JP4864195B2 - Coated copper powder - Google Patents
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- JP4864195B2 JP4864195B2 JP2000260964A JP2000260964A JP4864195B2 JP 4864195 B2 JP4864195 B2 JP 4864195B2 JP 2000260964 A JP2000260964 A JP 2000260964A JP 2000260964 A JP2000260964 A JP 2000260964A JP 4864195 B2 JP4864195 B2 JP 4864195B2
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Description
【０００１】
【発明の属する技術分野】
本発明は銅粒子の表面上にニッケル合金からなる中間被覆層及び銀からなる表面被覆層を有する被覆銅粒子からなる被覆銅粉に関し、特に、少量の添加で目的の導電性を得ることができ且つ導電性についての耐熱性を有するので、電磁波シールドや導電ペーストに用いるのに適している該被覆銅粉に関する。
【０００２】
【従来の技術】
コンピューターをはじめとする電子機器類においては、外部からの電磁波による影響を受けて誤作動が生じる問題がクローズアップされており、それで電磁波シールドを目的としたコンピュータの外装部における導電性向上手段について開発が進んでいる。この外装部の導電性向上の手段としては、電子機器類の軽量化の為に用いられている有機樹脂に導電性物質をフィラーとして添加する方法や、導電性物質を塗料化して外装部に塗布する方法等が一般的である。
【０００３】
この導電性物質に求められる重要な特性は当然のことながら導電性が高いことであり、コスト面も考え合わせると導電性物質として金属粉、特に金属超微粉が好ましく、中でも銀超微粉は耐酸化性にも優れている為、汎用されている。しかし、銀は金属粉の中でも高価な物質であるので、更なるコスト低減を目標として代替材料が求められている。
【０００４】
この要求にこたえる代替材料は銀の上記の特徴を損なわないものであることが重要であり、そのような代替材料の例として、特公平７−９７７１７号公報に記載の発明である「Ｃｕ粒子の核の表面に下から順に、Ｃｕ重量に対して、０．０１〜０．２％のＰｄの第１被覆層、１〜１０．０％のＮｉの第２被覆層、０．２〜５．０％のＡｇの第３被覆層を有する、Ａｇ、Ｎｉ被覆Ｃｕ粉末からなる電磁波シールドおよび導電ペースト用導電性粉末」があり、該公報には、耐酸化性をＮｉで出現させ、導電性をＡｇ及びＣｕで出現させることができると記載されている。
【０００５】
一方、電磁波シールド及び導電ペースト用導電性粉末として適したレベルの導電性である為には、少量の添加で目的の導電性を得られることが重要である。
また、電子機器類内の発熱をはじめ、高温環境下で電子機器類が使用されることも考慮した場合、そうした高温環境下においても導電性等が悪影響を受けないこと、即ち導電性についての耐熱性も要求される。
【０００６】
しかし、上記の特公平７−９７７１７号公報に記載のＡｇ、Ｎｉ被覆Ｃｕ粉末は導電性の面では改善されているものの、該公報には「少量の添加で安定した導電性が得られ且つ導電性についての耐熱性にも優れていて、電磁波シールドや導電ペーストに用いるのに適した粉末、さらに該粉末を含む導電ペースト」については何ら開示されておらず、未だ充分な技術とは言い難い。
【０００７】
【発明が解決しようとする課題】
上記したように、電磁波シールドや導電ペーストに用いるのに適した導電性粉末においては、少量の添加で安定した導電性が得られ且つ導電性についての耐熱性にも優れていることが重要である。
本発明は、これらの特性を満足し、電磁波シールドや導電ペーストに用いるのに適した被覆銅粉を提供することを課題としている。
【０００８】
【課題を解決するための手段】
本発明者等は上記の課題を達成する為に鋭意検討した結果、銅粒子の表面上に特定の合金元素を含有するニッケル合金からなる中間層を有し且つ銀からなる表面被覆層を有する被覆銅粒子からなる被覆銅粉が好ましいことを見いだし、本発明を完成した。
【０００９】
即ち、本発明の被覆銅粉は、銅粒子と、該銅粒子を被覆しており且つ合金元素としてリン及びタングステンを含有しているニッケル合金層又は合金元素としてホウ素及びコバルトを含有しているニッケル合金層と、該ニッケル合金層を被覆している銀層とからなる被覆銅粒子であって、ニッケル合金の含有率が全被覆銅粉の０．５〜１０質量％であり、リンの含有率がニッケル合金の１〜１５質量％であり、タングステンの含有率がニッケル合金の５〜２０質量％であり、ホウ素の含有率がニッケル合金の１〜１０質量％であり、コバルトの含有率がニッケル合金の５〜２５質量％であり、銀の含有率が全被覆銅粉の４〜１５質量％であることを特徴とする。
【００１０】
【発明の実施の形態】
本発明の被覆銅粉においては、ニッケル合金層中に合金元素としてリン及びタングステンを含有するか、又はホウ素及びコバルトを含有することが重要であり、これらの元素を含有したニッケル合金層が核となる銅粒子表面を緻密に被覆することにより被覆銅粉の導電性についての耐熱性（この被覆銅粉の導電性についての耐熱性を、以下、単に耐熱性と記載する）効果を高めることができる。
【００１１】
本発明の被覆銅粉においては、リン又はホウ素の含有率は好ましくはニッケル合金の０．１〜２０質量％であり、より好ましくはリンの含有率は１〜１５質量％であり、ホウ素の含有率は１〜１０質量％である。これらの含有率がニッケル合金の０．１質量％未満の場合には耐熱性向上の効果が少なく、また２０質量％を超える場合にはコスト増に見合った効果が得られないのみならず、導電性劣化等の悪影響を生じる傾向がある。
【００１２】
また、本発明の被覆銅粉においては、コバルト又はタングステンの含有率は好ましくはニッケル合金の１〜３０質量％であり、より好ましくはコバルトの含有率は５〜２５質量％であり、タングステンの含有率は５〜２０質量％である。これらの含有率がニッケル合金の１質量％未満の場合には耐熱性向上の効果が少なく、また３０質量％を超える場合にはコスト増に見合った効果が得られないのみならず、導電性劣化等の悪影響を生じる傾向がある。
【００１３】
また、本発明の被覆銅粉においては、ニッケル合金層が銅粒子の表面と銀からなる表面被覆層との中間に存在しているので、銀粉よりも安価であり、被覆銅粉の導電性を損なうこともない。本発明の被覆銅粉においては、ニッケル合金層を構成するニッケル合金の含有率は好ましくは全被覆銅粉の０．１〜１５質量％であり、より好ましくは０．５〜１５質量％であり、最も好ましくは０．５〜１０質量％である。このニッケル合金の含有率が全被覆銅粉の０．１質量％未満の場合には耐熱性向上の効果が少なく、また１５質量％を超える場合にはコスト増に見合った効果が得られないのみならず、導電性を劣化させるおそれがある。
【００１４】
本発明の被覆銅粉においては、銀被覆層が被覆銅粉の最表面に存在しているので導電性に優れている。銀の含有率は好ましくは全被覆銅粉の２〜２０質量％であり、より好ましくは３〜１５質量％であり、最も好ましくは４〜１０質量％である。この銀の含有率が２質量％未満の場合には目的とする導電性が得られず、また２０質量％を超える場合にはコスト増に見合った効果が得られない。
