JP2006040650A - Silver paste and its manufacturing method - Google Patents
Silver paste and its manufacturing method Download PDFInfo
- Publication number
- JP2006040650A JP2006040650A JP2004216705A JP2004216705A JP2006040650A JP 2006040650 A JP2006040650 A JP 2006040650A JP 2004216705 A JP2004216705 A JP 2004216705A JP 2004216705 A JP2004216705 A JP 2004216705A JP 2006040650 A JP2006040650 A JP 2006040650A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- rod
- silver powder
- silver paste
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 131
- 239000004332 silver Substances 0.000 title claims abstract description 131
- 238000004519 manufacturing process Methods 0.000 title abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 51
- 229940100890 silver compound Drugs 0.000 claims abstract description 16
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001000 micrograph Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
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- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 34
- 239000000843 powder Substances 0.000 abstract description 24
- 239000000243 solution Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
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- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000523 sample Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
本件出願に係る発明は、ロッド状銀粉を含む銀ペーストに関する。特に、低抵抗で且つ接続信頼性に優れた導体を形成出来る銀ペーストを提供する。 The invention according to the present application relates to a silver paste containing rod-shaped silver powder. In particular, a silver paste capable of forming a conductor having low resistance and excellent connection reliability is provided.
従来から、銀ペーストは、そのペースト内に球状若しくはフレーク状の粉粒形状を持つ銀粉を混合分散させ用いられてきた。そして、その銀ペーストは、一般的な低温焼成セラミック基板の回路形成等の焼成用途の他、特許文献１に開示されているようなプリント配線板の配線回路、ビアホール充填、部品実装用接着剤等の用途において、種々の樹脂成分と一緒に固化して用いる用途が存在している。後者のような用途においては、導電性フィラーとしての銀粉の粉粒同士が焼結することなく、粉粒同士の接触のみで電気的導電性を得るというのが一般的であった。 Conventionally, silver paste has been used by mixing and dispersing silver powder having a spherical or flaky particle shape in the paste. The silver paste is used for firing such as circuit formation of a general low-temperature fired ceramic substrate, as well as a printed circuit board wiring circuit, via hole filling, component mounting adhesive, etc. as disclosed in Patent Document 1. In other applications, there are applications in which it is solidified together with various resin components. In applications such as the latter, it has been common to obtain electrical conductivity only by contact between the powder particles without sintering the powder particles of the silver powder as the conductive filler.
近年は、回路の配線幅や配線膜厚等が著しく微細なものとなってきたため、銀ペーストを用いて形成した導体に対し、より低い電気抵抗率と高い接続信頼性が要求されてきた。従来の銀ペーストは、粉粒同士の接触により導電性を得ているため、さらなる低電気抵抗化を図るためには、粉粒同士の接触面積をさらに増やす必要があるが、一般に、接触面積を増やすために用いられているフレーク状銀粉は、粒子形状が不均一であり、かつ粒度分布が広いことから、さらなる微細配線の形成において、高い接続信頼性を得る事ができない。よって、銀粉の粉粒同士の接触面積を効率良く増やし、かつ微細配線での高い接続信頼を有する銀ペーストへの要求が高まってきた。一般に、この要求に応えるには、接触面積を増やすフレーク状銀粉の形状や粒度分布を均一にする検討がなされてきた。 In recent years, circuit wiring width, wiring film thickness, and the like have become extremely fine, and thus a lower electrical resistivity and higher connection reliability have been required for conductors formed using silver paste. Since the conventional silver paste obtains conductivity by contact between powder particles, it is necessary to further increase the contact area between the powder particles in order to further reduce electric resistance. The flaky silver powder used for the increase has a non-uniform particle shape and a wide particle size distribution, so that high connection reliability cannot be obtained in the formation of further fine wiring. Therefore, there has been a growing demand for a silver paste that efficiently increases the contact area between silver powder particles and has high connection reliability in fine wiring. In general, in order to meet this requirement, studies have been made to make the shape and particle size distribution of the flaky silver powder that increases the contact area uniform.
