JP2017210686A - Silver-coated copper alloy powder and production method therefor - Google Patents
Silver-coated copper alloy powder and production method therefor Download PDFInfo
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本発明は、銀被覆銅合金粉末およびその製造方法に関し、特に、導電ペーストなどに使用する銀被覆銅合金粉末およびその製造方法に関する。 The present invention relates to a silver-coated copper alloy powder and a method for producing the same, and more particularly to a silver-coated copper alloy powder used for a conductive paste and the like and a method for producing the same.
従来、印刷法などにより電子部品の電極や配線を形成するために、銀粉や銅粉などの導電性の金属粉末に溶剤、樹脂、分散剤などを配合して作製した導電ペーストが使用されている。 Conventionally, in order to form electrodes and wiring of electronic parts by printing methods, etc., conductive pastes prepared by blending a conductive metal powder such as silver powder or copper powder with a solvent, resin, dispersant, etc. have been used. .
しかし、銀粉は、体積抵抗率が極めて小さく、良好な導電性物質であるが、貴金属の粉末であるため、コストが高くなる。一方、銅粉は、体積抵抗率が低く、良好な導電性物質であるが、酸化され易いため、銀粉に比べて保存安定性（信頼性）に劣っている。 However, although silver powder has a very small volume resistivity and is a good conductive material, it is a noble metal powder, and thus costs are high. On the other hand, copper powder has a low volume resistivity and is a good conductive material. However, since it is easily oxidized, it has poor storage stability (reliability) compared to silver powder.
これらの問題を解消するために、導電ペーストに使用する金属粉末として、銅粉の表面を銀で被覆した銀被覆銅粉（例えば、特許文献１〜２参照）や、銅合金の表面を銀で被覆した銀被覆銅合金粉が提案されている（例えば、特許文献３〜４参照）。 In order to solve these problems, as the metal powder used for the conductive paste, silver-coated copper powder (for example, see Patent Documents 1 and 2) in which the surface of the copper powder is coated with silver, or the surface of the copper alloy is silver. A coated silver-coated copper alloy powder has been proposed (see, for example, Patent Documents 3 to 4).
しかし、特許文献１〜２の銀被覆銅粉では、銅粉の表面に銀で被覆されていない部分が存在すると、その部分から酸化が進行してしまうため、保存安定性（信頼性）が不十分になる。また、特許文献３〜４の銀被覆銅合金粉では、導電膜に使用した場合にその導電膜の体積抵抗率が高く（導電性が低く）なるという問題がある。 However, in the silver-coated copper powders of Patent Documents 1 and 2, if there is a part that is not coated with silver on the surface of the copper powder, oxidation proceeds from that part, and thus storage stability (reliability) is unsatisfactory. It will be enough. Further, the silver-coated copper alloy powders of Patent Documents 3 to 4 have a problem that when used in a conductive film, the volume resistivity of the conductive film is high (conductivity is low).
したがって、本発明は、このような従来の問題点に鑑み、保存安定性（信頼性）に優れるとともに体積抵抗率が低い導電膜を形成することができる銀被覆銅合金粉末およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention provides a silver-coated copper alloy powder capable of forming a conductive film having excellent storage stability (reliability) and low volume resistivity, and a method for producing the same. The purpose is to do.
本発明者らは、上記課題を解決するために鋭意研究した結果、１〜５０質量％のニッケルおよび亜鉛の少なくとも一種を含み、残部が銅および不可避不純物からなる組成を有する銅合金粉末を７〜５０質量％の銀含有層により被覆した後、銀含有層で被覆した銅合金粉末を表面処理剤で表面処理することにより、保存安定性（信頼性）に優れるとともに体積抵抗率が低い導電膜を形成することができる銀被覆銅合金粉末を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have found that a copper alloy powder containing at least one of 1 to 50% by mass of nickel and zinc and having the balance of copper and inevitable impurities having a composition of 7 to 7 After coating with a 50% by mass silver-containing layer, the copper alloy powder coated with the silver-containing layer is surface-treated with a surface treatment agent, whereby a conductive film having excellent storage stability (reliability) and low volume resistivity is obtained. The inventors have found that a silver-coated copper alloy powder that can be formed can be produced, and have completed the present invention.
すなわち、本発明による銀被覆銅合金粉末の製造方法は、１〜５０質量％のニッケルおよび亜鉛の少なくとも一種を含み、残部が銅および不可避不純物からなる組成を有する銅合金粉末を７〜５０質量％の銀含有層により被覆した後、銀含有層で被覆した銅合金粉末を表面処理剤で表面処理することを特徴とする。 That is, the method for producing a silver-coated copper alloy powder according to the present invention comprises 7 to 50% by mass of a copper alloy powder having a composition comprising 1 to 50% by mass of nickel and zinc and the balance consisting of copper and inevitable impurities. After the coating with the silver-containing layer, the copper alloy powder coated with the silver-containing layer is surface-treated with a surface treatment agent.
この銀被覆銅合金粉末の製造方法において、銀含有層が銀または銀化合物からなる層であるのが好ましい。表面処理剤は、脂肪酸またはベンゾトリアゾールであるのが好ましく、脂肪酸は、パルミチン酸、ステアリン酸およびオレイン酸からなる群から選ばれる１種以上であるのが好ましい。表面処理剤の量は、銀被覆銅合金粉末に対して０．１〜７質量％であるのが好ましい。表面処理は、銀含有層で被覆した銅合金粉末と表面処理剤とを混合して行ってもよいし、銀含有層で被覆した銅合金粉末のスラリーに表面処理剤を添加して行ってもよい。銅合金粉末は、アトマイズ法により製造するのが好ましく、銅合金粉末のレーザー回折式粒度分布装置により測定した累積５０％粒子径（Ｄ５０径）が０．１〜１５μｍであるのが好ましい。 In this method for producing a silver-coated copper alloy powder, the silver-containing layer is preferably a layer made of silver or a silver compound. The surface treatment agent is preferably a fatty acid or benzotriazole, and the fatty acid is preferably at least one selected from the group consisting of palmitic acid, stearic acid, and oleic acid. The amount of the surface treatment agent is preferably 0.1 to 7% by mass with respect to the silver-coated copper alloy powder. The surface treatment may be performed by mixing the copper alloy powder coated with the silver-containing layer and the surface treatment agent, or by adding the surface treatment agent to the slurry of the copper alloy powder coated with the silver-containing layer. Good. The copper alloy powder is preferably produced by an atomizing method, and the cumulative 50% particle diameter (D50 diameter) of the copper alloy powder measured by a laser diffraction particle size distribution device is preferably 0.1 to 15 μm.
また、本発明による銀被覆銅合金粉末は、１〜５０質量％のニッケルおよび亜鉛の少なくとも一種を含み、残部が銅および不可避不純物からなる組成を有する銅合金粉末が、７〜５０質量％の銀含有層により被覆され、炭素の含有量が０．１〜５質量％であることを特徴とする。 Further, the silver-coated copper alloy powder according to the present invention contains 1 to 50% by mass of nickel and zinc, and the copper alloy powder having a composition consisting of copper and inevitable impurities is 7 to 50% by mass of silver. It is covered with a containing layer, and the carbon content is 0.1 to 5% by mass.
この銀被覆銅合金粉末において、銀含有層が銀または銀化合物からなる層であるのが好ましい。また、銀被覆銅合金粉末のタップ密度が３．８ｇ／ｃｍ３以上であり、真密度に対するタップ密度の割合が４２〜５５％であるのが好ましい。また、銅合金粉末のレーザー回折式粒度分布装置により測定した累積５０％粒子径（Ｄ５０径）が０．１〜１５μｍであるのが好ましい。 In this silver-coated copper alloy powder, the silver-containing layer is preferably a layer made of silver or a silver compound. The tap density of the silver-coated copper alloy powder is preferably 3.8 g / cm 3 or more, and the ratio of the tap density to the true density is preferably 42 to 55%. The 50% cumulative particle diameter measured by a laser diffraction type particle size distribution apparatus of the copper alloy powder (D 50 diameter) is preferably a 0.1-15.
さらに、本発明による導電ペーストは、溶剤および樹脂を含み、導電性粉体として上記の銀被覆銅合金粉末を含むことを特徴とする。また、本発明による導電膜は、この導電ペーストが硬化または乾燥して形成されていることを特徴とする。 Furthermore, the conductive paste according to the present invention includes a solvent and a resin, and includes the above silver-coated copper alloy powder as a conductive powder. The conductive film according to the present invention is characterized in that the conductive paste is formed by curing or drying.
本発明によれば、保存安定性（信頼性）に優れるとともに体積抵抗率が低い導電膜を形成することができる銀被覆銅合金粉末およびその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the silver covering copper alloy powder which can form the electrically conductive film which is excellent in storage stability (reliability) and low volume resistivity, and its manufacturing method can be provided.
本発明による銀被覆銅合金粉末の製造方法の実施の形態では、１〜５０質量％のニッケルおよび亜鉛の少なくとも一種を含み、残部が銅および不可避不純物からなる組成を有する銅合金粉末を（銀被覆銅合金粉末に対して）７〜５０質量％の銀含有層（銀または銀化合物からなる層）により被覆した後、銀含有層で被覆した銅合金粉末を表面処理剤で表面処理する。 In the embodiment of the method for producing a silver-coated copper alloy powder according to the present invention, a copper alloy powder having a composition comprising at least one of nickel and zinc at 1 to 50% by mass and the balance consisting of copper and inevitable impurities (silver coated) After coating with 7 to 50% by mass of a silver-containing layer (a layer made of silver or a silver compound) with respect to the copper alloy powder, the copper alloy powder coated with the silver-containing layer is surface-treated with a surface treatment agent.
銅合金粉末は、湿式還元法、電解法、気相法などにより製造してもよいが、合金成分を溶解温度以上で溶解し、タンディッシュ下部から落下させながら高圧ガスまたは高圧水を衝突させて急冷凝固させることにより微粉末とする、（ガスアトマイズ法、水アトマイズ法などの）所謂アトマイズ法により製造するのが好ましい。特に、高圧水を吹き付ける、所謂水アトマイズ法により製造すると、粒子径が小さい銅合金粉末を得ることができるので、銅合金粉末を導電ペーストに使用した際に粒子間の接触点の増加による導電性の向上を図ることができる。 The copper alloy powder may be manufactured by a wet reduction method, an electrolytic method, a gas phase method, etc., but the alloy components are dissolved at a melting temperature or higher and collided with high-pressure gas or high-pressure water while dropping from the lower part of the tundish. It is preferable to produce by a so-called atomizing method (such as a gas atomizing method or a water atomizing method) to obtain a fine powder by rapid solidification. In particular, copper alloy powder with a small particle size can be obtained by manufacturing by the so-called water atomization method in which high-pressure water is sprayed. Therefore, when copper alloy powder is used in a conductive paste, conductivity due to an increase in contact points between particles is obtained. Can be improved.
銅合金粉末を銀含有層で被覆する方法として、銅と銀の置換反応を利用した還元法や、還元剤を用いる還元法により、銅合金粉末の表面に銀または銀化合物を析出させる方法を使用することができ、例えば、溶媒中に銅合金粉末と銀または銀化合物を含む溶液を攪拌しながら銅合金粉末の表面に銀または銀化合物を析出させる方法や、溶媒中に銅合金粉末および有機物を含む溶液と溶媒中に銀または銀化合物および有機物を含む溶液とを混合して攪拌しながら銅合金粉末の表面に銀または銀化合物を析出させる方法などを使用することができる。 As a method of coating the copper alloy powder with the silver-containing layer, a method of depositing silver or a silver compound on the surface of the copper alloy powder by a reduction method using a substitution reaction between copper and silver or a reduction method using a reducing agent is used. For example, a method of precipitating silver or a silver compound on the surface of a copper alloy powder while stirring a solution containing the copper alloy powder and silver or a silver compound in a solvent, or a method of depositing a copper alloy powder and an organic substance in a solvent. A method of precipitating silver or a silver compound on the surface of a copper alloy powder while mixing and stirring a solution containing silver or a solution containing a silver compound and an organic substance in a solvent can be used.