【００１５】
また、本発明の被覆銅粉においては、タップ密度は好ましくは４ｇ／ｃｍ3 以下であり、より好ましくは３．５ｇ／ｃｍ3 以下であり、最も好ましくは３ｇ／ｃｍ3 以下である。このタップ密度を４ｇ／ｃｍ3 以下にすることにより、導電ペーストを調製した時に被覆銅粉の粒子同士が適度にからみあうようになるので、電磁波シールド及び導電ペースト用導電性粉末として適したレベルの導電性を実現することができる。
【００１６】
また、本発明の被覆銅粉においては、核となる銅粒子として球形や多面体形状等の粒状品を含め、いかなる形状のものを用いても構わないが、非球形状、特に樹枝状、それを加工したフレーク状の銅粉、具体的には電解銅粉や機械的処理を加えたフレーク状銅粉でタップ密度が４ｇ／ｃｍ3 以下のものを用いることが好ましい。この理由は、通常、導電ペースト中への導電性粉末の充填性は高い方が好ましいと考えられるが、要求される導電性のレベルがさほど高くない場合は、粒子同士のからみが適度にある方が良いからである。
【００１７】
次に、本発明の被覆銅粉の好ましい製造方法の一例について述べる。タップ密度が４ｇ／ｃｍ3 以下の銅粉、好ましくは非球形でタップ密度が４ｇ／ｃｍ3 以下の電解銅粉を水中に分散させてスラリーとする。また、リン及びタングステンのイオン源を添加するか、又はホウ素及びコバルトのイオン源を添加した無電解ニッケル合金メッキ液を調製する。このスラリーと無電解ニッケル合金メッキ液とを混合して無電解メッキ処理を実施し、合金元素としてリン及びタングステンを含有するか、又はホウ素及びコバルトを含有するニッケル合金層を銅粒子の表面に形成する。その後、アンモニア性硝酸銀溶液中でロッシェル塩等を用いて銀被覆処理を実施することにより本発明の被覆銅粉を製造する。
【００１８】
前記した特公平７−９７７１７号公報に記載の製造方法においては、「Ｃｕ粉末にＰｄを被着した後、Ｎｉ水溶液に懸濁させ、これにヒドラジン等の還元剤を加えることでＮｉがＣｕ粉の表面に析出する」方法を採用しているが、かかる製造方法では、還元力の強い還元剤を用いている為、銅粉粒子表面上に析出する金属ニッケルの分布にバラツキが生じ、金属ニッケル被覆の緻密性が失われ、その結果、生地銅粉の酸化防止の点でも問題があるのみならず、金属ニッケル単独であるために導電性についての耐熱性の向上の点でも限界がある。
【００１９】
従って、市販の無電解ニッケルメッキ液、具体的にはニボロンＭ（ワールドメタル社製）、Ｎｉ−４２６（メルテックス社製）等にリン及びタングステンのイオン源を添加するか、又はホウ素及びコバルトのイオン源を添加して無電解ニッケル合金メッキ液を調製し、一方、銅粉を水中に分散させて銅粉スラリーを調製し、この無電解ニッケル合金メッキ液と銅粉スラリーとを混合し、３０〜１２０分間攪拌して銅粒子の表面に緻密なニッケル合金被覆を形成させれば良い。
【００２０】
上記無電解ニッケルメッキ液に添加するリンイオン源として、リン酸、リン酸アンモニウム、リン酸水素アンモニウム、リン酸水素ナトリウム、リン酸カリウム、リン酸ナトリウム、次亜リン酸カルシウム等を用いることができ、またホウ素イオン源としてオルトホウ酸、四ホウ酸ナトリウム、メタホウ酸ナトリウム、ペルオキソホウ酸ナトリウム、四ホウ酸カリウム、メタホウ酸カリウム、四ホウ酸アンモニウム、メタホウ酸アンモニウム等を用いることができる。
【００２１】
また、上記無電解ニッケルメッキ液に添加するコバルトイオン源として、塩化コバルト、硫酸コバルト、硝酸コバルト、臭化コバルト、ヨウ化コバルト等を用いることができ、またタングステンイオン源として、タングステン酸ナトリウム、タングステン酸カリウム、タングステン酸アンモニウム等を用いることができる。
【００２２】
【実施例】
以下に実施例及び比較例に基づいて本発明を具体的に説明する。
実施例１
電解銅粉（比表面積０．２ｍ2 ／ｇ、ＳＥＭ写真から見た平均粒子径１００ミクロン、タップ密度２．５ｇ／ｃｍ3 ）１０００ｇを水８．５Ｌ中に分散させてスラリーを調製した。また、メタホウ酸ナトリウム・四水和物３ｇをニッケルメッキ液（ワールドメタル社製、ニボロンＭ）６Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーと無電解ニッケル合金メッキ液とを混合し、１０分間攪拌した。その後、温度を４０℃まで上げ、３０分間攪拌して銅粒子の表面にホウ素含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００２３】
このようにして得られたホウ素含有ニッケル合金被覆銅粉を、水９Ｌ中にＥＤＴＡ３２ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液２００ｍＬ（硝酸銀３６ｇをアンモニア水溶液４４ｍＬに溶解させ、水を加えて２００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、更にロッシェル塩２８ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、下記の諸特性を下記の方法に従って評価した。それらの結果を第１表に示す。
【００２４】
（１）銀、ニッケル、リン、ホウ素、コバルト及びタングステンの含有率（質量％）
試料を酸に溶解させ、ＩＣＰ法により含有率を測定した。
（２）タップ密度（ｇ／ｃｍ3 ）
試料２００ｇを用いてパウダーテスターＰＴ−Ｅ型（ホソカワミクロン製）により測定した。
（３）粉体抵抗率（×１０-4Ω・ｃｍ）
試料２０ｇをプレス圧力５００ｋｇｆで圧縮し、ロレスタＡＰ及びロレスタＰＤ−４１型（何れも三菱化学製）により測定した。
【００２５】
（４）耐熱性
大気雰囲気中、１５６℃の加熱炉中に試料を８０時間保持した。上記（３）の測定法により得られた耐熱試験前の抵抗率と耐熱試験後の抵抗率より抵抗変化倍率を下記の式で求め、導電性についての耐熱性の評価とした。
抵抗変化倍率（倍）
＝｛耐熱試験後抵抗率（Ω・ｃｍ）／耐熱試験前抵抗率（Ω・ｃｍ）｝
【００２６】
（５）導電ペーストによる塗膜の表面抵抗率（×１０-2Ω／□）
試料６０質量部に、アクリルラッカーであるアクリック２０００ＧＬ（関西ペイント社製）を４０質量部加えてホモジナイザーにて混練してペースト化し、この導電ペーストをフィルム上に塗布し、７０℃で２０分乾燥させ、導電性膜を形成した。この塗膜の表面抵抗率をロレスタＡＰにより測定した。
【００２７】
実施例２
実施例１で用いた電解銅粉１０００ｇを水８．５Ｌ中に分散させてスラリーを調製した。また、メタホウ酸ナトリウム・四水和物４ｇをニッケルメッキ液（ワールドメタル社製、ニボロンＭ）６Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーと無電解ニッケル合金メッキ液とを混合し、１０分間攪拌した。その後、温度を４０℃まで上げ、３０分間攪拌して銅粒子の表面にホウ素含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００２８】
このようにして得られたホウ素含有ニッケル合金被覆銅粉を、水９ＬにＥＤＴＡ８０ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液５００ｍＬ（硝酸銀８６ｇをアンモニア水溶液１１０ｍＬに溶解させ、水を加えて５００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩７０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００２９】