従来の球状銀粉の製造には、特許文献２に記載したように有機還元剤と亜硫酸塩及びアルカリ若しくはアルカリ塩でｐＨ調整した溶液を還元反応温度１０℃〜５０℃で反応させ、銀粉末を得て銀ペーストに加工して用いられてきた。 For the production of conventional spherical silver powder, a solution adjusted in pH with an organic reducing agent, sulfite and alkali or alkali salt as described in Patent Document 2 is reacted at a reduction reaction temperature of 10 ° C. to 50 ° C. to obtain silver powder. Have been processed into silver paste.
また、銀ペーストを焼成して得られる導体の低抵抗化を図るため、他の手段として特許文献３にあるように、粉粒同士の接触面積の広く取れるフレーク銀粉（鱗片状銀粉）の使用も検討されてきた。フレーク銀粉は、銀粉の粉粒を物理的に塑性加工して押しつぶすことにより製造されるものであり、鱗片状銀粉と表現されることもある。確かに、フレーク銀粉は、その形状から容易に考えられるように、粉粒同士の接触面積を広く確保できるため焼成導体の低抵抗化には有効なものであった。 In addition, in order to reduce the resistance of the conductor obtained by firing the silver paste, as another means, as described in Patent Document 3, the use of flake silver powder (flaky silver powder) that can take a wide contact area between powder particles is also possible. Has been studied. Flake silver powder is produced by physically plastically processing and crushing silver powder particles, and may be expressed as scaly silver powder. Certainly, the flake silver powder is effective in reducing the resistance of the fired conductor because it can ensure a wide contact area between the powder grains, as easily considered from its shape.
更に、銀粉として、非特許文献１に開示されたようなロッド状銀粉が知られていたが、あくまでも実験的に製造可能なものと言われ、その量産手法に関しては、何ら確立されておらず、その使用方法に関しても確立されていなかった。
しかしながら、従来の銀ペースト技術において、銀ペーストを用いて形成する導体の低電気抵抗化を目指す場合には、銀ペースト内の銀粉の含有量を増加させ、導体密度を向上させ対応するのが一般的であるが、製品価格の上昇及び資源の無駄遣いを極力避ける観点から好ましくない。更に、銀粉の種類に応じて以下に述べるような問題があり、市場の要求を満足できるものではなかった。 However, in the conventional silver paste technology, when aiming to reduce the electrical resistance of the conductor formed using the silver paste, it is common to increase the content of the silver powder in the silver paste to improve the conductor density. However, it is not preferable from the viewpoint of avoiding an increase in product prices and wasteful resources. Furthermore, depending on the type of silver powder, there are problems as described below, which cannot satisfy market demands.
従来の球状銀粉の持つ問題： 従来の銀粉を含んだ銀ペーストを用いた回路形成においては、加熱温度が３００℃以下という非焼成若しくは低温焼成型の用途が多く、低抵抗化には粉粒同士の接触面積を増やす事が好ましいとされてきた。しかし、球状銀粉の接触面積を著しく増やすことは、その物理的形状から不可能である。そのため、ペースト中の銀粉含有量を増加させ導体を形成しても、得られた導体中の銀粉同士の接触密度が著しく向上することはなく、低抵抗化を図ることができなかった。球状銀粉を単独で用いる銀ペーストの場合、低電気抵抗化のみを考えると導体中の銀含有量が９５ｗｔ％前後となるように設計せざるを得なかった。 Problems with conventional spherical silver powder: In circuit formation using conventional silver paste containing silver powder, there are many non-fired or low-temperature fired applications where the heating temperature is 300 ° C. or less. It has been considered preferable to increase the contact area. However, it is impossible to significantly increase the contact area of the spherical silver powder because of its physical shape. Therefore, even if the silver powder content in the paste is increased to form a conductor, the contact density between the silver powders in the obtained conductor is not significantly improved, and the resistance cannot be reduced. In the case of a silver paste using spherical silver powder alone, it was necessary to design the silver content in the conductor to be around 95 wt% considering only the reduction in electrical resistance.