この溶媒としては、水、有機溶媒またはこれらを混合した溶媒を使用することができる。水と有機溶媒を混合した溶媒を使用する場合には、室温（２０〜３０℃）において液体になる有機溶媒を使用する必要があるが、水と有機溶媒の混合比率は、使用する有機溶媒により適宜調整することができる。また、溶媒として使用する水は、不純物が混入するおそれがなければ、蒸留水、イオン交換水、工業用水などを使用することができる。 As this solvent, water, an organic solvent, or a solvent in which these are mixed can be used. When using a mixed solvent of water and organic solvent, it is necessary to use an organic solvent that becomes liquid at room temperature (20 to 30 ° C.). The mixing ratio of water and organic solvent depends on the organic solvent used. It can be adjusted appropriately. In addition, as water used as a solvent, distilled water, ion-exchanged water, industrial water, or the like can be used as long as there is no fear that impurities are mixed therein.
銀含有層の原料として、銀イオンを溶液中に存在させる必要があるため、水や多くの有機溶媒に対して高い溶解度を有する硝酸銀を使用するのが好ましい。また、銅合金粉末を銀含有層で被覆する反応（銀被覆反応）をできるだけ均一に行うために、固体の硝酸銀ではなく、硝酸銀を溶媒（水、有機溶媒またはこれらを混合した溶媒）に溶解した硝酸銀溶液を使用するのが好ましい。なお、使用する硝酸銀溶液の量、硝酸銀溶液中の硝酸銀の濃度および有機溶媒の量は、目的とする銀含有層の量に応じて決定することができる。 Since silver ions need to be present in the solution as the raw material for the silver-containing layer, it is preferable to use silver nitrate having high solubility in water and many organic solvents. In addition, in order to carry out the reaction of covering the copper alloy powder with the silver-containing layer (silver coating reaction) as uniformly as possible, silver nitrate was dissolved in a solvent (water, an organic solvent or a mixed solvent thereof) instead of solid silver nitrate. It is preferred to use a silver nitrate solution. The amount of silver nitrate solution used, the concentration of silver nitrate in the silver nitrate solution, and the amount of organic solvent can be determined according to the amount of the target silver-containing layer.
銀含有層をより均一に形成するために、溶液中にキレート化剤を添加してもよい。キレート化剤としては、銀イオンと金属銅との置換反応により副生成する銅イオンなどが再析出しないように、銅イオンなどに対して錯安定度定数が高いキレート化剤を使用するのが好ましい。特に、銀被覆銅合金粉末のコアとなる銅合金粉末は主構成要素として銅を含んでいるので、銅との錯安定度定数に留意してキレート化剤を選択するのが好ましい。具体的には、キレート化剤として、エチレンジアミン四酢酸（ＥＤＴＡ）、イミノジ酢酸、ジエチレントリアミン、トリエチレンジアミンおよびこれらの塩からなる群から選ばれたキレート化剤を使用することができる。 In order to form the silver-containing layer more uniformly, a chelating agent may be added to the solution. As the chelating agent, it is preferable to use a chelating agent having a high complex stability constant with respect to copper ions or the like so that copper ions or the like by-produced by substitution reaction between silver ions and metallic copper do not reprecipitate. . In particular, since the copper alloy powder serving as the core of the silver-coated copper alloy powder contains copper as a main component, it is preferable to select a chelating agent while paying attention to the complex stability constant with copper. Specifically, a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriamine, triethylenediamine, and salts thereof can be used as the chelating agent.
銀被覆反応を安定かつ安全に行うために、溶液中にｐＨ緩衝剤を添加してもよい。このｐＨ緩衝剤として、炭酸アンモニウム、炭酸水素アンモニウム、アンモニア水、炭酸水素ナトリウムなどを使用することができる。 In order to perform the silver coating reaction stably and safely, a pH buffer may be added to the solution. As this pH buffering agent, ammonium carbonate, ammonium hydrogen carbonate, aqueous ammonia, sodium hydrogen carbonate, or the like can be used.
銀被覆反応の際には、銀塩を添加する前に溶液中に銅合金粉末を入れて攪拌し、銅合金粉末が溶液中に十分に分散している状態で、銀塩を含む溶液を添加するのが好ましい。この銀被覆反応の際の反応温度は、反応液が凝固または蒸発する温度でなければよいが、好ましくは２０〜８０℃、さらに好ましくは２５〜７０℃の範囲で設定する。また、反応時間は、銀または銀化合物の被覆量や反応温度によって異なるが、１分〜５時間の範囲で設定することができる。 In the silver coating reaction, before adding the silver salt, the copper alloy powder is put in the solution and stirred, and the solution containing the silver salt is added while the copper alloy powder is sufficiently dispersed in the solution. It is preferable to do this. The reaction temperature during the silver coating reaction may be a temperature at which the reaction solution is solidified or evaporated, but is preferably set in the range of 20 to 80 ° C, more preferably 25 to 70 ° C. Moreover, although reaction time changes with the coating amount of silver or a silver compound, and reaction temperature, it can set in the range of 1 minute-5 hours.
表面処理剤は、脂肪酸またはベンゾトリアゾールであるのが好ましい。この脂肪酸として、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、パルミトレイン酸、マルガリン酸、ステアリン酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、アラキジン酸、エイコサジエン酸、エイコサトリエン酸、エイコサテトラエン酸、アラキドン酸、ベヘン酸、リグノセリン酸、ネルボン酸、セロチン酸、モンタン酸、メリシン酸などを使用することができるが、パルミチン酸、ステアリン酸またはオレイン酸を使用するのが好ましい。 The surface treatment agent is preferably a fatty acid or benzotriazole. These fatty acids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid , Linoleic acid, linolenic acid, arachidic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melicic acid, etc. Although it is possible, it is preferred to use palmitic acid, stearic acid or oleic acid.
表面処理剤の添加量は、銀被覆銅合金粉末に対して０．１〜７質量％であるのが好ましく、０．３〜６質量％であるのがさらに好ましく、０．３〜５質量％であるのが最も好ましい。表面処理は、銀含有層で被覆した銅合金粉末と表面処理剤とを混合して行ってもよいし、銀含有層で被覆した銅合金粉末のスラリーに表面処理剤を添加して行ってもよい。このように銀被覆銅合金粉末を表面処理剤（好ましくは０．１〜７質量％の表面処理剤）で表面処理することにより、タップ密度を高めて分散性を向上させて、導電膜の体積抵抗率を低下させるとともに、耐酸化性を付与して、体積抵抗率の変化率を低下させることができる。 The addition amount of the surface treatment agent is preferably 0.1 to 7% by mass, more preferably 0.3 to 6% by mass, and 0.3 to 5% by mass with respect to the silver-coated copper alloy powder. Most preferably. The surface treatment may be performed by mixing the copper alloy powder coated with the silver-containing layer and the surface treatment agent, or by adding the surface treatment agent to the slurry of the copper alloy powder coated with the silver-containing layer. Good. In this way, by surface-treating the silver-coated copper alloy powder with a surface treatment agent (preferably 0.1 to 7% by mass of a surface treatment agent), the tap density is increased to improve dispersibility, and the volume of the conductive film is increased. The resistivity can be lowered and oxidation resistance can be imparted to reduce the rate of change in volume resistivity.
本発明による銀被覆銅合金粉末の実施の形態では、１〜５０質量％のニッケルおよび亜鉛の少なくとも一種を含み、残部が銅および不可避不純物からなる組成を有する銅合金粉末が、（銀被覆銅合金粉末に対して）７〜５０質量％の銀含有層（銀または銀化合物からなる層）により被覆され、炭素の含有量が０．１〜５質量％である。 In the embodiment of the silver-coated copper alloy powder according to the present invention, a copper alloy powder having a composition comprising at least one of 1 to 50% by mass of nickel and zinc and the balance consisting of copper and unavoidable impurities is (silver-coated copper alloy). It is covered with a silver content layer (layer consisting of silver or a silver compound) of 7 to 50% by mass (based on the powder), and the carbon content is 0.1 to 5% by mass.
この銀被覆銅合金粉末の銅合金粉末中のニッケルおよび亜鉛の少なくとも一種の含有量は、１〜５０質量％であり、１〜２０質量％であるのが好ましい。ニッケルおよび亜鉛の少なくとも一種の含有量が１質量％未満では、銅合金粉末中の銅の酸化が著しく、耐酸化性に問題が生じるので好ましくない。一方、５０質量％を超えると、銀被覆銅合金粉末の導電性に悪影響を及ぼすので好ましくない。 The content of at least one of nickel and zinc in the copper alloy powder of the silver-coated copper alloy powder is 1 to 50% by mass, and preferably 1 to 20% by mass. If the content of at least one kind of nickel and zinc is less than 1% by mass, copper in the copper alloy powder is significantly oxidized, which causes a problem in oxidation resistance. On the other hand, if it exceeds 50% by mass, the conductivity of the silver-coated copper alloy powder is adversely affected.
銀含有層の被覆量は、７〜５０質量％であり、８〜４５質量％であるのが好ましく、９〜４０質量％であるのがさらに好ましい。銀含有層の被覆量が７質量％未満では、銀被覆銅合金粉末の導電性に悪影響を及ぼすので好ましくない。一方、５０質量％を超えると、銀の使用量の増加によってコストが高くなるので好ましくない。 The coating amount of the silver-containing layer is 7 to 50% by mass, preferably 8 to 45% by mass, and more preferably 9 to 40% by mass. If the coating amount of the silver-containing layer is less than 7% by mass, the conductivity of the silver-coated copper alloy powder is adversely affected. On the other hand, if it exceeds 50 mass%, the cost increases due to an increase in the amount of silver used, which is not preferable.
この銀被覆銅合金粉末のタップ密度が３．８ｇ／ｃｍ３以上であるのが好ましく、３．９〜４．９ｃｍ３であるのがさらに好ましい。また、銀被覆銅合金粉末の真密度に対するタップ密度の割合が４２〜５５％であるのが好ましい。銀被覆銅合金粉末の真密度に対するタップ密度の割合が４２〜５５％であれば、この銀被覆銅合金粉末を導電性粉体として含む導電性ペーストを硬化して形成される導電膜中の粉末充填性が高く、銀被覆銅合金粒子間の接触確率が高くなり、導通パスを形成し易くなり、導電膜の体積抵抗率を低くすることができる。 Is preferably the tap density of the silver-coated copper alloy powder is 3.8 g / cm 3 or more, more preferably, it is 3.9~4.9cm 3. Moreover, it is preferable that the ratio of the tap density to the true density of the silver-coated copper alloy powder is 42 to 55%. If the ratio of the tap density to the true density of the silver-coated copper alloy powder is 42 to 55%, the powder in the conductive film formed by curing a conductive paste containing this silver-coated copper alloy powder as the conductive powder The filling property is high, the contact probability between the silver-coated copper alloy particles is high, it is easy to form a conduction path, and the volume resistivity of the conductive film can be lowered.
銅合金粉末の粒子径は、（ヘロス法によって）レーザー回折式粒度分布装置により測定した累積５０％粒子径（Ｄ５０径）が０．１〜１５μｍであるのが好ましく、０．３〜１０μｍであるのがさらに好ましく、１〜５μｍであるのが最も好ましい。累積５０％粒子径（Ｄ５０径）が０．１μｍ未満では、銀被覆銅合金粉末の導電性に悪影響を及ぼすので好ましくない。一方、１５μｍを超えると、微細な配線の形成が困難になるので好ましくない。 Particle size of the copper alloy powder (by Heroes method) 50% cumulative particle diameter measured by a laser diffraction type particle size distribution apparatus (D 50 diameter) is preferably in the range of 0.1-15, in 0.3~10μm More preferably, it is most preferably 1 to 5 μm. The cumulative 50% particle diameter (D 50 diameter) of less than 0.1 [mu] m, since an adverse effect on the conductivity of the silver-coated copper alloy powder is not preferable. On the other hand, if it exceeds 15 μm, it is not preferable because formation of fine wiring becomes difficult.
以下、本発明による銀被覆銅合金粉末およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the silver-coated copper alloy powder and the method for producing the same according to the present invention will be described in detail.