実施例３
実施例１で用いた電解銅粉１０００ｇを水８．５Ｌ中に分散させてスラリーを調製した。また、メタホウ酸ナトリウム・四水和物４ｇをニッケルメッキ液（ワールドメタル社製、ニボロンＭ）６Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーと無電解ニッケル合金メッキ液とを混合し、１０分間攪拌した。その後、温度を４０℃まで上げ、３０分間攪拌して銅粒子の表面にホウ素含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００３０】
このようにして得られたホウ素含有ニッケル合金被覆銅粉を、水９ＬにＥＤＴＡ１６０ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液１０００ｍＬ（硝酸銀１８０ｇをアンモニア水溶液２２０ｍＬに溶解させ、水を加えて１０００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩１４０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００３１】
実施例４
実施例１で用いた電解銅粉１０００ｇを水８．５Ｌ中に分散させてスラリーを調製した。また、メタホウ酸ナトリウム・四水和物４ｇ及び硫酸コバルト・七水和物１８ｇをニッケルメッキ液（ワールドメタル社製、ニボロンＭ）６Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーと無電解ニッケル合金メッキ液とを混合し、１０分間攪拌した。その後、温度を４０℃まで上げ、３０分間攪拌して銅粒子の表面にホウ素及びコバルト含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００３２】
このようにして得られたホウ素及びコバルト含有ニッケル合金被覆銅粉を、水９ＬにＥＤＴＡ３２ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液２００ｍＬ（硝酸銀３６ｇをアンモニア水溶液４４ｍＬに溶解させ、水を加えて２００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩２８ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００３３】
実施例５
実施例１で用いた電解銅粉１０００ｇを水１０Ｌ中に分散させてスラリーを調製した。また、次亜リン酸カルシウム５ｇをニッケルメッキ液（メルテックス社製、Ｎｉー４２６）６．５Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーにアクチベーター液（メルテックス社製、アクチベーター３５２）５ｍＬを添加し、５分間攪拌した後、無電解ニッケル合金メッキ液と混合し、１０分間攪拌した。その後、温度を７０℃まで上げ、３０分間攪拌して銅粒子の表面にリン含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００３４】
このようにして得られたリン含有ニッケル合金被覆銅粉を、水９ＬにＥＤＴＡ８０ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液５００ｍＬ（硝酸銀８６ｇをアンモニア水溶液１１０ｍＬに溶解させ、水を加えて５００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩７０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００３５】
実施例６
実施例１で用いた電解銅粉１０００ｇを水１０Ｌ中に分散させてスラリーを調製した。また、次亜リン酸カルシウム４ｇをニッケルメッキ液（メルテックス社製、Ｎｉー４２６）６．５Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーにアクチベーター液（メルテックス社製、アクチベーター３５２）５ｍＬを添加し、５分間攪拌した後、無電解ニッケル合金メッキ液と混合し、１０分間攪拌した。その後、温度を７０℃まで上げ、３０分間攪拌して銅粒子の表面にリン含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００３６】
このようにして得られたリン含有ニッケル合金被覆銅粉を、水９ＬにＥＤＴＡ１６０ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液１０００ｍＬ（硝酸銀１８０ｇをアンモニア水溶液２２０ｍＬに溶解させ、水を加えて１０００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩１４０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００３７】
実施例７
実施例１で用いた電解銅粉１０００ｇを水１０Ｌ中に分散させてスラリーを調製した。また、次亜リン酸カルシウム４ｇ及びタングステン酸ナトリウム１０ｇをニッケルメッキ液（メルテックス社製、Ｎｉー４２６）６．５Ｌに添加し、溶解させて無電解ニッケル合金メッキ液を調製した。このスラリーにアクチベーター液（メルテックス社製、アクチベーター３５２）５ｍＬを添加し、５分間攪拌した後、無電解ニッケル合金メッキ液と混合し、１０分間攪拌した。その後、温度を７０℃まで上げ、３０分間攪拌して銅粒子の表面にリン及びタングステン含有ニッケル合金被覆を形成させた。その後、常法に従ってろ過し、洗浄を行った。
【００３８】
このようにして得られたリン及びタングステン含有ニッケル合金被覆銅粉を、水９ＬにＥＤＴＡ１６０ｇを溶解させた溶液中に分散させ、そのスラリーに硝酸銀溶液１０００ｍＬ（硝酸銀１８０ｇをアンモニア水溶液２２０ｍＬに溶解させ、水を加えて１０００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩１４０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００３９】
比較例１
実施例１で用いた電解銅粉１０００ｇを、水９ＬにＥＤＴＡ１６０ｇを溶解させた溶液中に分散させてスラリーを調製し、そのスラリーに硝酸銀溶液１０００ｍＬ（硝酸銀１８０ｇをアンモニア水溶液２２０ｍＬに溶解させ、水を加えて１０００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩１４０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って銀被覆銅粉を得た。
この銀被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００４０】
比較例２