従来のフレーク銀粉の持つ問題： 従来のフレーク銀粉を用いて銀ペーストに加工し、導体を形成すると、その形状故に導体密度を向上させ、導体の低電気抵抗化が可能であった。このフレーク銀粉を用いる銀ペーストの場合、低電気抵抗化のみを考えるとフレーク銀粉の含有量が９０ｗｔ％〜９５ｗｔ％程度となるものが採用されてきた。従来のフレーク銀粉を用いる限り、近年のファインピッチ化した回路形成等には全く対応できない銀ペーストしか得られないのである。なぜなら、従来の製造方法で得られる銀粉の粉粒中には、粒子径が１０μｍを超える粗粒を含んでいる。その結果、スクリーン印刷法を用いて、微細回路を精度良く描こうとしても、スクリーンが目詰まりを起こし、回路断線を引き起こす可能性が高くなるのである。そして、従来のフレーク銀粉は、略球状の粉粒を物理的に塑性変形して製造する物であり、出来上がるフレーク銀粉の粉粒形状を制御することが困難であり、粉粒の凝集を防止するために添加する滑剤による粉粒表面の汚染があり、不純物含有量が多くなると言う欠点が存在していた。 Problems of conventional flake silver powder : When a conventional paste silver powder is used to form a silver paste and a conductor is formed, the conductor density is improved because of its shape, and the electrical resistance of the conductor can be reduced. In the case of the silver paste using this flake silver powder, what has the content of flake silver powder of about 90 wt% to 95 wt% has been adopted considering only low electric resistance. As long as the conventional flake silver powder is used, only a silver paste that is completely incompatible with the recent fine pitch circuit formation can be obtained. This is because the particles of silver powder obtained by the conventional manufacturing method include coarse particles having a particle diameter exceeding 10 μm. As a result, even if an attempt is made to draw a fine circuit with high accuracy using the screen printing method, there is a high possibility that the screen will be clogged and cause a circuit disconnection. The conventional flake silver powder is produced by physically plastically deforming substantially spherical powder particles, and it is difficult to control the powder particle shape of the resulting flake silver powder, thereby preventing the aggregation of the powder particles. For this reason, there is a disadvantage that the surface of the powder particles is contaminated by the lubricant added to increase the impurity content.
以上に述べた球状銀粉及びフレーク銀粉の持つ欠点は、その粉体特性及び粉粒の物理的形状に依存するところが大きく、今後の微細配線でかつ高い信頼性を有する導体を形成するための銀ペーストを作成するという点に関しての、根本的な問題解決は困難と判断出来る。ところが、市場では、国際的な技術競争や価格競争を勝ち抜いていくために、銀ペーストを用いて形成する導体のさらなる微細化と低抵抗化や、より安価で経済的な銀ペーストの製造が可能な銀粉を求める声が高くなってきている。 The disadvantages of the spherical silver powder and flake silver powder described above largely depend on the powder characteristics and the physical shape of the powder, and silver paste for forming a conductor with high reliability and high reliability in the future. It can be judged that it is difficult to solve the fundamental problem in terms of creating However, in order to win international technological competition and price competition in the market, it is possible to further reduce the size and resistance of conductors formed using silver paste, and to manufacture cheaper and more economical silver paste. There is a growing demand for new silver powder.
そこで、本件発明者等は、鋭意研究を行った結果、以下に述べるロッド銀粉を導電性フィラーとして用いた銀ペーストを採用することで、従来にない銀ペーストを得るに到ったのである。以下、「銀ペースト」と「銀ペーストの製造方法」とに分けて説明する。 Thus, as a result of intensive studies, the present inventors have obtained an unprecedented silver paste by adopting a silver paste using rod silver powder described below as a conductive filler. Hereinafter, the description will be divided into “silver paste” and “silver paste production method”.
＜銀ペースト＞
本件発明に係る銀ペーストは、ロッド状銀粉と樹脂成分と有機溶剤とからなる銀ペーストにおいて、前記ロッド状銀粉の粉粒は針状であり、走査型電子顕微鏡像から判断できる一次粒子の平均長径Ｌが１０μｍ以下である。
<Silver paste>
The silver paste according to the present invention is a silver paste composed of a rod-shaped silver powder, a resin component, and an organic solvent, wherein the rod-shaped silver powder particles are needle-shaped, and the average major axis of primary particles that can be determined from a scanning electron microscope image L is 10 μm or less.
