, esters, ketones, alcohols, or mixtures thereof are used.
バインダー及び有機溶剤は、用途即ち電磁波用、導電性
ペースト用或いは導電性接着剤用箋使用目的に適したも
のが選択される。The binder and organic solvent are selected to be suitable for the purpose of use, ie, electromagnetic waves, conductive paste, or conductive adhesive tape.
又、必要に応して金属粉の沈降を防止する目的で酸化ポ
リエチレン、ポリアミド系樹脂及び微粉末シリカ等を添
加する事も出来る。Further, if necessary, polyethylene oxide, polyamide resin, finely powdered silica, etc. can be added for the purpose of preventing precipitation of metal powder.
例えば、電磁波シールド用導電性塗料組成物は、銀被覆
銅粉、メチルメタクリレート樹脂等のバインダー、トル
エン、キシレン、メチルエチルケトン、ブチルセロソル
ブ等の混合溶剤及び微粉末シリカ等の沈降防止剤をデ４
シルバー等を使用して １充分混線分散して得
る事が出来る。For example, a conductive coating composition for electromagnetic shielding may contain silver-coated copper powder, a binder such as methyl methacrylate resin, a mixed solvent such as toluene, xylene, methyl ethyl ketone, butyl cellosolve, and an anti-settling agent such as finely powdered silica.
It can be obtained by dispersing the crosstalk sufficiently by using silver or the like.
銀被覆銅粉とバインダーの割合は、銀被覆銅粉／バイン
ダー（重量比）が１〜６の範囲が好ましい。この値より
小さい場合、生成した塗膜が脆くなる傾向があり、又こ
の値より大きい場合、塗膜の導電性が悪化する傾向があ
る。The ratio of silver-coated copper powder to binder is preferably in the range of 1 to 6 (weight ratio) of silver-coated copper powder/binder. If it is smaller than this value, the resulting coating film tends to become brittle, and if it is larger than this value, the electrical conductivity of the coating film tends to deteriorate.
沈降防止剤は、銀被覆銅粉に対して０．５〜５重量％の
範囲が好ましい。０．５％未満の場合、充分な沈降防止
効果がなく、５％を越えても沈降防止効果はそれほど上
昇しない。The amount of the anti-settling agent is preferably 0.5 to 5% by weight based on the silver-coated copper powder. If it is less than 0.5%, there is no sufficient anti-sedimentation effect, and if it exceeds 5%, the anti-sedimentation effect does not increase much.
又、導電性塗料組成物中の銀被覆銅粉、バインダー及び
沈降防止剤の合計量は２０〜８０重量％の範囲が好まし
い。Further, the total amount of the silver-coated copper powder, binder and antisettling agent in the conductive coating composition is preferably in the range of 20 to 80% by weight.
以下本発明について、実施例を挙げて更に詳しく説明す
る。The present invention will be described in more detail below with reference to Examples.
（ホ）本発明の効果
本発明の導電性塗料組成物は、導電性が高く且つ耐酸化
性に優れ、即ち耐久性のある塗膜を与える。(e) Effects of the present invention The conductive coating composition of the present invention has high conductivity and excellent oxidation resistance, that is, provides a durable coating film.
又、安価なためコスト的に有利である。In addition, it is inexpensive and therefore advantageous in terms of cost.
（へ）実施例
実施例１
銅粉（福田金属箔製、ＣＥＩＩＩＯ）４００ｇ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）１１を加えて４０
０ｒｐｍで攪拌しながら室温で、下記組成の銀錯塩溶液
を３０分間で滴下し、′更に１時間攪拌を続は銀被覆銅
粉を得た。(F) Examples Example 1 After degreasing 400 g of copper powder (manufactured by Fukuda Metal Foil Co., Ltd., CEIIIO) with an alkaline aqueous solution and removing the oxide film with dilute sulfuric acid, distilled water (hereinafter abbreviated as water) 11 was added to
While stirring at 0 rpm and at room temperature, a silver complex salt solution having the following composition was added dropwise over 30 minutes, followed by further stirring for 1 hour to obtain silver-coated copper powder.
銀錯塩溶液の組成
硝酸銀 ６．４ｇ炭酸アン
モニウム ５０ ｇアンモニア水（
？１１度２９Ｗ／Ｖ ％） １００ ｇ水
１１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３７８ｇであり
、銀含有量は１．０６重量％であった。Composition of silver complex salt solution Silver nitrate 6.4 g Ammonium carbonate 50 g Aqueous ammonia (
? 11 degrees 29W/V%) 100g water
11 After washing this silver-coated copper powder until the pH of the washing water becomes 7,
Vacuum dried at ℃. The yield of silver-coated copper powder was 378 g, and the silver content was 1.06% by weight.
この銀被覆銅粉６０ｇと下記組成のポリメチルメタクリ
レート溶液１５０ｇを、ホモジナイザーを使用して３０
００ｒｐｍで３０分間混合して塗料を製造した。Using a homogenizer, 60 g of this silver-coated copper powder and 150 g of a polymethyl methacrylate solution having the following composition were mixed for 30 g.