［実施例１］
銅７．２ｋｇと亜鉛０．８ｋｇを加熱した溶湯をタンディッシュ下部から落下させながら高圧水を吹付けて急冷凝固させ、得られた合金粉末をろ過し、水洗し、乾燥し、解砕し、分級して、銅合金粉末（銅−亜鉛合金粉末）を得た。
[Example 1]
While dropping molten metal heated to 7.2 kg of copper and 0.8 kg of zinc from the bottom of the tundish, high pressure water is sprayed and rapidly solidified. The resulting alloy powder is filtered, washed with water, dried and crushed. Classification was performed to obtain a copper alloy powder (copper-zinc alloy powder).
このようにして得られた（銀被覆前の）銅合金粉末の組成および粒度分布を求めたところ、銅合金粉末中の銅（Ｃｕ）の含有量は９０．２質量％、亜鉛（Ｚｎ）の含有量は９．８質量％であり、銅合金粉末はＣｕ９０Ｚｎ１０合金の粉末であった。また、銅合金粉末の累積１０％粒子径（Ｄ１０）は０．６μｍ、累積５０％粒子径（Ｄ５０）は１．７μｍ、累積９０％粒子径（Ｄ９０）は３．２μｍであった。なお、銅合金粉末中の銅および亜鉛の含有量は、銅合金粉末（約２．５ｇ）を塩化ビニル製リング（内径３．２ｍｍ×厚さ４ｍｍ）内に敷き詰めた後、錠剤型の成型圧縮機（株式会社前川試験製作所製の型番ＢＲＥ−５０）により１００ｋＮの荷重をかけて、銅合金粉末のペレットを作製し、このペレットをサンプルホルダー（開口径３．０ｃｍ）に入れて蛍光Ｘ線分析装置（株式会社リガク製のＲＩＸ２０００）内の測定位置にセットし、測定雰囲気を減圧下（８．０Ｐａ）とし、Ｘ線出力を５０ｋＶ、５０ｍＡとした条件で測定した結果から、装置に付属のソフトウェアで自動計算することによって求め、ナトリウム未満の軽元素を除いた成分の比率を算出した。また、銅合金粉末の粒度分布は、レーザー回折式粒度分布装置（ＳＹＭＰＡＴＥＣ社製のヘロス粒度分布測定装置（ＨＥＬＯＳ＆ＲＯＤＯＳ））により測定して、累積１０％粒子径（Ｄ１０）、累積５０％粒子径（Ｄ５０）、累積９０％粒子径（Ｄ９０）を求めた。 When the composition and particle size distribution of the copper alloy powder thus obtained (before silver coating) were determined, the copper (Cu) content in the copper alloy powder was 90.2% by mass, and zinc (Zn) The content was 9.8% by mass, and the copper alloy powder was a Cu 90 Zn 10 alloy powder. The cumulative 10% particle size (D 10 ) of the copper alloy powder was 0.6 μm, the cumulative 50% particle size (D 50 ) was 1.7 μm, and the cumulative 90% particle size (D 90 ) was 3.2 μm. . The content of copper and zinc in the copper alloy powder was determined by placing the copper alloy powder (about 2.5 g) in a vinyl chloride ring (inner diameter: 3.2 mm × thickness: 4 mm) and then compressing the tablet mold. A copper alloy powder pellet was produced by applying a load of 100 kN using a machine (model number BRE-50 manufactured by Maekawa Test Co., Ltd.), and this pellet was placed in a sample holder (opening diameter: 3.0 cm) and subjected to fluorescent X-ray analysis. Software attached to the device from the measurement results set in the measurement position in the device (RIX2000 manufactured by Rigaku Co., Ltd.), the measurement atmosphere under reduced pressure (8.0 Pa), and the X-ray output of 50 kV and 50 mA. It calculated | required by calculating automatically and calculated the ratio of the component except the light element less than sodium. The particle size distribution of the copper alloy powder is measured by a laser diffraction type particle size distribution device (Hellos particle size distribution measuring device (HELOS & RODOS) manufactured by SYMPATEC), and the cumulative particle size is 10% (D 10 ) and the cumulative particle size is 50%. (D 50 ), cumulative 90% particle diameter (D 90 ) was determined.
また、ＥＤＴＡ−２Ｎａ二水和物６１．９ｇと炭酸アンモニウム６１．９ｇを純水７２０ｇに溶解した溶液（溶液１）と、ＥＤＴＡ−２Ｎａ二水和物１３６．５ｇと炭酸アンモニウム６８．２ｇを純水５４４ｇに溶解した溶液に、硝酸銀２２．７ｇを純水７０ｇに溶解した溶液を加えて得られた溶液（溶液２）を用意した。 Further, a solution (solution 1) in which 61.9 g of EDTA-2Na dihydrate and 61.9 g of ammonium carbonate were dissolved in 720 g of pure water, 136.5 g of EDTA-2Na dihydrate and 68.2 g of ammonium carbonate were purified. A solution obtained by adding a solution obtained by dissolving 22.7 g of silver nitrate in 70 g of pure water to a solution dissolved in 544 g of water was prepared (solution 2).
次に、窒素雰囲気下において、得られた銅合金粉末（銅−亜鉛合金粉末）１３０ｇを溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅合金粉末（銅−亜鉛合金粉末）が分散した溶液に溶液２を加えて１時間攪拌した後、ろ過し、水洗し、乾燥して、銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）を得た。 Next, 130 g of the obtained copper alloy powder (copper-zinc alloy powder) was added to the solution 1 in a nitrogen atmosphere, and the temperature was raised to 35 ° C. while stirring. The solution 2 is added to the solution in which the copper alloy powder (copper-zinc alloy powder) is dispersed, and the mixture is stirred for 1 hour, then filtered, washed with water, and dried to obtain a silver-coated copper alloy powder (silver-coated copper-zinc alloy powder). )
次に、得られた銀被覆銅合金粉末８０ｇとパルミチン酸０．２４ｇ（銀被覆銅合金粉末に対して０．３質量％）をカッターミルに入れ、２０秒間の解砕を２回行うことによって、パルミチン酸で表面処理された銀被覆銅合金粉末を得た。 Next, 80 g of the obtained silver-coated copper alloy powder and 0.24 g of palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) are put into a cutter mill, and pulverized for 20 seconds twice. A silver-coated copper alloy powder surface-treated with palmitic acid was obtained.
このようにして得られた銀被覆銅合金粉末の組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めた。 The composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content of the silver-coated copper alloy powder thus obtained were determined.
銀被覆銅合金粉末中の銅および亜鉛の含有量は、銀被覆前の銅合金粉末中の銅および亜鉛の含有量と同様の方法により、銀被覆銅合金粉末のペレットを作製して求めた。また、銀被覆銅合金粉末の断面を集束イオンビーム（ＦＩＢ）加工観察装置（日本電子株式会社製のＪＥＭ−９３１０ＦＩＢ）によって加工した後、電界放出形走査電子顕微鏡（ＦＥ−ＳＥＭ）（日本電子株式会社製のＪＳＭ−６７００Ｆ）によって観察したところ、銅合金粉末の表面が銀で被覆されていることが確認された。また、銀被覆銅合金粉末の銀（Ａｇ）の被覆量も、銀被覆銅合金粉末中の銅および亜鉛の含有量と同様の方法により求めた。その結果、銀被覆銅合金粉末の銀の被覆量は１０．９質量％、銅の含有量は８１．６質量％、亜鉛の含有量は７．５質量％であった。 The contents of copper and zinc in the silver-coated copper alloy powder were determined by preparing pellets of silver-coated copper alloy powder by the same method as the contents of copper and zinc in the copper alloy powder before silver coating. Further, after processing the cross section of the silver-coated copper alloy powder with a focused ion beam (FIB) processing observation apparatus (JEM-9310FIB manufactured by JEOL Ltd.), a field emission scanning electron microscope (FE-SEM) (JEOL Ltd.) Observation with JSM-6700F) made by the company confirmed that the surface of the copper alloy powder was coated with silver. The silver (Ag) coating amount of the silver-coated copper alloy powder was also determined by the same method as the copper and zinc contents in the silver-coated copper alloy powder. As a result, the silver coating amount of the silver-coated copper alloy powder was 10.9% by mass, the copper content was 81.6% by mass, and the zinc content was 7.5% by mass.
銀被覆銅合金粉末の粒度分布は、銀被覆前の銅合金粉末の粒度分布と同様の方法により求めた。その結果、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は０．９μｍ、累積５０％粒子径（Ｄ５０）は２．４μｍ、累積９０％粒子径（Ｄ９０）は４．２μｍであった。 The particle size distribution of the silver-coated copper alloy powder was determined by the same method as the particle size distribution of the copper alloy powder before silver coating. As a result, the silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 0.9 μm, a cumulative 50% particle diameter (D 50 ) of 2.4 μm, and a cumulative 90% particle diameter (D 90 ) of 4.2 μm. Met.
銀被覆銅合金粉末のＢＥＴ比表面積は、ＢＥＴ比表面積測定装置（ユアサイオニクス株式会社製の４ソーブＵＳ）を用いてＢＥＴ法により求めた。その結果、銀被覆銅合金粉末のＢＥＴ比表面積は０．５４ｍ２／ｇであった。 The BET specific surface area of the silver-coated copper alloy powder was determined by the BET method using a BET specific surface area measuring apparatus (4 Sorb US manufactured by Yours IONICS Inc.). As a result, the BET specific surface area of the silver-coated copper alloy powder was 0.54 m 2 / g.
銀被覆銅合金粉末のタップ密度は、特開２００７−２６３８６０号公報に記載された方法と同様に、銀被覆銅合金粉末を内径６ｍｍの有底円筒形の容器に充填して銀被覆銅合金粉末層を形成し、この銀被覆銅合金粉末層に上部から０．１６Ｎ／ｍ２の圧力を加えた後、銀被覆銅合金粉末層の高さを測定し、この銀被覆銅合金粉末層の高さの測定値と、充填された銀被覆銅合金粉末の重量とから、銀被覆銅合金粉末の密度を求めて、銀被覆銅合金粉末のタップ密度とした。その結果、銀被覆銅合金粉末のタップ密度は４．２ｇ／ｃｍ３であった。また、この銀被覆銅合金粉末の真密度を算出すると８．９７ｇ／ｃｍ３であり、真密度に対するタップ密度の比は４７％であった。 The tap density of the silver-coated copper alloy powder is the same as the method described in Japanese Patent Application Laid-Open No. 2007-263860, and the silver-coated copper alloy powder is filled into a bottomed cylindrical container having an inner diameter of 6 mm. After forming a layer and applying a pressure of 0.16 N / m 2 from the top to the silver-coated copper alloy powder layer, the height of the silver-coated copper alloy powder layer is measured, and the height of the silver-coated copper alloy powder layer is measured. From the measured value of the thickness and the weight of the filled silver-coated copper alloy powder, the density of the silver-coated copper alloy powder was determined and used as the tap density of the silver-coated copper alloy powder. As a result, the tap density of the silver-coated copper alloy powder was 4.2 g / cm 3 . Further, the true density of the silver-coated copper alloy powder was calculated to be 8.97 g / cm 3 , and the ratio of the tap density to the true density was 47%.
銀被覆銅合金粉末中の酸素含有量は、酸素・窒素分析装置（ＬＥＣＯ社製のＴＣ−４３６型）により測定した。その結果、銀被覆銅合金粉末中の酸素含有量は０．１５質量％であった。 The oxygen content in the silver-coated copper alloy powder was measured by an oxygen / nitrogen analyzer (TC-436 type manufactured by LECO). As a result, the oxygen content in the silver-coated copper alloy powder was 0.15% by mass.
銀被覆銅合金粉末中の炭素含有量は、炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ−２２０Ｖ）により測定した。その結果、銀被覆銅合金粉末中の炭素含有量は０．２３質量％であった。 The carbon content in the silver-coated copper alloy powder was measured with a carbon / sulfur analyzer (EMIA-220V manufactured by Horiba, Ltd.). As a result, the carbon content in the silver-coated copper alloy powder was 0.23% by mass.