ペーストを構成するロッド状銀粉： このロッド状銀粉の粉粒は、文字通り「ロッド（竿）」の形状を備えている。このロッド状銀粉の走査型電子顕微鏡像を図１に示している。本件発明で、ロッド状銀粉を用いたのは、粉粒形状が非常に特異な形状をしており、その粉粒同士の接触点が、ロッド状銀粉の粉粒の長径方向に沿った距離分確保できる。そのため、銀ペースト中の含有量が低くとも、銀ペーストに加工して形成した導体回路の電気的導通性を確実に確保し、回路の導電信頼性を高めることができるからである。 Rod-shaped silver powder constituting the paste: The rod-shaped silver powder particles literally have the shape of “rod”. A scanning electron microscope image of this rod-shaped silver powder is shown in FIG. In the present invention, the rod-shaped silver powder is used because the particle shape is very unique, and the contact point between the particles is the distance along the major axis direction of the rod-shaped silver powder particles. It can be secured. For this reason, even if the content in the silver paste is low, the electrical conductivity of the conductor circuit formed by processing into the silver paste can be reliably ensured, and the conductivity reliability of the circuit can be improved.
そして、次に走査型電子顕微鏡像の画像により得られる一次粒子の平均長径Ｌが１０μｍ以下という微粒のロッド状銀粉としての粉体特性が求められるのである。このように長い長径を持つことにより、粉粒同士の接触点が増加し、銀ペーストに加工したときの銀粉含有量が低くとも電気的導通特性に優れた導体形成が可能となるのである。そして、ロッド状銀粉の粉粒の平均長径が１０μｍを超えると、以下に述べる銀ペーストに加工して、スクリーン印刷法で回路形状を形成しようとしたときのスクリーンの目詰まりが飛躍的に起こりやすくなるのである。ここで、平均長径Ｌとは、走査型電子顕微鏡像の画像により得られる５０個の一次粒子の長径を測定し、平均して求めた長径のことである。更に、ロッド状銀粉の粉粒の平均長径が８．０μｍ以下となると、銀ペーストで形成した回路形状をファインピッチ化することが可能となり好ましい。更に、ロッド状銀粉の粉粒の平均長径が５．０μｍ以下となると、焼成加工したときの導体の表面粗さが飛躍的に滑らかなものとなり更に好ましいのである。 And the powder characteristic as a fine rod-shaped silver powder whose average long diameter L of the primary particle obtained from the image of a scanning electron microscope image is 10 micrometers or less is calculated | required next. By having such a long major axis, the contact point between the powder particles increases, and it becomes possible to form a conductor with excellent electrical conduction characteristics even when the silver powder content is low when processed into a silver paste. And when the average major axis of the rod-shaped silver powder particles exceeds 10 μm, the screen is clogged easily when it is processed into the silver paste described below and the circuit shape is formed by the screen printing method. It becomes. Here, the average major axis L is the major axis obtained by measuring and averaging the major axis of 50 primary particles obtained from the image of the scanning electron microscope image. Furthermore, when the average major axis of the rod-shaped silver powder particles is 8.0 μm or less, it is preferable because the circuit shape formed with the silver paste can be made into a fine pitch. Further, when the average major axis of the rod-shaped silver powder particles is 5.0 μm or less, the surface roughness of the conductor when fired is remarkably smooth, which is further preferable.