The paint was prepared by mixing at 00 rpm for 30 minutes.
ポリメチルメタクリレート １０ 重量％トルエ
ン ４０ ％メチルエチルケ
トン １８．８ ％酢酸ブチル
” ３１．２ ％この塗料をスプレーガンを使用
して、縦１５ｃｍ、横１５ｃｍ、厚さ３ ｍｍのＡＢＳ
板に５０μｍの膜厚に塗布した。得られた塗膜の表面抵
抗は０．０８Ω／口であり、優れた導電性を示した。Polymethyl methacrylate 10% by weight Toluene 40% Methyl ethyl ketone 18.8% Butyl acetate
” 31.2% Use a spray gun to apply this paint to an ABS piece measuring 15cm long, 15cm wide and 3mm thick.
It was applied to a plate to a film thickness of 50 μm. The surface resistance of the resulting coating film was 0.08Ω/hole, indicating excellent electrical conductivity.
又、スペクトルアナライザー（タケダ理研製）を使用し
て、ｌＯ〜１００１００Ｏの周波数帯に於ける電界及び
磁界のシールド効果を測定した。Further, using a spectrum analyzer (manufactured by Takeda Riken), the shielding effect of electric and magnetic fields in the frequency band of 1O to 100,100O was measured.
結果を図１及び図２に示す。The results are shown in FIGS. 1 and 2.
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、０゜ｌΩ／口と表面抵抗の
変化は小く、スス１及び図２に示すように電界及び磁界
のシールド効果の変化も小さかった。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 chamber at 70°C and 93% relative humidity for 20 days. The change in resistance was small, and as shown in Soot 1 and FIG. 2, the change in the shielding effect of electric and magnetic fields was also small.
又、８５℃の恒温槽中に試料を２０日間放置後の表面抵
抗は、０．０９Ω／口とその変化は小さく優れた耐久性
を示した。Further, the surface resistance after leaving the sample in a constant temperature bath at 85° C. for 20 days was 0.09 Ω/mouth, showing excellent durability with little change.
実施例２
以下の組成の銀錯塩溶液を使用した他は実施例１と同様
に銀被覆銅粉を製造した。Example 2 Silver-coated copper powder was produced in the same manner as in Example 1, except that a silver complex salt solution having the following composition was used.
銀錯塩溶液の組成
硝酸銀 ４０ｇ炭酸アン
モニウム ７５ｇアンモニア水（濃
度２９Ｗ／Ｖ％） １５０ｇ水
ｌｌ！銀被覆銅粉
の収量は３９４ｇであり、銀含有量は６．３重量％であ
った。Composition of silver complex salt solution Silver nitrate 40g Ammonium carbonate 75g Ammonia water (concentration 29W/V%) 150g Water
ll! The yield of silver-coated copper powder was 394 g, and the silver content was 6.3% by weight.
この銀被覆銅粉を実施例１と同様にして塗料化し、ＡＢ
Ｓ板に５０μｍの膜厚に塗布した。得られた塗膜の表面
抵抗は０．０５Ω／口であり、優れた導電性を示した。This silver-coated copper powder was made into a paint in the same manner as in Example 1, and AB
It was applied to an S plate to a film thickness of 50 μm. The surface resistance of the resulting coating film was 0.05Ω/mouth, indicating excellent electrical conductivity.
更に、７０℃、相対湿度９３％の恒温恒湿槽中に試料を
２０日間放置後の塗膜の表面抵抗は０゜０５Ω／口と全
く表面抵抗の変化はなく、又８５℃の恒温槽中に試料を
２０日間放置後の表面抵抗 ）も、０．０５
Ω／口と全く変化がなく、優れた耐久性を示した。Furthermore, after leaving the sample in a constant temperature and humidity chamber at 70℃ and 93% relative humidity for 20 days, the surface resistance of the coating film was 0.05Ω/mouth, with no change in surface resistance at all, and when placed in a constant temperature chamber at 85℃. The surface resistance after leaving the sample for 20 days) is also 0.05
There was no change at all from Ω/mouth, indicating excellent durability.
比較例
銅粉（福田金属箔製、ＣＥＩＩＩＯ）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、
空気に触れないように乾燥後、実施例１と同様にして塗
料化し、ＡＢＳ板に５０μｍの膜厚に塗布した。得られ
た塗膜の表面抵抗は０．６０Ω／口と高い値を示した。Comparative Example Copper powder (manufactured by Fukuda Metal Foil Co., Ltd., CEIIIO) was degreased with an alkaline aqueous solution and oxide film removed with dilute sulfuric acid.
After drying to avoid exposure to air, it was made into a paint in the same manner as in Example 1, and applied to an ABS board to a film thickness of 50 μm. The surface resistance of the resulting coating film was as high as 0.60Ω/mouth.