次に、得られた銀被覆銅合金粉末８．９２ｇと、熱硬化型樹脂としてビスフェノールＦ型エポキシ樹脂（株式会社ＡＤＥＫＡ製のアデカレジンＥＰ−４９０１Ｅ）０．７９ｇと、三フッ化ホウ素モノエチルアミン０．０４ｇと、溶媒としてブチルカルビトールアセテート０．２４ｇと、オレイン酸０．０１ｇとを混練脱泡機で混合した後、三本ロールを５回パスして均一に分散させることによって導電ペーストを得た。 Next, 8.92 g of the obtained silver-coated copper alloy powder, 0.79 g of bisphenol F type epoxy resin (Adeka Resin EP-4901E manufactured by ADEKA Corporation) as a thermosetting resin, and 0.73 g of boron trifluoride monoethylamine. 04 g, 0.24 g of butyl carbitol acetate as a solvent, and 0.01 g of oleic acid were mixed by a kneading defoaming machine, and then a three-roll was passed five times to uniformly disperse to obtain a conductive paste. .
この導電ペーストをスクリーン印刷法によってアルミナ基板上に（線幅５００μｍ、線長３７．５ｍｍのパターンに）印刷した後、大気中において２００℃で４０分間焼成して硬化させることによって導電膜を形成し、得られた導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 This conductive paste is printed on an alumina substrate by a screen printing method (in a pattern having a line width of 500 μm and a line length of 37.5 mm), and then baked and cured in the atmosphere at 200 ° C. for 40 minutes to form a conductive film. The volume resistivity of the obtained conductive film was calculated and the storage stability (reliability) was evaluated.
導電膜の体積抵抗率は、得られた導電膜のライン抵抗を二端子型抵抗率計（日置電機株式会社製の３５４０ミリオームハイテスタ）により測定し、膜厚を表面粗さ形状測定機（株式会社東京精密製のサーフコム１５００ＤＸ型）により測定して、体積抵抗率（Ω・ｃｍ）＝ライン抵抗（Ω）×膜厚（ｃｍ）×線幅（ｃｍ）／線長（ｃｍ）により算出した。その結果、導電膜の体積抵抗率は１０６μΩ・ｃｍであった。 For the volume resistivity of the conductive film, the line resistance of the obtained conductive film was measured with a two-terminal type resistivity meter (3540 mOhm HiTester manufactured by Hioki Electric Co., Ltd.), and the film thickness was measured with a surface roughness shape measuring instrument (stock) It was measured by a surfcom 1500DX type manufactured by Tokyo Seimitsu Co., Ltd., and calculated by volume resistivity (Ω · cm) = line resistance (Ω) × film thickness (cm) × line width (cm) / line length (cm). As a result, the volume resistivity of the conductive film was 106 μΩ · cm.
導電膜の保存安定性（信頼性）は、一定温度（１５０℃）に保たれた試験室内において１週間保存した導電膜の体積抵抗率（１週間保存後の体積抵抗率）を算出し、体積抵抗率の変化率（％）＝｛（１週間保存後の体積抵抗率）−（初期の体積抵抗率）｝×１００／（初期の体積抵抗率）によって評価した。その結果、１週間保存後の体積抵抗率は１２１μΩ・ｃｍであり、体積抵抗率の変化率は１４％であった。同様に２週間保存後の体積抵抗率を算出して、２週間の保存安定性（信頼性）を評価したところ、２週間保存後の体積抵抗率は１３７μΩ・ｃｍであり、体積抵抗率の変化率は２９％であった。 The storage stability (reliability) of the conductive film is calculated by calculating the volume resistivity (volume resistivity after storage for one week) of the conductive film stored for one week in a test chamber maintained at a constant temperature (150 ° C.). Resistivity change rate (%) = {(Volume resistivity after 1 week storage) − (Initial volume resistivity)} × 100 / (Initial volume resistivity) As a result, the volume resistivity after storage for 1 week was 121 μΩ · cm, and the rate of change in volume resistivity was 14%. Similarly, the volume resistivity after storage for 2 weeks was calculated and the storage stability (reliability) for 2 weeks was evaluated. The volume resistivity after storage for 2 weeks was 137 μΩ · cm, and the volume resistivity changed. The rate was 29%.
これらの結果を表１〜表４に示す。なお、表１において、銀含有層で被覆した銅合金粉末と表面処理剤とを混合して行った表面処理を「方式１」、銀含有層で被覆した銅合金粉末のスラリーに表面処理剤を添加して行った表面処理を「方式２」で示している。 These results are shown in Tables 1 to 4. In Table 1, the surface treatment performed by mixing the copper alloy powder coated with the silver-containing layer and the surface treatment agent is “method 1”, and the surface treatment agent is applied to the slurry of the copper alloy powder coated with the silver-containing layer. The surface treatment performed by the addition is indicated by “Method 2”.
［実施例２］
窒素雰囲気下において、実施例１と同様の銅合金粉末（銅−亜鉛合金粉末）１３０ｇを実施例１と同様の溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅−亜鉛合金粉末が分散した溶液に実施例１と同様の溶液２を加えて３０分間攪拌することにより、銀により被覆された銅−亜鉛合金粒子（銀被覆銅合金粒子）を含むスラリーを得た。
[Example 2]
Under a nitrogen atmosphere, 130 g of the same copper alloy powder (copper-zinc alloy powder) as in Example 1 was added to the same solution 1 as in Example 1, and the temperature was raised to 35 ° C. while stirring. A solution containing copper-zinc alloy particles (silver-coated copper alloy particles) coated with silver is prepared by adding the same solution 2 as in Example 1 to the solution in which the copper-zinc alloy powder is dispersed and stirring for 30 minutes. Obtained.
このスラリーに、パルミチン酸をアルコールに溶解させて得られた溶液８．７ｇ（パルミチン酸濃度５質量％）を添加し、さらに３０分間攪拌した後、ろ過し、水洗し、乾燥して、得られた粉末８０ｇをカッターミルに入れ、２０秒間の解砕を２回行うことによって、（銀被覆銅合金粉末に対して０．３質量％の）パルミチン酸で表面処理された銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）を得た。 To this slurry, 8.7 g of a solution obtained by dissolving palmitic acid in alcohol (palmitic acid concentration 5 mass%) was added, stirred for another 30 minutes, filtered, washed with water, and dried. The silver-coated copper alloy powder surface-treated with palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) was put into a cutter mill and pulverized for 20 seconds twice. Silver-coated copper-zinc alloy powder) was obtained.
このようにして得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 For the silver-coated copper alloy powder thus obtained, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は１０．３質量％、銅の含有量は８２．２質量％、亜鉛の含有量は７．５質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．２μｍ、累積５０％粒子径（Ｄ５０）は２．９μｍ、累積９０％粒子径（Ｄ９０）は５．０μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４２ｍ２／ｇ、タップ密度は４．９ｇ／ｃｍ３、真密度（計算値８．９６ｇ／ｃｍ３）に対するタップ密度の比は５５％であった。また、銀被覆銅合金粉末中の酸素含有量は０．１１質量％、炭素含有量は０．１９質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は９７μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１０５μΩ・ｃｍであり、体積抵抗率の変化率は８％であった。さらに、２週間保存後の体積抵抗率は１１３μΩ・ｃｍであり、体積抵抗率の変化率は１６％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 10.3% by mass, the copper content was 82.2% by mass, and the zinc content was 7.5% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.2 μm, a cumulative 50% particle diameter (D 50 ) of 2.9 μm, and a cumulative 90% particle diameter (D 90 ) of 5.0 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.42 m 2 / g, a tap density of 4.9 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 8.96 g / cm 3 ) is 55%. there were. The oxygen content in the silver-coated copper alloy powder was 0.11% by mass, and the carbon content was 0.19% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 97 μΩ · cm. The volume resistivity after storage for 1 week was 105 μΩ · cm, and the rate of change in volume resistivity was 8%. Furthermore, the volume resistivity after storage for 2 weeks was 113 μΩ · cm, and the rate of change in volume resistivity was 16%. These results are shown in Tables 1 to 4.
［比較例１］
表面処理を行わなかった以外は、実施例１と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 1]
The silver-coated copper alloy powder obtained by the same method as in Example 1 except that the surface treatment was not performed, the composition, the particle size distribution, the BET specific surface area, the tap density, the true density by the same method as in Example 1. The ratio of tap density to oxygen, the oxygen content, and the carbon content were determined, and the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は１０．８質量％、銅の含有量は８１．４質量％、亜鉛の含有量は７．８質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は０．８μｍ、累積５０％粒子径（Ｄ５０）は２．１μｍ、累積９０％粒子径（Ｄ９０）は３．６μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．７９ｍ２／ｇ、タップ密度は３．７ｇ／ｃｍ３、真密度（計算値８．９７ｇ／ｃｍ３）に対するタップ密度の比は４１％であった。また、銀被覆銅合金粉末中の酸素含有量は０．１５質量％、炭素含有量は０．０２質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１９０μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は２３３μΩ・ｃｍであり、体積抵抗率の変化率は２３％であった。さらに、２週間保存後の体積抵抗率は２６６μΩ・ｃｍであり、体積抵抗率の変化率は４０％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 10.8% by mass, the copper content was 81.4% by mass, and the zinc content was 7.8% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 0.8 μm, a cumulative 50% particle diameter (D 50 ) of 2.1 μm, and a cumulative 90% particle diameter (D 90 ) of 3.6 μm. there were. Further, the BET specific surface area of the silver-coated copper alloy powder is 0.79 m 2 / g, the tap density is 3.7 g / cm 3 , and the ratio of the tap density to the true density (calculated value 8.97 g / cm 3 ) is 41%. there were. The oxygen content in the silver-coated copper alloy powder was 0.15% by mass, and the carbon content was 0.02% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 190 μΩ · cm. The volume resistivity after storage for 1 week was 233 μΩ · cm, and the rate of change in volume resistivity was 23%. Further, the volume resistivity after storage for 2 weeks was 266 μΩ · cm, and the rate of change in volume resistivity was 40%. These results are shown in Tables 1 to 4.
［実施例３］
ＥＤＴＡ−２Ｎａ二水和物６１．９ｇと炭酸アンモニウム６１．９ｇを純水７２０ｇに溶解した溶液（溶液１）と、ＥＤＴＡ−２Ｎａ二水和物３０７．１ｇと炭酸アンモニウム１５３．５ｇを純水１２２３ｇに溶解した溶液に、硝酸銀５１．２ｇを純水１５８ｇに溶解した溶液を加えて得られた溶液（溶液２）を用意し、窒素雰囲気下において、実施例１と同様の銅合金粉末（銅−亜鉛合金粉末）１３０ｇを実施例１と同様の溶液１に加えた以外は、実施例１と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Example 3]
A solution (solution 1) of 61.9 g of EDTA-2Na dihydrate and 61.9 g of ammonium carbonate dissolved in 720 g of pure water, 307.1 g of EDTA-2Na dihydrate and 153.5 g of ammonium carbonate, 1223 g of pure water A solution obtained by adding 51.2 g of silver nitrate in 158 g of pure water to the solution dissolved in (a solution 2) was prepared, and the same copper alloy powder (copper- The silver-coated copper alloy powder obtained by the same method as in Example 1 except that 130 g of the zinc alloy powder) was added to the same solution 1 as in Example 1, the composition and particle size by the same method as in Example 1. The distribution, the BET specific surface area, the tap density, the ratio of the tap density to the true density, the oxygen content and the carbon content are obtained, and the volume resistivity of the conductive film is calculated and maintained in the same manner as in Example 1. Were evaluated for stability (reliability).