更に、ロッド状銀粉を構成する粉粒には、比表面積が３．０ｍ２／ｇ以下であるという粉体特性を備えることが好ましい。この比表面積は、実測した比表面積であり、ロッド銀粉試料２．００ｇを１５０℃で１時間の減圧による脱気処理を行った後、モノソーブ（カンタクロム社製）を用いてＢＥＴ１点法で測定したものである。比表面積の値が大きな場合には、ペースト化したときのペースト粘度が高くなり、銀ペーストの取扱が困難となる。ここで言うロッド状銀粉の表面状態は比較的に滑らかであるが、比表面積が３．０ｍ２／ｇを超えるとペースト粘度が増大する傾向が顕著になるのである。更に、比表面積が２．５ｍ２／ｇ以下となると、ペーストを構成する有機剤の種類によらず低粘度化が達成できるので、より好ましいものとなる。 Furthermore, it is preferable that the powder particles constituting the rod-shaped silver powder have a powder characteristic that the specific surface area is 3.0 m 2 / g or less. This specific surface area is an actually measured specific surface area, and was measured by a BET one-point method using monosorb (manufactured by Kantachrome Co., Ltd.) after degassing the rod silver powder sample 2.00 g at 150 ° C. for 1 hour under reduced pressure. Is. When the value of the specific surface area is large, the paste viscosity becomes high when it is made into a paste, and handling of the silver paste becomes difficult. The surface state of the rod-shaped silver powder referred to here is relatively smooth, but when the specific surface area exceeds 3.0 m 2 / g, the tendency of the paste viscosity to increase becomes remarkable. Furthermore, when the specific surface area is 2.5 m 2 / g or less, a low viscosity can be achieved regardless of the type of organic agent constituting the paste, which is more preferable.
更に、前記ロッド状銀粉の粉粒の結晶子径（１１１）は３０ｎｍ以上である事が好ましいのである。ここで結晶子径を、「結晶子（１１１）」と標記したのは、Ｘ線回折による（１１１）面のシグナル強度を持って換算したときの結晶子径を用いたのである。通常の大半の微細配線用途のペーストに用いられる球状銀粉やフレーク銀粉は、平均粒子径が０．３〜２μｍ程度であり、この粒子径範囲の結晶子径（１１１）は、１０ｎｍ〜３０ｎｍレベルであり、これに比べれば、本件発明に係るロッド状銀粉の結晶子径は非常に大きなものであると言える。本件発明で用いたロッド状銀粉は、その粒子の長径が長くなるほど、結晶子径も大きくなる。従って、逆に考えれば、ロッド状銀粉の粒子が微粒化すればするほど、結晶子径が３０ｎｍに近づくのである。このことから、以下に述べる製造方法において、一方向凝固法と同様に、一定の結晶方向に配向した電気化学的結晶成長が起こることでロッド状となっていると推測出来る。 Furthermore, the crystallite diameter (111) of the rod-shaped silver powder is preferably 30 nm or more. Here, the crystallite diameter is indicated as “crystallite (111)” because the crystallite diameter when converted with the signal intensity of the (111) plane by X-ray diffraction is used. Spherical silver powder and flake silver powder used in most pastes for use in fine wiring usually have an average particle diameter of about 0.3 to 2 μm, and the crystallite diameter (111) in this particle diameter range is on the order of 10 nm to 30 nm. Yes, compared to this, it can be said that the crystallite diameter of the rod-shaped silver powder according to the present invention is very large. The rod-shaped silver powder used in the present invention has a larger crystallite diameter as the longer diameter of the particles becomes longer. Therefore, conversely, the more the rod-shaped silver powder particles are atomized, the closer the crystallite diameter is to 30 nm. From this, it can be inferred that, in the manufacturing method described below, as in the unidirectional solidification method, electrochemical crystal growth oriented in a certain crystal direction occurs to form a rod shape.
この結晶子径は、電気抵抗率と耐熱収縮性との相関関係が一般的に言われている。即ち、結晶子径が大きな程、電気抵抗率が低くなり、また、耐熱収縮性に優れていると言われる。即ち、結晶子径が大きな銀粉を用いて銀ペーストを製造し、この銀ペーストで導体形成を行った場合、低抵抗率化が達成でき、かつ、焼成前後の回路形状の寸法安定変化率が小さくなり寸法安定性に優れるものとなる。本件発明に係るロッド状銀粉の場合、この優れた導体の低抵抗率化と耐熱収縮特性が得られるものと考えられる。 The crystallite diameter is generally said to have a correlation between electrical resistivity and heat shrinkage. That is, it is said that the larger the crystallite diameter, the lower the electrical resistivity and the better the heat shrinkage resistance. That is, when a silver paste is produced using silver powder having a large crystallite diameter and a conductor is formed using this silver paste, a low resistivity can be achieved, and the dimensional stability change rate of the circuit shape before and after firing is small. Therefore, the dimensional stability is excellent. In the case of the rod-shaped silver powder according to the present invention, it is considered that this excellent conductor resistivity and heat shrinkage characteristics can be obtained.