アトマイズ銅粉（比表面積０．１２ｍ2 ／ｇ、ＳＥＭ写真から見た平均粒子径３０ミクロン、タップ密度４．５ｇ／ｃｍ3 ）１０００ｇを、水９ＬにＥＤＴＡ１６０ｇを溶解させた溶液中に分散させてスラリーを調製し、そのスラリーに硝酸銀溶液１０００ｍＬ（硝酸銀１８０ｇをアンモニア水溶液２２０ｍＬに溶解させ、水を加えて１０００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩１４０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って銀被覆銅粉を得た。
この銀被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００４１】
比較例３
実施例１で用いた電解銅粉１０００ｇを塩化パラジウム水溶液（パラジウムとして０．３ｇ／Ｌの濃度）２Ｌ中に浸漬して銅粒子の表面にパラジウムを被着させた。その後、硫酸ニッケル水溶液（ニッケルとして２ｇ／Ｌの濃度）６Ｌ中に懸濁させ、６０℃に保ちながらヒドラジン・１水和物１０ｇを加えてパラジウム被覆銅粒子の表面にニッケルを析出させた。ろ別したパラジウム・ニッケル被覆銅粉を、水９ＬにＥＤＴＡ１６０ｇを溶解させた溶液中に分散させてスラリーとし、そのスラリーに硝酸銀溶液１０００ｍＬ（硝酸銀１８０ｇをアンモニア水溶液２２０ｍＬに溶解させ、水を加えて１０００ｍＬとした水溶液）を添加し、３０分間攪拌を行い、ロッシェル塩１４０ｇを添加し、３０分間攪拌を行い、その後、常法に従って水洗し、乾燥を行って被覆銅粉を得た。
この被覆銅粉について、実施例１と同様に諸特性を評価した。それらの結果を第１表に示す。
【００４２】
【表１】
第１表のデータからも分かる通り、合金元素としてリン及びタングステンを含有するか、又はホウ素及びコバルトを含有する本発明の被覆銅粉は、その他の被覆銅粉に較べて導電性、特に耐熱試験後の導電性に優れているのみならず、抵抗変化倍率が小さく、耐熱性が向上している。
【００４４】
【発明の効果】
本発明のニッケル合金中間被覆層及び銀表面被覆層を有する被覆銅粒子からなる被覆銅粉は、少量の添加で安定した導電性が得られ且つ耐熱性にも優れているので、電磁波シールドや導電ペーストに用いるのに適している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coated copper powder composed of coated copper particles having an intermediate coating layer composed of a nickel alloy and a surface coating layer composed of silver on the surface of the copper particles, and in particular, the desired conductivity can be obtained with a small amount of addition. And since it has heat resistance about electroconductivity, it is related with this coating | coated copper powder suitable for using for an electromagnetic wave shield or an electrically conductive paste.
[0002]
[Prior art]
In electronic devices such as computers, the problem of malfunction caused by the influence of external electromagnetic waves has been highlighted, and we have developed a means to improve conductivity in the exterior of computers for the purpose of electromagnetic shielding. Is progressing. As a means for improving the conductivity of the exterior part, a method of adding a conductive substance as a filler to an organic resin used for reducing the weight of electronic devices, or coating a conductive substance into a coating part is applied. The method of doing is common.
[0003]
Of course, the important characteristic required for this conductive material is that it is highly conductive. Considering the cost, metal powder, especially metal ultrafine powder is preferable as the conductive material, and silver ultrafine powder is particularly resistant to oxidation. Because of its excellent properties, it is widely used. However, since silver is an expensive substance among metal powders, an alternative material is required for further cost reduction.
[0004]
It is important that an alternative material that meets this requirement does not impair the above-mentioned characteristics of silver. As an example of such an alternative material, the invention described in Japanese Patent Publication No. 7-97717 “Cu particles In order from the bottom on the surface of the core, the first coating layer of 0.01 to 0.2% Pd, the second coating layer of Ni of 1 to 10.0%, and 0.2 to 5. Electromagnetic wave shield made of Ag, Ni-coated Cu powder and conductive powder for conductive paste having a third coating layer of 0% Ag ”, and in this publication, oxidation resistance appears in Ni, and conductivity is improved. It is described that it can appear in Ag and Cu.