その結果、銀被覆銅合金粉末の銀の被覆量は２１．８質量％、銅の含有量は７１．６質量％、亜鉛の含有量は６．６質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．７μｍ、累積５０％粒子径（Ｄ５０）は４．１μｍ、累積９０％粒子径（Ｄ９０）は７．２μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４６ｍ２／ｇ、タップ密度は３．９ｇ／ｃｍ３、真密度（計算値９．１６ｇ／ｃｍ３）に対するタップ密度の比は４３％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２４質量％、炭素含有量は０．２０質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は７０μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は７４μΩ・ｃｍであり、体積抵抗率の変化率は６％であった。さらに、２週間保存後の体積抵抗率は７８μΩ・ｃｍであり、体積抵抗率の変化率は１１％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.8% by mass, the copper content was 71.6% by mass, and the zinc content was 6.6% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.7 μm, a cumulative 50% particle diameter (D 50 ) of 4.1 μm, and a cumulative 90% particle diameter (D 90 ) of 7.2 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.46 m 2 / g, a tap density of 3.9 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.16 g / cm 3 ) of 43%. there were. The oxygen content in the silver-coated copper alloy powder was 0.24% by mass, and the carbon content was 0.20% by mass. Moreover, the volume resistivity (initial volume resistivity) of the conductive film was 70 μΩ · cm. The volume resistivity after storage for 1 week was 74 μΩ · cm, and the rate of change in volume resistivity was 6%. Furthermore, the volume resistivity after storage for 2 weeks was 78 μΩ · cm, and the rate of change in volume resistivity was 11%. These results are shown in Tables 1 to 4.
［比較例２］
表面処理を行わなかった以外は、実施例３と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 2]
The silver-coated copper alloy powder obtained by the same method as in Example 3 except that the surface treatment was not performed, the composition, the particle size distribution, the BET specific surface area, the tap density, the true density by the same method as in Example 1. The ratio of tap density to oxygen, the oxygen content, and the carbon content were determined, and the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２２．５質量％、銅の含有量は７１．０質量％、亜鉛の含有量は６．５質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は３．０μｍ、累積９０％粒子径（Ｄ９０）は５．３μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．６８ｍ２／ｇ、タップ密度は３．５ｇ／ｃｍ３、真密度（計算値９．１７ｇ／ｃｍ３）に対するタップ密度の比は３８％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２０質量％、炭素含有量は０．０４質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は９８μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１０９μΩ・ｃｍであり、体積抵抗率の変化率は１１％であった。さらに、２週間保存後の体積抵抗率は１１９μΩ・ｃｍであり、体積抵抗率の変化率は２１％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 22.5% by mass, the copper content was 71.0% by mass, and the zinc content was 6.5% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 3.0 μm, and a cumulative 90% particle diameter (D 90 ) of 5.3 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.68 m 2 / g, a tap density of 3.5 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.17 g / cm 3 ) of 38%. there were. The oxygen content in the silver-coated copper alloy powder was 0.20% by mass, and the carbon content was 0.04% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 98 μΩ · cm. The volume resistivity after storage for 1 week was 109 μΩ · cm, and the rate of change in volume resistivity was 11%. Further, the volume resistivity after storage for 2 weeks was 119 μΩ · cm, and the rate of change in volume resistivity was 21%. These results are shown in Tables 1 to 4.
［実施例４］
銅７．６ｋｇと亜鉛０．４ｋｇを加熱した溶湯をタンディッシュ下部から落下させながら高圧水を吹付けて急冷凝固させ、得られた合金粉末をろ過し、水洗し、乾燥し、解砕し、分級して、銅合金粉末（銅−亜鉛合金粉末）を得た。
[Example 4]
While dropping molten metal heated from 7.6 kg of copper and 0.4 kg of zinc from the bottom of the tundish, high-pressure water is sprayed and rapidly solidified. The resulting alloy powder is filtered, washed with water, dried, crushed, Classification was performed to obtain a copper alloy powder (copper-zinc alloy powder).
このようにして得られた（銀被覆前の）銅合金粉末について、実施例１と同様の方法により、組成および粒度分布を求めたところ、銅合金粉末中の銅の含有量は９５．１質量％、亜鉛の含有量は４．９質量％であり、銅合金粉末はＣｕ９５Ｚｎ５合金の粉末であった。また、銅合金粉末の累積１０％粒子径（Ｄ１０）は０．７μｍ、累積５０％粒子径（Ｄ５０）は２．０μｍ、累積９０％粒子径（Ｄ９０）は３．６μｍであった。 With respect to the copper alloy powder thus obtained (before silver coating), the composition and the particle size distribution were determined in the same manner as in Example 1. The copper content in the copper alloy powder was 95.1 masses. %, The zinc content was 4.9% by mass, and the copper alloy powder was a Cu 95 Zn 5 alloy powder. Further, the cumulative 10% particle diameter (D 10 ) of the copper alloy powder was 0.7 μm, the cumulative 50% particle diameter (D 50 ) was 2.0 μm, and the cumulative 90% particle diameter (D 90 ) was 3.6 μm. .
次に、窒素雰囲気下において、得られた銅−亜鉛合金粉末１３０ｇを実施例１と同様の溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅−亜鉛合金粉末が分散した溶液に実施例３と同様の溶液２を加えて１時間攪拌して後、ろ過し、水洗し、乾燥して、銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）を得た。 Next, 130 g of the obtained copper-zinc alloy powder was added to the same solution 1 as in Example 1 and heated to 35 ° C. with stirring in a nitrogen atmosphere. The same solution 2 as in Example 3 was added to the solution in which the copper-zinc alloy powder was dispersed, stirred for 1 hour, filtered, washed with water, and dried to obtain a silver-coated copper alloy powder (silver-coated copper-zinc Alloy powder) was obtained.
次に、得られた銀被覆銅合金粉末８０ｇとパルミチン酸０．２４ｇ（銀被覆銅合金粉末に対して０．３質量％）をカッターミルに入れ、２０秒間の解砕を２回行うことによって、パルミチン酸で表面処理された銀被覆銅合金粉末を得た。 Next, 80 g of the obtained silver-coated copper alloy powder and 0.24 g of palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) are put into a cutter mill, and pulverized for 20 seconds twice. A silver-coated copper alloy powder surface-treated with palmitic acid was obtained.
このようにして得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 For the silver-coated copper alloy powder thus obtained, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．６質量％、銅の含有量は７５．２質量％、亜鉛の含有量は３．２質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．２μｍ、累積５０％粒子径（Ｄ５０）は２．８μｍ、累積９０％粒子径（Ｄ９０）は４．７μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４６ｍ２／ｇ、タップ密度は４．９ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は５３％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２７質量％、炭素含有量は０．２５質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は６９μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は７８μΩ・ｃｍであり、体積抵抗率の変化率は１３％であった。さらに、２週間保存後の体積抵抗率は８８μΩ・ｃｍであり、体積抵抗率の変化率は２８％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.6% by mass, the copper content was 75.2% by mass, and the zinc content was 3.2% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.2 μm, a cumulative 50% particle diameter (D 50 ) of 2.8 μm, and a cumulative 90% particle diameter (D 90 ) of 4.7 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.46 m 2 / g, a tap density of 4.9 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.22 g / cm 3 ) is 53%. there were. The oxygen content in the silver-coated copper alloy powder was 0.27% by mass, and the carbon content was 0.25% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 69 μΩ · cm. The volume resistivity after storage for 1 week was 78 μΩ · cm, and the rate of change in volume resistivity was 13%. Furthermore, the volume resistivity after storage for 2 weeks was 88 μΩ · cm, and the rate of change in volume resistivity was 28%. These results are shown in Tables 1 to 4.
［実施例５］
銀被覆銅合金粉末８０ｇをパルミチン酸２．４ｇ（銀被覆銅合金粉末に対して３質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Example 5]
The silver-coated copper alloy powder obtained by the same method as in Example 4 except that 80 g of the silver-coated copper alloy powder was surface-treated with 2.4 g of palmitic acid (3 mass% with respect to the silver-coated copper alloy powder) The composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were determined by the same method as in Example 1, and the conductivity was determined by the same method as in Example 1. The volume resistivity of the film was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２２．２質量％、銅の含有量は７４．８質量％、亜鉛の含有量は３．０質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は３．０μｍ、累積９０％粒子径（Ｄ９０）は５．６μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．６５ｍ２／ｇ、タップ密度は４．１ｇ／ｃｍ３、真密度（計算値９．２３ｇ／ｃｍ３）に対するタップ密度の比は４４％であった。また、銀被覆銅合金粉末中の酸素含有量は０．７０質量％、炭素含有量は２．０９質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は４９μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は５１μΩ・ｃｍであり、体積抵抗率の変化率は４％であった。さらに、２週間保存後の体積抵抗率は５５μΩ・ｃｍであり、体積抵抗率の変化率は１２％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 22.2% by mass, the copper content was 74.8% by mass, and the zinc content was 3.0% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 3.0 μm, and a cumulative 90% particle diameter (D 90 ) of 5.6 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.65 m 2 / g, a tap density of 4.1 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.23 g / cm 3 ) is 44%. there were. The oxygen content in the silver-coated copper alloy powder was 0.70% by mass, and the carbon content was 2.09% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 49 μΩ · cm. The volume resistivity after storage for 1 week was 51 μΩ · cm, and the rate of change in volume resistivity was 4%. Furthermore, the volume resistivity after storage for 2 weeks was 55 μΩ · cm, and the rate of change in volume resistivity was 12%. These results are shown in Tables 1 to 4.
［実施例６］
銀被覆銅合金粉末８０ｇをパルミチン酸４ｇ（銀被覆銅合金粉末に対して５質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Example 6]
The silver-coated copper alloy powder obtained in the same manner as in Example 4 except that 80 g of the silver-coated copper alloy powder was surface-treated with 4 g of palmitic acid (5% by mass with respect to the silver-coated copper alloy powder). 1, the composition, the particle size distribution, the BET specific surface area, the tap density, the ratio of the tap density to the true density, the oxygen content, and the carbon content were obtained. The volume resistivity was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２２．３質量％、銅の含有量は７４．８質量％、亜鉛の含有量は２．９質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．２μｍ、累積５０％粒子径（Ｄ５０）は２．９μｍ、累積９０％粒子径（Ｄ９０）は５．６μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．７３ｍ２／ｇ、タップ密度は３．９ｇ／ｃｍ３、真密度（計算値９．２３ｇ／ｃｍ３）に対するタップ密度の比は４２％であった。また、銀被覆銅合金粉末中の酸素含有量は０．９４質量％、炭素含有量は３．４３質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は７０μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は６７μΩ・ｃｍであり、体積抵抗率の変化率は−４％であった。さらに、２週間保存後の体積抵抗率は７０μΩ・ｃｍであり、体積抵抗率の変化率は０％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 22.3% by mass, the copper content was 74.8% by mass, and the zinc content was 2.9% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.2 μm, a cumulative 50% particle diameter (D 50 ) of 2.9 μm, and a cumulative 90% particle diameter (D 90 ) of 5.6 μm. there were. Further, the BET specific surface area of the silver-coated copper alloy powder is 0.73 m 2 / g, the tap density is 3.9 g / cm 3 , and the ratio of the tap density to the true density (calculated value 9.23 g / cm 3 ) is 42%. there were. The oxygen content in the silver-coated copper alloy powder was 0.94% by mass, and the carbon content was 3.43% by mass. Moreover, the volume resistivity (initial volume resistivity) of the conductive film was 70 μΩ · cm. The volume resistivity after storage for 1 week was 67 μΩ · cm, and the rate of change in volume resistivity was −4%. Further, the volume resistivity after storage for 2 weeks was 70 μΩ · cm, and the rate of change in volume resistivity was 0%. These results are shown in Tables 1 to 4.
［比較例３］
表面処理を行わなかった以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 3]
The silver-coated copper alloy powder obtained by the same method as in Example 4 except that the surface treatment was not performed, the composition, the particle size distribution, the BET specific surface area, the tap density, the true density by the same method as in Example 1. The ratio of tap density to oxygen, the oxygen content, and the carbon content were determined, and the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．６質量％、銅の含有量は７５．２質量％、亜鉛の含有量は３．２質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は３．０μｍ、累積９０％粒子径（Ｄ９０）は５．０μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．６４ｍ２／ｇ、タップ密度は３．７ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は４０％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２４質量％、炭素含有量は０．０６質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１０８μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１２６μΩ・ｃｍであり、体積抵抗率の変化率は１７％であった。さらに、２週間保存後の体積抵抗率は１３８μΩ・ｃｍであり、体積抵抗率の変化率は２８％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.6% by mass, the copper content was 75.2% by mass, and the zinc content was 3.2% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 3.0 μm, and a cumulative 90% particle diameter (D 90 ) of 5.0 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.64 m 2 / g, a tap density of 3.7 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.22 g / cm 3 ) of 40%. there were. The oxygen content in the silver-coated copper alloy powder was 0.24% by mass, and the carbon content was 0.06% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 108 μΩ · cm. The volume resistivity after storage for 1 week was 126 μΩ · cm, and the rate of change in volume resistivity was 17%. Further, the volume resistivity after storage for 2 weeks was 138 μΩ · cm, and the rate of change in volume resistivity was 28%. These results are shown in Tables 1 to 4.