また、ロッド状銀粉のみを用いた銀ペーストの場合、その特異な形状と高い結晶性から、得られた導体中の銀粉含有量が９０ｗｔ％以下であっても、微細配線用途に十分な低抵抗化が可能であり、良好な導電性を備える導体を得る事が可能となるのである。 In addition, in the case of a silver paste using only rod-shaped silver powder, low resistance sufficient for fine wiring applications even if the silver powder content in the obtained conductor is 90 wt% or less due to its unique shape and high crystallinity Therefore, it is possible to obtain a conductor having good conductivity.
ペーストを構成する樹脂成分： 本来であれば、銀ペーストを構成する樹脂成分を特に限定する必要は無いと考える。しかしながら、上述した如き微粒のロッド状銀粉をフィラーとして用いることを前提に、ロッド状銀粉の良好な分散性を確保できる組成を採用しなければならない。また、本件発明に係る銀ペーストはファインピッチな回路形成が可能でかつ、低抵抗化となることを目的としており、採用される焼成温度以下で溶媒が除去でき、しかもファインピッチ回路形成用途に適したペースト性能を確保できる樹脂組成を採用しなければならない。 Resin component constituting the paste: Originally, it is considered that there is no need to particularly limit the resin component constituting the silver paste. However, on the premise that the fine rod-shaped silver powder as described above is used as a filler, a composition that can ensure good dispersibility of the rod-shaped silver powder must be adopted. Further, the silver paste according to the present invention is capable of forming a fine pitch circuit and lowering the resistance, can remove the solvent at a temperature not higher than the employed baking temperature, and is suitable for a fine pitch circuit forming application. The resin composition must ensure the paste performance.
これらのことを考慮して、エポキシ樹脂、ポリエステル樹脂、ケイ素樹脂、ユリア樹脂、アクリル樹脂、セルロース樹脂から選ばれる１種以上を含む組成を採用するのが望ましいのである。 In view of these matters, it is desirable to employ a composition containing at least one selected from an epoxy resin, a polyester resin, a silicon resin, a urea resin, an acrylic resin, and a cellulose resin.
これらの樹脂成分を、より具体的に特定すれば、次のようになる。ａ）エポキシ樹脂とは、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型、ノボラック型、クレゾールノボラック型、グリシジルアミン型、グリシジルエーテル型、脂肪族型、複素環式型エポキシ樹脂等である。 If these resin components are specified more specifically, they are as follows. a) The epoxy resin includes bisphenol A type, bisphenol F type, bisphenol AD type, novolac type, cresol novolac type, glycidylamine type, glycidyl ether type, aliphatic type, and heterocyclic type epoxy resin.
ｂ）ポリエステル樹脂とは、ポリエチレンテレフタレート、ポリプロピレングリコールマレエートフタレート、ポリプロピレングリコールフマレートフタレート、ポリプロピレングリコールマレート、ポリプロピレングリコールフマレート、ポリプロピレングリコールアジペートマレート等のジカルボン酸とグリコールの重合物等である。 b) The polyester resin is a polymer of dicarboxylic acid and glycol such as polyethylene terephthalate, polypropylene glycol maleate phthalate, polypropylene glycol fumarate phthalate, polypropylene glycol maleate, polypropylene glycol fumarate, polypropylene glycol adipate maleate, and the like.