[0005]
On the other hand, in order to achieve a level of conductivity suitable as an electromagnetic shielding and conductive powder for conductive paste, it is important that the desired conductivity can be obtained with a small amount of addition.
In consideration of heat generation in electronic devices and the use of electronic devices in high-temperature environments, conductivity and the like are not adversely affected in such high-temperature environments. Sex is also required.
[0006]
However, although the Ag and Ni-coated Cu powder described in the above Japanese Patent Publication No. 7-97717 is improved in terms of conductivity, the publication states that “stable conductivity can be obtained with a small amount of addition and conductivity. The powder is also excellent in heat resistance, and is not disclosed at all for a powder suitable for use in electromagnetic wave shields and conductive pastes, and further, a conductive paste containing the powders.
[0007]
[Problems to be solved by the invention]
As described above, in a conductive powder suitable for use in electromagnetic wave shields and conductive pastes, it is important that stable conductivity is obtained with a small amount of addition and that the heat resistance of the conductivity is excellent. .
An object of the present invention is to provide a coated copper powder that satisfies these characteristics and is suitable for use in an electromagnetic wave shield or a conductive paste.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have an intermediate layer made of a nickel alloy containing a specific alloy element on the surface of the copper particles and a surface coating layer made of silver. The present inventors have found that a coated copper powder made of copper particles is preferable and completed the present invention.
[0009]
That is, the coated copper powder of the present invention comprises a copper particle and a nickel alloy layer covering the copper particle and containing phosphorus and tungsten as alloy elements or nickel containing boron and cobalt as alloy elements. an alloy layer, a coated copper particles made of silver layer covering the nickel alloy layer is 0.5 to 10 mass% of the content of the nickel alloy full-coated copper powder, the phosphorus content Is 1 to 15 mass% of the nickel alloy, the tungsten content is 5 to 20 mass% of the nickel alloy, the boron content is 1 to 10 mass% of the nickel alloy, and the cobalt content is nickel. It is 5 to 25% by mass of the alloy, and the silver content is 4 to 15% by mass of the total coated copper powder.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the coated copper powder of the present invention, it is important that the nickel alloy layer contains phosphorus and tungsten as alloy elements, or contains boron and cobalt , and the nickel alloy layer containing these elements is the core. By densely coating the surface of the resulting copper particles, the effect of heat resistance on the conductivity of the coated copper powder (the heat resistance regarding the conductivity of the coated copper powder is hereinafter simply referred to as heat resistance) can be enhanced. .
[0011]
In-coated copper powder of the present invention, including Yuritsu of Li down or boron is 0.1 to 20 mass% preferably nickel alloy, more preferably from 1 to 15 wt% and the content of phosphorus, The content rate of boron is 1-10 mass%. When the content is less than 0.1% by mass of the nickel alloy, the effect of improving the heat resistance is small, and when it exceeds 20% by mass, the effect corresponding to the increase in cost is not obtained, There is a tendency to cause adverse effects such as sex deterioration.
[0012]
In the coated copper powder of the present invention, the content of co Baltic or tungsten is from 1 to 30% by weight of preferably a nickel alloy, more preferably the content of cobalt is 5 to 25 wt%, The content of tungsten is 5 to 20% by mass. When the content is less than 1% by mass of the nickel alloy, the effect of improving the heat resistance is small, and when it exceeds 30% by mass, not only an effect commensurate with the increase in cost is obtained, but also the conductivity deterioration. It tends to cause adverse effects such as.
[0013]
In the coated copper powder of the present invention, since the nickel alloy layer exists between the surface of the copper particles and the surface coating layer made of silver, it is cheaper than the silver powder and the conductivity of the coated copper powder is reduced. There is no loss. In the coated copper powder of the present invention, the content of the nickel alloy constituting the nickel alloy layer is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass of the total coated copper powder. Most preferably, it is 0.5 to 10% by mass. When the content of this nickel alloy is less than 0.1% by mass of the total coated copper powder, the effect of improving heat resistance is small, and when it exceeds 15% by mass, the effect corresponding to the increase in cost cannot be obtained. In addition, the conductivity may be deteriorated.
[0014]
In the coated copper powder of this invention, since the silver coating layer exists in the outermost surface of the coated copper powder, it is excellent in electroconductivity. The silver content is preferably 2 to 20% by mass of the total coated copper powder, more preferably 3 to 15% by mass, and most preferably 4 to 10% by mass. When the silver content is less than 2% by mass, the intended conductivity cannot be obtained, and when it exceeds 20% by mass, an effect commensurate with the cost increase cannot be obtained.
[0015]
In the coated copper powder of the present invention, the tap density is preferably 4 g / cm 3 or less, more preferably 3.5 g / cm 3 or less, and most preferably 3 g / cm 3 or less. By setting the tap density to 4 g / cm 3 or less, the coated copper powder particles are appropriately entangled with each other when the conductive paste is prepared. Can be realized.
[0016]
In addition, in the coated copper powder of the present invention, any shape may be used as the core copper particles including granular products such as spherical and polyhedral shapes, but non-spherical shapes, particularly dendritic shapes, It is preferable to use processed flaky copper powder, specifically, electrolytic copper powder or flaky copper powder subjected to mechanical treatment and having a tap density of 4 g / cm 3 or less. The reason for this is that it is generally considered that a higher filling property of the conductive powder in the conductive paste is preferable, but if the required level of conductivity is not so high, the particles are moderately entangled. Because it is good.