［比較例４］
銀被覆銅合金粉末８０ｇをパルミチン酸０．０４ｇ（銀被覆銅合金粉末に対して０．０５質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 4]
Silver-coated copper alloy powder obtained by the same method as in Example 4 except that 80 g of silver-coated copper alloy powder was surface-treated with 0.04 g of palmitic acid (0.05% by mass with respect to silver-coated copper alloy powder). In the same manner as in Example 1, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were determined, and in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２２．２質量％、銅の含有量は７４．９質量％、亜鉛の含有量は２．９質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は２．９μｍ、累積９０％粒子径（Ｄ９０）は５．４μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．５９ｍ２／ｇ、タップ密度は３．５ｇ／ｃｍ３、真密度（計算値９．２３ｇ／ｃｍ３）に対するタップ密度の比は３８％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２６質量％、炭素含有量は０．０８質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は７４μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は８８μΩ・ｃｍであり、体積抵抗率の変化率は１９％であった。さらに、２週間保存後の体積抵抗率は１００μΩ・ｃｍであり、体積抵抗率の変化率は３５％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 22.2% by mass, the copper content was 74.9% by mass, and the zinc content was 2.9% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 2.9 μm, and a cumulative 90% particle diameter (D 90 ) of 5.4 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.59 m 2 / g, a tap density of 3.5 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.23 g / cm 3 ) of 38%. there were. The oxygen content in the silver-coated copper alloy powder was 0.26% by mass, and the carbon content was 0.08% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 74 μΩ · cm. The volume resistivity after storage for 1 week was 88 μΩ · cm, and the rate of change in volume resistivity was 19%. Further, the volume resistivity after storage for 2 weeks was 100 μΩ · cm, and the rate of change in volume resistivity was 35%. These results are shown in Tables 1 to 4.
［比較例５］
銀被覆銅合金粉末８０ｇをパルミチン酸８ｇ（銀被覆銅合金粉末に対して１０質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 5]
The silver-coated copper alloy powder obtained by the same method as in Example 4 except that 80 g of the silver-coated copper alloy powder was surface-treated with 8 g of palmitic acid (10% by mass with respect to the silver-coated copper alloy powder). 1, the composition, the particle size distribution, the BET specific surface area, the tap density, the ratio of the tap density to the true density, the oxygen content, and the carbon content were obtained. The volume resistivity was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２２．４質量％、銅の含有量は７４．６質量％、亜鉛の含有量は３．０質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は３．０μｍ、累積９０％粒子径（Ｄ９０）は５．９μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．８８ｍ２／ｇ、タップ密度は３．０ｇ／ｃｍ３、真密度（計算値９．２３ｇ／ｃｍ３）に対するタップ密度の比は３３％であった。また、銀被覆銅合金粉末中の酸素含有量は１．７０質量％、炭素含有量は６．５３質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１１３０μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は４００μΩ・ｃｍであり、体積抵抗率の変化率は−６５％であった。さらに、２週間保存後の体積抵抗率は３６６μΩ・ｃｍであり、体積抵抗率の変化率は−６８％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 22.4% by mass, the copper content was 74.6% by mass, and the zinc content was 3.0% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 3.0 μm, and a cumulative 90% particle diameter (D 90 ) of 5.9 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.88 m 2 / g, a tap density of 3.0 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.23 g / cm 3 ) of 33%. there were. The oxygen content in the silver-coated copper alloy powder was 1.70% by mass, and the carbon content was 6.53% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 1130 μΩ · cm. The volume resistivity after storage for 1 week was 400 μΩ · cm, and the rate of change in volume resistivity was −65%. Furthermore, the volume resistivity after storage for 2 weeks was 366 μΩ · cm, and the rate of change in volume resistivity was −68%. These results are shown in Tables 1 to 4.
［実施例７］
パルミチン酸の代わりにステアリン酸０．２４ｇ（銀被覆銅合金粉末に対して０．３質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Example 7]
A silver-coated copper alloy powder (silver) obtained by the same method as in Example 4 except that 0.24 g of stearic acid (0.3% by mass based on the silver-coated copper alloy powder) was used instead of palmitic acid. For coated copper-zinc alloy powder), the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were determined in the same manner as in Example 1. By the same method as in Example 1, the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．６質量％、銅の含有量は７５．３質量％、亜鉛の含有量は３．１質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は３．０μｍ、累積９０％粒子径（Ｄ９０）は４．９μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４０ｍ２／ｇ、タップ密度は４．４ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は４８％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２９質量％、炭素含有量は０．３０質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は９３μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１０６μΩ・ｃｍであり、体積抵抗率の変化率は１４％であった。さらに、２週間保存後の体積抵抗率は１１８μΩ・ｃｍであり、体積抵抗率の変化率は２７％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.6% by mass, the copper content was 75.3% by mass, and the zinc content was 3.1% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 3.0 μm, and a cumulative 90% particle diameter (D 90 ) of 4.9 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.40 m 2 / g, a tap density of 4.4 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.22 g / cm 3 ) of 48%. there were. The oxygen content in the silver-coated copper alloy powder was 0.29% by mass, and the carbon content was 0.30% by mass. Moreover, the volume resistivity (initial volume resistivity) of the conductive film was 93 μΩ · cm. The volume resistivity after storage for 1 week was 106 μΩ · cm, and the rate of change in volume resistivity was 14%. Further, the volume resistivity after storage for 2 weeks was 118 μΩ · cm, and the rate of change in volume resistivity was 27%. These results are shown in Tables 1 to 4.
［実施例８］
パルミチン酸の代わりにオレイン酸０．２４ｇ（銀被覆銅合金粉末に対して０．３質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Example 8]
The silver-coated copper alloy powder obtained by the same method as in Example 4 except that 0.24 g of oleic acid (0.3% by mass with respect to the silver-coated copper alloy powder) was surface-treated instead of palmitic acid. The composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were determined by the same method as in Example 1, and the conductivity was determined by the same method as in Example 1. The volume resistivity of the film was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．７質量％、銅の含有量は７５．２質量％、亜鉛の含有量は３．１質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は３．０μｍ、累積９０％粒子径（Ｄ９０）は５．０μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４６ｍ２／ｇ、タップ密度は４．５ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は４９％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２８質量％、炭素含有量は０．２５質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は８１μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は８９μΩ・ｃｍであり、体積抵抗率の変化率は１０％であった。さらに、２週間保存後の体積抵抗率は９８μΩ・ｃｍであり、体積抵抗率の変化率は２１％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.7% by mass, the copper content was 75.2% by mass, and the zinc content was 3.1% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 3.0 μm, and a cumulative 90% particle diameter (D 90 ) of 5.0 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.46 m 2 / g, a tap density of 4.5 g / cm 3 , and a tap density ratio of 49% to a true density (calculated value of 9.22 g / cm 3 ). there were. The oxygen content in the silver-coated copper alloy powder was 0.28% by mass, and the carbon content was 0.25% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 81 μΩ · cm. Further, the volume resistivity after storage for 1 week was 89 μΩ · cm, and the rate of change in volume resistivity was 10%. Furthermore, the volume resistivity after storage for 2 weeks was 98 μΩ · cm, and the rate of change in volume resistivity was 21%. These results are shown in Tables 1 to 4.
［実施例９］
パルミチン酸の代わりにベンゾトリアゾール（ＢＴＡ）０．０８ｇ（銀被覆銅合金粉末に対して０．１質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Example 9]
A silver-coated copper alloy obtained by the same method as in Example 4 except that 0.08 g of benzotriazole (BTA) (0.1% by mass based on the silver-coated copper alloy powder) was used instead of palmitic acid. For the powder, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were determined by the same method as in Example 1, and the same method as in Example 1 Thus, the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．６質量％、銅の含有量は７５．６質量％、亜鉛の含有量は２．８質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は２．９μｍ、累積９０％粒子径（Ｄ９０）は４．９μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．６３ｍ２／ｇ、タップ密度は４．１ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は４４％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２３質量％、炭素含有量は０．１２質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１０６μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１０１μΩ・ｃｍであり、体積抵抗率の変化率は−５％であった。さらに、２週間保存後の体積抵抗率は１０１μΩ・ｃｍであり、体積抵抗率の変化率は−５％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.6% by mass, the copper content was 75.6% by mass, and the zinc content was 2.8% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 2.9 μm, and a cumulative 90% particle diameter (D 90 ) of 4.9 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.63 m 2 / g, a tap density of 4.1 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.22 g / cm 3 ) of 44%. there were. The oxygen content in the silver-coated copper alloy powder was 0.23% by mass, and the carbon content was 0.12% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 106 μΩ · cm. The volume resistivity after storage for 1 week was 101 μΩ · cm, and the rate of change in volume resistivity was −5%. Furthermore, the volume resistivity after storage for 2 weeks was 101 μΩ · cm, and the rate of change in volume resistivity was −5%. These results are shown in Tables 1 to 4.
［実施例１０］
窒素雰囲気下において、実施例４と同様の銅合金粉末（銅−亜鉛合金粉末）１３０ｇを実施例１と同様の溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅−亜鉛合金粉末が分散した溶液に実施例３と同様の溶液２を加えて３０分間攪拌することにより、銀により被覆された銅−亜鉛合金粒子（銀被覆銅合金粒子）を含むスラリーを得た。
[Example 10]
Under a nitrogen atmosphere, 130 g of the same copper alloy powder (copper-zinc alloy powder) as in Example 4 was added to the same solution 1 as in Example 1, and the temperature was raised to 35 ° C. while stirring. A solution containing copper-zinc alloy particles coated with silver (silver-coated copper alloy particles) is prepared by adding the same solution 2 as in Example 3 to the solution in which the copper-zinc alloy powder is dispersed and stirring for 30 minutes. Obtained.
このスラリーに、パルミチン酸をアルコールに溶解させて得られた溶液１６．３ｇ（パルミチン酸濃度３質量％）を添加し、さらに３０分間攪拌した後、ろ過し、水洗し、乾燥して、得られた粉末８０ｇをカッターミルに入れ、２０秒間の解砕を２回行うことによって、（銀被覆銅合金粉末に対して０．３質量％の）パルミチン酸で表面処理された銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）を得た。 To this slurry was added 16.3 g of a solution obtained by dissolving palmitic acid in alcohol (palmitic acid concentration 3% by mass), and the mixture was further stirred for 30 minutes, filtered, washed with water, and dried. The silver-coated copper alloy powder surface-treated with palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) was put into a cutter mill and pulverized for 20 seconds twice. Silver-coated copper-zinc alloy powder) was obtained.
このようにして得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 For the silver-coated copper alloy powder thus obtained, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．６質量％、銅の含有量は７５．３質量％、亜鉛の含有量は３．１質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．８μｍ、累積５０％粒子径（Ｄ５０）は４．１μｍ、累積９０％粒子径（Ｄ９０）は７．２μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４４ｍ２／ｇ、タップ密度は４．０ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は４３％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２１質量％、炭素含有量は０．２０質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は６３μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は６６μΩ・ｃｍであり、体積抵抗率の変化率は５％であった。さらに、２週間保存後の体積抵抗率は７３μΩ・ｃｍであり、体積抵抗率の変化率は１６％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.6% by mass, the copper content was 75.3% by mass, and the zinc content was 3.1% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.8 μm, a cumulative 50% particle diameter (D 50 ) of 4.1 μm, and a cumulative 90% particle diameter (D 90 ) of 7.2 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.44 m 2 / g, a tap density of 4.0 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.22 g / cm 3 ) of 43%. there were. The oxygen content in the silver-coated copper alloy powder was 0.21% by mass, and the carbon content was 0.20% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 63 μΩ · cm. The volume resistivity after storage for 1 week was 66 μΩ · cm, and the rate of change in volume resistivity was 5%. Further, the volume resistivity after storage for 2 weeks was 73 μΩ · cm, and the rate of change in volume resistivity was 16%. These results are shown in Tables 1 to 4.