又、７０℃、相対湿度９３％の恒温恒湿槽中に放置した
ところ、３日後の表面抵抗は既に３゜２４Ω／口であっ
た。Furthermore, when it was left in a constant temperature and humidity chamber at 70°C and relative humidity of 93%, the surface resistance after 3 days was already 3°24Ω/mouth.
図１は、実施例１の導電性塗料組成物の電界シールド効
果を示したもので、縦軸は減衰率（ｄＢ）、横軸は周波
数（ＭＨｚ）、実線は初期値、点線は７０℃相対湿度９
３％の恒温恒湿槽中に試料を２０日間放置後の値である
。
図２は、実施例１の導電性塗料組成物の磁界シールド効
果を示したもので、縦軸は減衰率（ｄＢ）、横軸は周波
数（ＭＨｚ）、実線は初期値、点線は７０℃相対湿度９
３％の恒温恒湿槽中に試料を２０日間放置後の値である
。
特許出願人 日産化学工業株式会社
ノｑ ５ＬＴｔ、 ＭＦＩＩ
５ｏｏ ｌｏｏ。
ンｉ１ｚｇ、ピ；；に；、 ）１ｈ
手続補正書（自発）
昭和６０年６り／３日Figure 1 shows the electric field shielding effect of the conductive paint composition of Example 1, where the vertical axis is the attenuation rate (dB), the horizontal axis is the frequency (MHz), the solid line is the initial value, and the dotted line is the 70°C relative Humidity 9
This is the value after the sample was left in a constant temperature and humidity chamber of 3% for 20 days. Figure 2 shows the magnetic field shielding effect of the conductive coating composition of Example 1, where the vertical axis is the attenuation rate (dB), the horizontal axis is the frequency (MHz), the solid line is the initial value, and the dotted line is the 70°C relative Humidity 9
This is the value after the sample was left in a constant temperature and humidity chamber of 3% for 20 days. Patent applicant: Nissan Chemical Industries, Ltd. Noq 5LTt, MFII 5oo loo. i1zg, p;;ni;, )1h Procedural amendment (voluntary) June 3, 1985
Claims (1)
する銀錯塩溶液を使用して金属銅粉の表面に金属銀を置
換析出させて得られる銀被覆銅粉よりなる導電性塗料組
成物A conductive coating composition made of silver-coated copper powder obtained by displacing and depositing metallic silver 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.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP559185A JPS61163975A (en) | 1985-01-16 | 1985-01-16 | Electrically conductive paint composition |
| 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 |
|---|---|---|---|
| JP559185A JPS61163975A (en) | 1985-01-16 | 1985-01-16 | Electrically conductive paint composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61163975A true JPS61163975A (en) | 1986-07-24 |
Family
ID=11615477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP559185A Pending JPS61163975A (en) | 1984-05-14 | 1985-01-16 | Electrically conductive paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61163975A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006093398A1 (en) * | 2005-03-04 | 2006-09-08 | Inktec Co., Ltd. | Conductive inks and manufacturing method thereof |
| KR100658492B1 (en) | 2005-03-21 | 2006-12-15 | 주식회사 잉크테크 | Conductive inks and their methods for forming thin layers |
| KR100701851B1 (en) | 2006-03-14 | 2007-03-30 | 주식회사 잉크테크 | Antibacterial Composition Containing Organic Silver Complexes, Antibacterial Treatment Methods Using The Same And Antibacterial Formed Article |
| 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 |
| KR100727451B1 (en) * | 2005-04-26 | 2007-06-13 | 주식회사 잉크테크 | Metal-based inks |
| KR100776180B1 (en) | 2006-08-07 | 2007-11-16 | 주식회사 잉크테크 | Manufacturing methods for metal clad laminates |
| WO2009145504A2 (en) * | 2008-04-10 | 2009-12-03 | 주식회사 잉크테크 | Ink composition for optoelectronic device |
| JP2010500475A (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 silver nanoparticles and silver ink composition comprising silver nanoparticles produced thereby |
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|---|---|---|---|---|
| JPS5533788A (en) * | 1978-07-06 | 1980-03-10 | Leclanche Sa | Low water long life alkaline primary battery |
| JPS56155259A (en) * | 1980-05-01 | 1981-12-01 | Fukuda Kinzoku Hakufun Kogyo Kk | Electrically conductive paint employing silver-copper composite powder |
| JPS5981303A (en) * | 1982-11-02 | 1984-05-11 | Toyobo Co Ltd | Actinic ray-curable conductive composition |
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1985
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5533788A (en) * | 1978-07-06 | 1980-03-10 | Leclanche Sa | Low water long life alkaline primary battery |
| JPS56155259A (en) * | 1980-05-01 | 1981-12-01 | Fukuda Kinzoku Hakufun Kogyo Kk | Electrically conductive paint employing silver-copper composite powder |
| JPS5981303A (en) * | 1982-11-02 | 1984-05-11 | Toyobo Co Ltd | Actinic ray-curable conductive composition |
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