[0017]
Next, an example of a preferable method for producing the coated copper powder of the present invention will be described. A copper powder having a tap density of 4 g / cm 3 or less, preferably a non-spherical copper powder having a tap density of 4 g / cm 3 or less, is dispersed in water to form a slurry. Further, it is preferred to add an ion source of phosphorus and tungsten, or to prepare an electroless nickel alloy plating solution added with ion-source of boric Moto及beauty co Baltic. The slurry and the electroless nickel alloy plating solution by mixing implement an electroless plating process, or containing phosphorus及beauty tungsten as an alloying element, or a copper nickel alloy layer containing boric iodine and cobalt Form on the surface of the particles. Then, the covering copper powder of this invention is manufactured by implementing silver coating processing using Rochelle salt etc. in an ammoniacal silver nitrate solution.
[0018]
In the manufacturing method described in the above-mentioned Japanese Patent Publication No. 7-97717, “After depositing Pd on Cu powder, it is suspended in an Ni aqueous solution, and Ni is added to Cu powder by adding a reducing agent such as hydrazine to this. However, in this manufacturing method, since a reducing agent having a strong reducing power is used, the distribution of metallic nickel deposited on the surface of the copper powder particles varies, and the metallic nickel The denseness of the coating is lost, and as a result, there is a problem not only in terms of preventing the oxidation of the dough copper powder, but also there is a limit in terms of improving the heat resistance with respect to conductivity because it is made of metallic nickel alone.
[0019]
Thus, commercially available electroless nickel plating solution, specifically Niboron M (manufactured by World Metal Corporation) for, Ni - 426 or the addition of phosphorus and ion source tungsten (Meltex Co., Ltd.), or boric-containing及beauty co added Baltic ion-source of an electroless nickel alloy plating solution prepared, whereas, the copper powder was dispersed in water to prepare a copper powder slurry, the electroless nickel alloy plating solution and copper powder The slurry may be mixed and stirred for 30 to 120 minutes to form a dense nickel alloy coating on the surface of the copper particles.
[0020]
As a phosphorus ion source to be added to the electroless nickel plating solution, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, sodium hydrogen phosphate, potassium phosphate, sodium phosphate, calcium hypophosphite, etc. can be used. As an ion source, orthoboric acid, sodium tetraborate, sodium metaborate, sodium peroxoborate, potassium tetraborate, potassium metaborate, ammonium tetraborate, ammonium metaborate and the like can be used.
[0021]
Also, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt bromide, cobalt iodide, etc. can be used as the cobalt ion source added to the electroless nickel plating solution, and sodium tungstate, tungsten, etc. can be used as the tungsten ion source. Potassium acid, ammonium tungstate, and the like can be used.
[0022]
【Example】
The present invention will be specifically described below based on examples and comparative examples.
Example 1
A slurry was prepared by dispersing 1000 g of electrolytic copper powder (specific surface area 0.2 m 2 / g, average particle diameter 100 microns as seen from SEM photograph, tap density 2.5 g / cm 3 ) in 8.5 L of water. Moreover, 3 g of sodium metaborate tetrahydrate was added to 6 L of nickel plating solution (Niboron M, manufactured by World Metal Co.) and dissolved to prepare an electroless nickel alloy plating solution. This slurry and the electroless nickel alloy plating solution were mixed and stirred for 10 minutes. Thereafter, the temperature was raised to 40 ° C. and stirred for 30 minutes to form a boron-containing nickel alloy coating on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0023]
The boron-containing nickel alloy-coated copper powder thus obtained is dispersed in a solution in which 32 g of EDTA is dissolved in 9 L of water, and 200 mL of silver nitrate solution (36 g of silver nitrate is dissolved in 44 mL of aqueous ammonia solution) in the slurry. In addition, 200 mL of an aqueous solution) was added, and the mixture was stirred for 30 minutes. Further, 28 g of Rochelle salt was added, and the mixture was stirred for 30 minutes.
About this coating | coated copper powder, the following various characteristics were evaluated in accordance with the following method. The results are shown in Table 1.
[0024]
(1) Silver, nickel, phosphorus, boron, cobalt and tungsten content (mass%)
The sample was dissolved in acid and the content was measured by ICP method.
(2) Tap density (g / cm 3 )
Measurement was performed with a powder tester PT-E type (manufactured by Hosokawa Micron Corporation) using 200 g of a sample.
(3) Powder resistivity (× 10 -4 Ω · cm)
A 20 g sample was compressed at a press pressure of 500 kgf and measured with a Loresta AP and Loresta PD-41 type (both manufactured by Mitsubishi Chemical).
[0025]
(4) The sample was kept in a heating furnace at 156 ° C. for 80 hours in a heat-resistant air atmosphere. From the resistivity before the heat resistance test and the resistivity after the heat resistance test obtained by the measurement method of (3) above, the resistance change magnification was obtained by the following formula, and the heat resistance of the conductivity was evaluated.
Resistance change magnification (times)
= {Resistivity after heat test (Ω · cm) / Resistivity before heat test (Ω · cm)}
[0026]
(5) Surface resistivity of coating film with conductive paste (× 10 -2 Ω / □)
Acrylic lacquer, Acrylic 2000GL (manufactured by Kansai Paint Co., Ltd.), 40 parts by mass, is added to 60 parts by mass of the sample, kneaded with a homogenizer to form a paste. To form a conductive film. The surface resistivity of this coating film was measured by Loresta AP.