［比較例６］
パルミチン酸の代わりにイミダゾール０．０８ｇ（銀被覆銅合金粉末に対して０．１質量％）で表面処理した以外は、実施例４と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 6]
For silver-coated copper alloy powder obtained by the same method as in Example 4 except that surface treatment was performed with 0.08 g of imidazole (0.1% by mass based on silver-coated copper alloy powder) instead of palmitic acid. The composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained by the same method as in Example 1, and the conductive film was obtained by the same method as in Example 1. The volume resistivity was calculated and the storage stability (reliability) was evaluated.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．４質量％、銅の含有量は７５．８質量％、亜鉛の含有量は２．８質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．２μｍ、累積５０％粒子径（Ｄ５０）は２．９μｍ、累積９０％粒子径（Ｄ９０）は４．８μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．６４ｍ２／ｇ、タップ密度は３．７ｇ／ｃｍ３、真密度（計算値９．２２ｇ／ｃｍ３）に対するタップ密度の比は４０％であった。また、銀被覆銅合金粉末中の酸素含有量は０．２５質量％、炭素含有量は０．０９質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は２１７μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は２５６μΩ・ｃｍであり、体積抵抗率の変化率は１８％であった。さらに、２週間保存後の体積抵抗率は２７９μΩ・ｃｍであり、体積抵抗率の変化率は２９％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.4% by mass, the copper content was 75.8% by mass, and the zinc content was 2.8% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.2 μm, a cumulative 50% particle diameter (D 50 ) of 2.9 μm, and a cumulative 90% particle diameter (D 90 ) of 4.8 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.64 m 2 / g, a tap density of 3.7 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.22 g / cm 3 ) of 40%. there were. The oxygen content in the silver-coated copper alloy powder was 0.25% by mass, and the carbon content was 0.09% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 217 μΩ · cm. The volume resistivity after storage for 1 week was 256 μΩ · cm, and the rate of change in volume resistivity was 18%. Further, the volume resistivity after storage for 2 weeks was 279 μΩ · cm, and the rate of change in volume resistivity was 29%. These results are shown in Tables 1 to 4.
［実施例１１］
銅７．８４ｋｇと亜鉛０．１６ｋｇを加熱した溶湯をタンディッシュ下部から落下させながら高圧水を吹付けて急冷凝固させ、得られた合金粉末をろ過し、水洗し、乾燥し、解砕し、分級して、銅合金粉末（銅−亜鉛合金粉末）を得た。
[Example 11]
While dropping molten metal heated to 7.84 kg of copper and 0.16 kg of zinc from the lower part of the tundish, high pressure water was sprayed and rapidly solidified, and the resulting alloy powder was filtered, washed with water, dried and crushed. Classification was performed to obtain a copper alloy powder (copper-zinc alloy powder).
このようにして得られた（銀被覆前の）銅合金粉末について、実施例１と同様の方法により、組成および粒度分布を求めたところ、銅合金粉末中の銅の含有量は９８．１質量％、亜鉛の含有量は１．９質量％であり、銅合金粉末はＣｕ９８Ｚｎ２合金の粉末であった。また、銅合金粉末の累積１０％粒子径（Ｄ１０）は０．５μｍ、累積５０％粒子径（Ｄ５０）は１．６μｍ、累積９０％粒子径（Ｄ９０）は３．１μｍであった。 The copper alloy powder thus obtained (before silver coating) was determined for its composition and particle size distribution by the same method as in Example 1. The copper content in the copper alloy powder was 98.1 masses. %, The zinc content was 1.9% by mass, and the copper alloy powder was a Cu 98 Zn 2 alloy powder. The cumulative 10% particle diameter (D 10 ) of the copper alloy powder was 0.5 μm, the cumulative 50% particle diameter (D 50 ) was 1.6 μm, and the cumulative 90% particle diameter (D 90 ) was 3.1 μm. .
次に、窒素雰囲気下において、得られた銅−亜鉛合金粉末１３０ｇを実施例１と同様の溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅−亜鉛合金粉末が分散した溶液に実施例３と同様の溶液２を加えて１時間攪拌して後、ろ過し、水洗し、乾燥して、銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）を得た。 Next, 130 g of the obtained copper-zinc alloy powder was added to the same solution 1 as in Example 1 and heated to 35 ° C. with stirring in a nitrogen atmosphere. The same solution 2 as in Example 3 was added to the solution in which the copper-zinc alloy powder was dispersed, stirred for 1 hour, filtered, washed with water, and dried to obtain a silver-coated copper alloy powder (silver-coated copper-zinc Alloy powder) was obtained.
次に、得られた銀被覆銅合金粉末８０ｇとパルミチン酸０．２４ｇ（銀被覆銅合金粉末に対して０．３質量％）をカッターミルに入れ、２０秒間の解砕を２回行うことによって、パルミチン酸で表面処理された銀被覆銅合金粉末を得た。 Next, 80 g of the obtained silver-coated copper alloy powder and 0.24 g of palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) are put into a cutter mill, and pulverized for 20 seconds twice. A silver-coated copper alloy powder surface-treated with palmitic acid was obtained.
このようにして得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 For the silver-coated copper alloy powder thus obtained, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．８質量％、銅の含有量は７７．１質量％、亜鉛の含有量は１．１質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．５μｍ、累積５０％粒子径（Ｄ５０）は３．２μｍ、累積９０％粒子径（Ｄ９０）は５．２μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．５０ｍ２／ｇ、タップ密度は４．１ｇ／ｃｍ３、真密度（計算値９．２６ｇ／ｃｍ３）に対するタップ密度の比は４４％であった。また、銀被覆銅合金粉末中の酸素含有量は０．３８質量％、炭素含有量は０．２５質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１２６μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１４７μΩ・ｃｍであり、体積抵抗率の変化率は１７％であった。さらに、２週間保存後の体積抵抗率は１６４μΩ・ｃｍであり、体積抵抗率の変化率は３０％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.8% by mass, the copper content was 77.1% by mass, and the zinc content was 1.1% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.5 μm, a cumulative 50% particle diameter (D 50 ) of 3.2 μm, and a cumulative 90% particle diameter (D 90 ) of 5.2 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.50 m 2 / g, a tap density of 4.1 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.26 g / cm 3 ) is 44%. there were. The oxygen content in the silver-coated copper alloy powder was 0.38% by mass, and the carbon content was 0.25% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 126 μΩ · cm. The volume resistivity after storage for 1 week was 147 μΩ · cm, and the rate of change in volume resistivity was 17%. Further, the volume resistivity after storage for 2 weeks was 164 μΩ · cm, and the rate of change in volume resistivity was 30%. These results are shown in Tables 1 to 4.
［実施例１２］
窒素雰囲気下において、実施例１１と同様の銅合金粉末（銅−亜鉛合金粉末）１３０ｇを実施例１と同様の溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅−亜鉛合金粉末が分散した溶液に実施例３と同様の溶液２を加えて３０分間攪拌することにより、銀により被覆された銅−亜鉛合金粒子（銀被覆銅合金粒子）を含むスラリーを得た。
[Example 12]
Under a nitrogen atmosphere, 130 g of the same copper alloy powder (copper-zinc alloy powder) as in Example 11 was added to the same solution 1 as in Example 1, and the temperature was raised to 35 ° C. while stirring. A solution containing copper-zinc alloy particles coated with silver (silver-coated copper alloy particles) is prepared by adding the same solution 2 as in Example 3 to the solution in which the copper-zinc alloy powder is dispersed and stirring for 30 minutes. Obtained.
このスラリーに、パルミチン酸をアルコールに溶解させて得られた溶１６．３ｇ（パルミチン酸濃度３質量％）を添加し、さらに３０分間攪拌した後、ろ過し、水洗し、乾燥して、得られた粉末８０ｇをカッターミルに入れ、２０秒間の解砕を２回行うことによって、（銀被覆銅合金粉末に対して０．３質量％の）パルミチン酸で表面処理された銀被覆銅合金粉末（銀被覆銅−亜鉛合金粉末）を得た。 To this slurry was added 16.3 g (palmitic acid concentration 3 mass%) obtained by dissolving palmitic acid in alcohol, and the mixture was further stirred for 30 minutes, filtered, washed with water, and dried. The silver-coated copper alloy powder surface-treated with palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) was put into a cutter mill and pulverized for 20 seconds twice. Silver-coated copper-zinc alloy powder) was obtained.
このようにして得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 For the silver-coated copper alloy powder thus obtained, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２１．６質量％、銅の含有量は７７．４質量％、亜鉛の含有量は１．０質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は２．２μｍ、累積５０％粒子径（Ｄ５０）は４．９μｍ、累積９０％粒子径（Ｄ９０）は８．２μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．４３ｍ２／ｇ、タップ密度は３．９ｇ／ｃｍ３、真密度（計算値９．２６ｇ／ｃｍ３）に対するタップ密度の比は４２％であった。また、銀被覆銅合金粉末中の酸素含有量は０．３０質量％、炭素含有量は０．２０質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１０２μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１１２μΩ・ｃｍであり、体積抵抗率の変化率は１０％であった。さらに、２週間保存後の体積抵抗率は１２３μΩ・ｃｍであり、体積抵抗率の変化率は２１％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 21.6% by mass, the copper content was 77.4% by mass, and the zinc content was 1.0% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 2.2 μm, a cumulative 50% particle diameter (D 50 ) of 4.9 μm, and a cumulative 90% particle diameter (D 90 ) of 8.2 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.43 m 2 / g, a tap density of 3.9 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.26 g / cm 3 ) is 42%. there were. The oxygen content in the silver-coated copper alloy powder was 0.30% by mass, and the carbon content was 0.20% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 102 μΩ · cm. The volume resistivity after storage for 1 week was 112 μΩ · cm, and the rate of change in volume resistivity was 10%. Furthermore, the volume resistivity after storage for 2 weeks was 123 μΩ · cm, and the rate of change in volume resistivity was 21%. These results are shown in Tables 1 to 4.
［比較例７］
表面処理を行わなかった以外は、実施例１１と同様の方法により得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 7]
The silver-coated copper alloy powder obtained by the same method as in Example 11 except that the surface treatment was not performed, the composition, the particle size distribution, the BET specific surface area, the tap density, the true density by the same method as in Example 1. The ratio of tap density to oxygen, the oxygen content, and the carbon content were determined, and the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は２２．１質量％、銅の含有量は７６．７質量％、亜鉛の含有量は１．２質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．３μｍ、累積５０％粒子径（Ｄ５０）は２．９μｍ、累積９０％粒子径（Ｄ９０）は４．８μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．９１ｍ２／ｇ、タップ密度は３．６ｇ／ｃｍ３、真密度（計算値９．２６ｇ／ｃｍ３）に対するタップ密度の比は３９％であった。また、銀被覆銅合金粉末中の酸素含有量は０．３７質量％、炭素含有量は０．０５質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は１５７μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は１９６μΩ・ｃｍであり、体積抵抗率の変化率は２５％であった。さらに、２週間保存後の体積抵抗率は２３１μΩ・ｃｍであり、体積抵抗率の変化率は４７％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 22.1% by mass, the copper content was 76.7% by mass, and the zinc content was 1.2% by mass. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.3 μm, a cumulative 50% particle diameter (D 50 ) of 2.9 μm, and a cumulative 90% particle diameter (D 90 ) of 4.8 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.91 m 2 / g, a tap density of 3.6 g / cm 3 and a ratio of the tap density to the true density (calculated value of 9.26 g / cm 3 ) of 39%. there were. The oxygen content in the silver-coated copper alloy powder was 0.37% by mass, and the carbon content was 0.05% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 157 μΩ · cm. Further, the volume resistivity after storage for 1 week was 196 μΩ · cm, and the rate of change in volume resistivity was 25%. Furthermore, the volume resistivity after storage for 2 weeks was 231 μΩ · cm, and the rate of change in volume resistivity was 47%. These results are shown in Tables 1 to 4.