[0027]
Example 2
A slurry was prepared by dispersing 1000 g of the electrolytic copper powder used in Example 1 in 8.5 L of water. Further, 4 g of sodium metaborate tetrahydrate was added to 6 L of a nickel plating solution (Niboron M, manufactured by World Metal Co.) and dissolved to prepare an electroless nickel alloy plating solution. This slurry and the electroless nickel alloy plating solution were mixed and stirred for 10 minutes. Thereafter, the temperature was raised to 40 ° C. and stirred for 30 minutes to form a boron-containing nickel alloy coating on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0028]
The thus obtained boron-containing nickel alloy-coated copper powder is dispersed in a solution of 80 g of EDTA dissolved in 9 L of water, and 500 mL of silver nitrate solution (86 g of silver nitrate is dissolved in 110 mL of aqueous ammonia solution) and water is added to the slurry. The resulting mixture was stirred for 30 minutes, added with 70 g of Rochelle salt, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0029]
Example 3
A slurry was prepared by dispersing 1000 g of the electrolytic copper powder used in Example 1 in 8.5 L of water. Further, 4 g of sodium metaborate tetrahydrate was added to 6 L of a nickel plating solution (Niboron M, manufactured by World Metal Co.) and dissolved to prepare an electroless nickel alloy plating solution. This slurry and the electroless nickel alloy plating solution were mixed and stirred for 10 minutes. Thereafter, the temperature was raised to 40 ° C. and stirred for 30 minutes to form a boron-containing nickel alloy coating on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0030]
The thus obtained boron-containing nickel alloy-coated copper powder is dispersed in a solution of 160 g of EDTA in 9 L of water, and 1000 mL of silver nitrate solution (180 g of silver nitrate is dissolved in 220 mL of aqueous ammonia solution) is added to the slurry. The resulting solution was stirred for 30 minutes, added with 140 g of Rochelle salt, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0031]
Example 4
A slurry was prepared by dispersing 1000 g of the electrolytic copper powder used in Example 1 in 8.5 L of water. Further, 4 g of sodium metaborate tetrahydrate and 18 g of cobalt sulfate heptahydrate were added to 6 L of nickel plating solution (World Metal Co., Niboron M) and dissolved to prepare an electroless nickel alloy plating solution. . This slurry and the electroless nickel alloy plating solution were mixed and stirred for 10 minutes. Thereafter, the temperature was raised to 40 ° C. and stirred for 30 minutes to form a boron and cobalt-containing nickel alloy coating on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0032]
The thus obtained boron and cobalt-containing nickel alloy-coated copper powder was dispersed in a solution of 32 g of EDTA in 9 L of water, and 200 mL of a silver nitrate solution (36 g of silver nitrate was dissolved in 44 mL of an aqueous ammonia solution) Was added, and the mixture was stirred for 30 minutes, 28 g of Rochelle salt was added, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0033]
Example 5
A slurry was prepared by dispersing 1000 g of the electrolytic copper powder used in Example 1 in 10 L of water. Further, 5 g of calcium hypophosphite was added to 6.5 L of a nickel plating solution (Ni-426, manufactured by Meltex Co.), and dissolved to prepare an electroless nickel alloy plating solution. To this slurry, 5 mL of an activator solution (Meltex, Activator 352) was added, stirred for 5 minutes, mixed with an electroless nickel alloy plating solution, and stirred for 10 minutes. Thereafter, the temperature was raised to 70 ° C. and stirred for 30 minutes to form a phosphorus-containing nickel alloy coating on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0034]
The phosphorus-containing nickel alloy-coated copper powder thus obtained is dispersed in a solution of 80 g of EDTA dissolved in 9 L of water, and 500 mL of silver nitrate solution (86 g of silver nitrate is dissolved in 110 mL of aqueous ammonia solution) and water is added to the slurry. The resulting mixture was stirred for 30 minutes, added with 70 g of Rochelle salt, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0035]
Example 6
A slurry was prepared by dispersing 1000 g of the electrolytic copper powder used in Example 1 in 10 L of water. Further, 4 g of calcium hypophosphite was added to 6.5 L of a nickel plating solution (Ni-426, manufactured by Meltex Co.), and dissolved to prepare an electroless nickel alloy plating solution. To this slurry, 5 mL of an activator solution (Meltex, Activator 352) was added, stirred for 5 minutes, mixed with an electroless nickel alloy plating solution, and stirred for 10 minutes. Thereafter, the temperature was raised to 70 ° C. and stirred for 30 minutes to form a phosphorus-containing nickel alloy coating on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0036]
The phosphorus-containing nickel alloy-coated copper powder thus obtained was dispersed in a solution of 160 g of EDTA dissolved in 9 L of water, 1000 mL of a silver nitrate solution (180 g of silver nitrate was dissolved in 220 mL of an aqueous ammonia solution, and water was added to the slurry. The resulting solution was stirred for 30 minutes, added with 140 g of Rochelle salt, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0037]
Example 7
A slurry was prepared by dispersing 1000 g of the electrolytic copper powder used in Example 1 in 10 L of water. Moreover, 4 g of calcium hypophosphite and 10 g of sodium tungstate were added to 6.5 L of nickel plating solution (Meltex, Ni-426) and dissolved to prepare an electroless nickel alloy plating solution. To this slurry, 5 mL of an activator solution (Meltex, Activator 352) was added, stirred for 5 minutes, mixed with an electroless nickel alloy plating solution, and stirred for 10 minutes. Thereafter, the temperature was raised to 70 ° C. and stirred for 30 minutes to form a nickel alloy coating containing phosphorus and tungsten on the surface of the copper particles. Then, it filtered and wash | cleaned according to the conventional method.
[0038]
The thus obtained phosphorus and tungsten-containing nickel alloy-coated copper powder was dispersed in a solution of 160 g of EDTA in 9 L of water, and 1000 mL of silver nitrate solution (180 g of silver nitrate was dissolved in 220 mL of aqueous ammonia solution) Was added, and the mixture was stirred for 30 minutes, 140 g of Rochelle salt was added, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0039]
Comparative Example 1
1000 g of the electrolytic copper powder used in Example 1 was dispersed in a solution of 160 g of EDTA dissolved in 9 L of water to prepare a slurry. In this slurry, 1000 mL of silver nitrate solution (180 g of silver nitrate was dissolved in 220 mL of aqueous ammonia solution and water was added. In addition, an aqueous solution (1000 mL) was added and stirred for 30 minutes, 140 g of Rochelle salt was added, stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain silver-coated copper powder.
Various characteristics of this silver-coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0040]
Comparative Example 2
1000 g of atomized copper powder (specific surface area 0.12 m 2 / g, average particle size 30 micron as seen from SEM photograph, tap density 4.5 g / cm 3 ) was dispersed in a solution of 160 g of EDTA in 9 L of water. A slurry is prepared, and 1000 mL of a silver nitrate solution (an aqueous solution in which 180 g of silver nitrate is dissolved in 220 mL of an aqueous ammonia solution and added to water to 1000 mL) is added to the slurry, stirred for 30 minutes, and 140 g of Rochelle salt is added for 30 minutes. Stirring was then performed, followed by washing with water according to a conventional method and drying to obtain a silver-coated copper powder.
Various characteristics of this silver-coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0041]
Comparative Example 3
1000 g of the electrolytic copper powder used in Example 1 was immersed in 2 L of an aqueous palladium chloride solution (concentration of 0.3 g / L as palladium) to deposit palladium on the surfaces of the copper particles. Thereafter, the suspension was suspended in 6 L of an aqueous nickel sulfate solution (concentration of 2 g / L as nickel), and 10 g of hydrazine monohydrate was added while maintaining the temperature at 60 ° C. to precipitate nickel on the surface of the palladium-coated copper particles. The palladium / nickel-coated copper powder separated by filtration is dispersed in a solution of 160 g of EDTA in 9 L of water to form a slurry, and 1000 mL of a silver nitrate solution (180 g of silver nitrate is dissolved in 220 mL of an aqueous ammonia solution and 1000 mL of water is added to the slurry. Was added and the mixture was stirred for 30 minutes, 140 g of Rochelle salt was added, the mixture was stirred for 30 minutes, then washed with water and dried according to a conventional method to obtain coated copper powder.
Various characteristics of this coated copper powder were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[0042]
[Table 1]
As it can be seen from the data in Table 1, or containing phosphorus and tungsten as an alloying element, or coated copper powder of the present invention containing boric iodine and cobalt, the conductive compared to other coated copper powder Especially, not only is it excellent in conductivity after the heat test, but also the resistance change magnification is small and the heat resistance is improved.
[0044]
【Effect of the invention】
The coated copper powder comprising the coated copper particles having the nickel alloy intermediate coating layer and the silver surface coating layer of the present invention provides stable conductivity with a small amount of addition and is excellent in heat resistance. Suitable for use in pastes.
Claims (6)
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| WO2006085481A1 (en) * | 2005-02-09 | 2006-08-17 | Sekisui Chemical Co., Ltd. | Electrically conductive fine particles, anisotropic electrically conductive material, and electrically conductive connection method |
| JP4942333B2 (en) | 2005-11-29 | 2012-05-30 | 住友金属鉱山株式会社 | Nickel powder, method for producing the same, and polymer PTC element using the nickel powder |
| KR20110034604A (en) * | 2008-06-23 | 2011-04-05 | 파커-한니핀 코포레이션 | Emi shielding materials |
| CN102260385B (en) * | 2010-05-31 | 2013-07-24 | 比亚迪股份有限公司 | Positive temperature coefficient material and thermistor containing same |
| US20120061698A1 (en) * | 2010-09-10 | 2012-03-15 | Toscano Lenora M | Method for Treating Metal Surfaces |
| CN103650063B (en) * | 2011-07-28 | 2016-01-20 | 积水化学工业株式会社 | Electroconductive particle, electric conducting material and connection structural bodies |
| KR101941721B1 (en) * | 2011-12-21 | 2019-01-23 | 세키스이가가쿠 고교가부시키가이샤 | Conductive particles, conductive material, and connection structure |
| CN104170023B (en) | 2012-03-06 | 2016-12-28 | 东洋油墨Sc控股株式会社 | Electrically conductive microparticle and manufacture method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
| JP6478308B2 (en) * | 2012-11-28 | 2019-03-06 | 積水化学工業株式会社 | Conductive particles, conductive materials, and connection structures |
| US10056505B2 (en) * | 2013-03-15 | 2018-08-21 | Inkron Ltd | Multi shell metal particles and uses thereof |
| FI20135253L (en) * | 2013-03-15 | 2014-09-16 | Inkron Ltd | Multilayer metal particles and their use |
| CN106605270B (en) * | 2014-08-28 | 2019-03-08 | E.I.内穆尔杜邦公司 | Cupric electrocondution slurry and thus manufactured electrode |
| CN104972111A (en) * | 2015-06-27 | 2015-10-14 | 铜陵铜基粉体科技有限公司 | High-conductivity spherical copper powder and method for manufacturing the same |
| CN104972109A (en) * | 2015-06-27 | 2015-10-14 | 铜陵铜基粉体科技有限公司 | High-adsorbability spherical copper powder and method for manufacturing the same |
| CN104972110A (en) * | 2015-06-27 | 2015-10-14 | 铜陵铜基粉体科技有限公司 | Electromagnetic interference resistant spherical copper powder and method for manufacturing the same |
| CN110629135B (en) * | 2019-10-21 | 2021-07-06 | 常德力元新材料有限责任公司 | Preparation method of nickel-silver alloy material |
| JPWO2023167302A1 (en) * | 2022-03-04 | 2023-09-07 |
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| JPS5229835A (en) * | 1975-09-02 | 1977-03-07 | Asahi Glass Co Ltd | Improved filler for synthetic resin |
| JPS5954444A (en) * | 1982-09-01 | 1984-03-29 | Nippon Steel Corp | Casting mold for continuous casting of iron and steel |
| JPS60162779A (en) * | 1984-02-06 | 1985-08-24 | Nippon Chem Ind Co Ltd:The | Silver plated composition and its manufacture |
| JPH0797717B2 (en) * | 1986-02-21 | 1995-10-18 | 三菱マテリアル株式会社 | Cu powder coated with Ag and Ni |
| JPS6327567A (en) * | 1986-07-18 | 1988-02-05 | Mitsubishi Electric Corp | Electrically conductive paste |
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| JP3832938B2 (en) * | 1997-08-12 | 2006-10-11 | 日本化学工業株式会社 | Electroless silver plating powder and method for producing the same |
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