［実施例１３］
銅６．４ｋｇとニッケル０．８ｋｇと亜鉛０．８ｋｇを加熱した溶湯をタンディッシュ下部から落下させながら高圧水を吹付けて急冷凝固させ、得られた合金粉末をろ過し、水洗し、乾燥し、解砕し、分級して、銅合金粉末（銅−ニッケル−亜鉛合金粉末）を得た。
[Example 13]
While dropping molten metal heated from 6.4 kg of copper, 0.8 kg of nickel and 0.8 kg of zinc from the bottom of the tundish, it is rapidly solidified by spraying high pressure water, and the resulting alloy powder is filtered, washed with water and dried. And then pulverized and classified to obtain a copper alloy powder (copper-nickel-zinc alloy powder).
このようにして得られた（銀被覆前の）銅合金粉末の組成および粒度分布を求めたところ、銅合金粉末中の銅の含有量は８２．９質量％、ニッケル（Ｎｉ）の含有量は１０．２質量％、亜鉛の含有量は６．９質量％であり、銅合金粉末はＣｕ８０Ｎｉ１０Ｚｎ１０合金の粉末であった。また、銅合金粉末の累積１０％粒子径（Ｄ１０）は０．７μｍ、累積５０％粒子径（Ｄ５０）は１．８μｍ、累積９０％粒子径（Ｄ９０）は３．３μｍであった。なお、銅合金粉末中の銅、ニッケルおよび亜鉛の含有量は、実施例１において銅合金粉末中の銅および亜鉛の含有量を求めた方法と同様の方法により求め、銅合金粉末の粒度分布は、実施例１と同様の方法により求めた。 When the composition and particle size distribution of the copper alloy powder thus obtained (before silver coating) were determined, the copper content in the copper alloy powder was 82.9% by mass, and the nickel (Ni) content was The content of zinc was 10.2% by mass, and the content of zinc was 6.9% by mass. The copper alloy powder was a Cu 80 Ni 10 Zn 10 alloy powder. The cumulative 10% particle size (D 10 ) of the copper alloy powder was 0.7 μm, the cumulative 50% particle size (D 50 ) was 1.8 μm, and the cumulative 90% particle size (D 90 ) was 3.3 μm. . The contents of copper, nickel and zinc in the copper alloy powder were determined by the same method as the method for determining the contents of copper and zinc in the copper alloy powder in Example 1, and the particle size distribution of the copper alloy powder was It was determined by the same method as in Example 1.
次に、窒素雰囲気下において、得られた銅−ニッケル−亜鉛合金粉末１３０ｇを実施例１と同様の溶液１に加えて、攪拌しながら３５℃まで昇温させた。この銅−ニッケル−亜鉛合金粉末が分散した溶液に実施例１と同様の溶液２を加えて１時間攪拌して後、ろ過し、水洗し、乾燥して、銀被覆銅合金粉末（銀被覆銅−ニッケル−亜鉛合金粉末）を得た。 Next, 130 g of the obtained copper-nickel-zinc alloy powder was added to the same solution 1 as in Example 1 and heated to 35 ° C. with stirring in a nitrogen atmosphere. A solution 2 similar to that of Example 1 was added to the solution in which the copper-nickel-zinc alloy powder was dispersed, stirred for 1 hour, filtered, washed with water, and dried to obtain a silver-coated copper alloy powder (silver-coated copper). -Nickel-zinc alloy powder).
次に、得られた銀被覆銅合金粉末８０ｇとパルミチン酸０．２４ｇ（銀被覆銅合金粉末に対して０．３質量％）をカッターミルに入れ、２０秒間の解砕を２回行うことによって、パルミチン酸で表面処理された銀被覆銅合金粉末を得た。 Next, 80 g of the obtained silver-coated copper alloy powder and 0.24 g of palmitic acid (0.3% by mass with respect to the silver-coated copper alloy powder) are put into a cutter mill, and pulverized for 20 seconds twice. A silver-coated copper alloy powder surface-treated with palmitic acid was obtained.
このようにして得られた銀被覆銅合金粉末について、実施例１と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。 For the silver-coated copper alloy powder thus obtained, the composition, particle size distribution, BET specific surface area, tap density, ratio of tap density to true density, oxygen content and carbon content were obtained in the same manner as in Example 1. The volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 1.
その結果、銀被覆銅合金粉末の銀の被覆量は１１．０質量％、銅の含有量は７５．０質量％、ニッケルの含有量は９．１質量％、亜鉛の含有量は４．９質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．１μｍ、累積５０％粒子径（Ｄ５０）は２．６μｍ、累積９０％粒子径（Ｄ９０）は４．５μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．５０ｍ２／ｇ、タップ密度は４．３ｇ／ｃｍ３、真密度（計算値９．０２ｇ／ｃｍ３）に対するタップ密度の比は４８％であった。また、銀被覆銅合金粉末中の酸素含有量は０．１７質量％、炭素含有量は０．３２質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は２５２μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は２４９μΩ・ｃｍであり、体積抵抗率の変化率は−１％であった。さらに、２週間保存後の体積抵抗率は２４９μΩ・ｃｍであり、体積抵抗率の変化率は−１％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 11.0% by mass, the copper content was 75.0% by mass, the nickel content was 9.1% by mass, and the zinc content was 4.9. It was mass%. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.1 μm, a cumulative 50% particle diameter (D 50 ) of 2.6 μm, and a cumulative 90% particle diameter (D 90 ) of 4.5 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.50 m 2 / g, a tap density of 4.3 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.02 g / cm 3 ) of 48%. there were. The oxygen content in the silver-coated copper alloy powder was 0.17% by mass, and the carbon content was 0.32% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 252 μΩ · cm. The volume resistivity after storage for 1 week was 249 μΩ · cm, and the rate of change in volume resistivity was −1%. Furthermore, the volume resistivity after storage for 2 weeks was 249 μΩ · cm, and the rate of change in volume resistivity was −1%. These results are shown in Tables 1 to 4.
［比較例８］
表面処理を行わなかった以外は、実施例１３と同様の方法により得られた銀被覆銅合金粉末について、実施例１３と同様の方法により、組成、粒度分布、ＢＥＴ比表面積、タップ密度、真密度に対するタップ密度の比、酸素含有量および炭素含有量を求めるとともに、実施例１３と同様の方法により、導電膜の体積抵抗率の算出と保存安定性（信頼性）の評価を行った。
[Comparative Example 8]
Except that the surface treatment was not performed, the composition, particle size distribution, BET specific surface area, tap density, true density of the silver-coated copper alloy powder obtained by the same method as in Example 13 were the same as in Example 13. The ratio of the tap density to oxygen, the oxygen content, and the carbon content were determined, and the volume resistivity of the conductive film was calculated and the storage stability (reliability) was evaluated by the same method as in Example 13.
その結果、銀被覆銅合金粉末の銀の被覆量は１１．１質量％、銅の含有量は７４．９質量％、ニッケルの含有量は９．２質量％、亜鉛の含有量は４．８質量％であった。また、銀被覆銅合金粉末の累積１０％粒子径（Ｄ１０）は１．０μｍ、累積５０％粒子径（Ｄ５０）は２．４μｍ、累積９０％粒子径（Ｄ９０）は４．０μｍであった。また、銀被覆銅合金粉末のＢＥＴ比表面積は０．７５ｍ２／ｇ、タップ密度は３．５ｇ／ｃｍ３、真密度（計算値９．０２ｇ／ｃｍ３）に対するタップ密度の比は３９％であった。また、銀被覆銅合金粉末中の酸素含有量は０．１６質量％、炭素含有量は０．０３質量％であった。また、導電膜の体積抵抗率（初期の体積抵抗率）は３３１μΩ・ｃｍであった。また、１週間保存後の体積抵抗率は３４５μΩ・ｃｍであり、体積抵抗率の変化率は４％であった。さらに、２週間保存後の体積抵抗率は３３９μΩ・ｃｍであり、体積抵抗率の変化率は２％であった。これらの結果を表１〜表４に示す。 As a result, the silver coating amount of the silver-coated copper alloy powder was 11.1% by mass, the copper content was 74.9% by mass, the nickel content was 9.2% by mass, and the zinc content was 4.8%. It was mass%. The silver-coated copper alloy powder has a cumulative 10% particle diameter (D 10 ) of 1.0 μm, a cumulative 50% particle diameter (D 50 ) of 2.4 μm, and a cumulative 90% particle diameter (D 90 ) of 4.0 μm. there were. The silver-coated copper alloy powder has a BET specific surface area of 0.75 m 2 / g, a tap density of 3.5 g / cm 3 , and a ratio of the tap density to the true density (calculated value of 9.02 g / cm 3 ) of 39%. there were. The oxygen content in the silver-coated copper alloy powder was 0.16% by mass, and the carbon content was 0.03% by mass. Further, the volume resistivity (initial volume resistivity) of the conductive film was 331 μΩ · cm. The volume resistivity after storage for 1 week was 345 μΩ · cm, and the rate of change in volume resistivity was 4%. Furthermore, the volume resistivity after storage for 2 weeks was 339 μΩ · cm, and the rate of change in volume resistivity was 2%. These results are shown in Tables 1 to 4.
表１〜表４からわかるように、実施例１〜２と比較例１、実施例３と比較例２、実施例４〜６と比較例３、実施例１１〜１２と比較例７、実施例１３と比較例８を比較すると、銀被覆銅合金粉末を表面処理剤で表面処理することにより、タップ密度を高めて分散性を向上させて、導電膜の体積抵抗率を低下させるとともに、体積抵抗率の変化率を低下させることができる。また、実施例４〜６と比較例４〜５を比較すると、表面処理剤の添加量は、銀被覆銅合金粉末に対して０．０５質量％では少な過ぎ、１０質量％では多過ぎるのがわかる。さらに、実施例７〜１０と比較例６との比較からわかるように、表面処理剤としてイミダゾールを使用するよりも、パルミチン酸、ステアリン酸、オレイン酸、ベンゾトリアゾール（ＢＴＡ）などを使用した方が、タップ密度を高めて分散性を向上させて、導電膜の体積抵抗率を低下させるとともに、体積抵抗率の変化率を低下させることができる。 As can be seen from Tables 1 to 4, Examples 1 and 2 and Comparative Example 1, Example 3 and Comparative Example 2, Examples 4 to 6 and Comparative Example 3, Examples 11 to 12 and Comparative Example 7, Example 13 and Comparative Example 8 are compared, surface treatment of the silver-coated copper alloy powder with a surface treatment agent increases the tap density and improves dispersibility, lowers the volume resistivity of the conductive film, and reduces the volume resistance. The rate of change of rate can be reduced. Further, when Examples 4 to 6 and Comparative Examples 4 to 5 are compared, the amount of the surface treatment agent added is too small at 0.05% by mass relative to the silver-coated copper alloy powder, and it is excessive at 10% by mass. Recognize. Furthermore, as can be seen from the comparison between Examples 7 to 10 and Comparative Example 6, it is better to use palmitic acid, stearic acid, oleic acid, benzotriazole (BTA), etc. than to use imidazole as the surface treatment agent. In addition to increasing the tap density and improving dispersibility, the volume resistivity of the conductive film can be reduced, and the rate of change in volume resistivity can be reduced.
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| JPS62179566A (en) * | 1986-01-31 | 1987-08-06 | Toyobo Co Ltd | Electrically conductive resin composition |
| JPH0378906A (en) * | 1989-08-23 | 1991-04-04 | Furukawa Electric Co Ltd:The | Conductive paste |
| JP2012167337A (en) * | 2011-02-15 | 2012-09-06 | Dowa Electronics Materials Co Ltd | Method of manufacturing silver coated flake copper powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS62179566A (en) * | 1986-01-31 | 1987-08-06 | Toyobo Co Ltd | Electrically conductive resin composition |
| JPH0378906A (en) * | 1989-08-23 | 1991-04-04 | Furukawa Electric Co Ltd:The | Conductive paste |
| JP2012167337A (en) * | 2011-02-15 | 2012-09-06 | Dowa Electronics Materials Co Ltd | Method of manufacturing silver coated flake copper powder |
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