そして、ここで言うポリエステルの合成には、以下に述べるジカルボン酸類とグリコール類とを縮合反応させて得られるのであることが望ましいのである。ジカルボン酸類としては、テレフタル酸、イソフタル酸、オルソフタル酸、２，６−ナフタレンジカルボン酸などの芳香族ジカルボン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、ドデカンジカルボン酸、アゼライン酸等の脂肪族ジカルボン酸、炭素数１２〜２８の２塩基酸、１，４−シクロヘキサンジカルボン酸、１，３ーシクロヘキサンジカルボン酸、１，２−シクロヘキサンジカルボン酸、４−メチルヘキサヒドロ無水フタル酸、３−メチルヘキサヒドロ無水フタル酸、２−メチルヘキサヒドロ無水フタル酸、ジカルボキシ水素添加ビスフェノールＡ、ジカルボキシ水素添加ビスフェノールＳ、ダイマー酸、水素添加ダイマー酸、水素添加ナフタレンジカルボン酸、トリシクロデカンジカルボン酸などの脂環族ジカルボン酸等である。 And it is desirable for the synthesis | combination of the polyester said here to obtain by carrying out the condensation reaction of the dicarboxylic acids and glycols which are described below. Dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and azelaic acid. Dicarboxylic acid, dibasic acid having 12 to 28 carbon atoms, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexa Fats such as hydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxy hydrogenated bisphenol A, dicarboxy hydrogenated bisphenol S, dimer acid, hydrogenated dimer acid, hydrogenated naphthalenedicarboxylic acid, tricyclodecane dicarboxylic acid Cyclic dicarboxylic acid, etc. A.
グリコールには、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−１，５−ペンタンジオール、２，２−ジエチル−１，３−プロパンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，９−ノナンジオール、１，１０−デカンジオール、１，４−シクロヘキサンジメタノール、１，３−シクロヘキサンジメタノール、１，２−シクロヘキサンジメタノール、ダイマージオール等を用いるのである。 The glycol includes ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5- Pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, dimer diol, and the like are used.
ｃ）ケイ素樹脂とは、アミノ変性シリコーン、エポキシ変性シリコーン、カルボキシル変性シリコーン、カルビノール変性シリコーン、メタクリル変性シリコーン、メルカプト変性シリコーン、フェノール変性シリコーン、ポリエーテル変性シリコーン、ポリエステル変性シリコーン、アルキッド変性シリコーン、アクリル変性シリコーン、メチルスチリル変性シリコーン、アルキル変性シリコーン、フッ素変性シリコーン等である。 c) Silicone resin means amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, polyether-modified silicone, polyester-modified silicone, alkyd-modified silicone, acrylic Modified silicone, methylstyryl-modified silicone, alkyl-modified silicone, fluorine-modified silicone, and the like.
ｄ）ユリア樹脂とは、アミン変性ユリア樹脂、ブタノール変性ユリア樹脂等である。 d) The urea resin is an amine-modified urea resin, a butanol-modified urea resin, or the like.
ｅ）アクリル樹脂とは、ポリアクリル酸、ポリメタクリル酸、ポリアクリル酸メチル、ポリメタクリル酸メチル、ポリイタコン酸、ポリアクリル酸塩、ポリメタクリル酸塩、ポリイタコン酸塩等である。 e) Acrylic resin includes polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, polyitaconic acid, polyacrylate, polymethacrylate, polyitaconate, and the like.
ｆ）セルロース樹脂とは、メチルセルロース、エチルセルロース、プロピルセルロース、ブチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシブチルセルロース、アセチルセルロース等である。 f) The cellulose resin is methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose, acetyl cellulose, or the like.
これらは１種でも２種以上を同時に用いても構わないのである。これらに関しても、分散させる銀粉が容易に分散し、且つ、銀粉の粉粒表面の変質を防止することが可能だからである。 These may be used alone or in combination of two or more. Also in these respects, the silver powder to be dispersed can be easily dispersed, and alteration of the surface of the silver powder particles can be prevented.
銀粉とペーストとの配合バランス： 更に、本件発明に係る銀ペーストのロッド状銀粉と有機成分との配合バランスを適正なものとしなければ、良好な回路形状を形成できるものとはならない。そこで、本件発明者等が、鋭意研究の結果、銀ペーストを用いて導体を形成し、その後１８０℃程度で焼成して得られた導体中のロッド状銀粉含有量が、７５ｗｔ％以上、より好ましくは８０〜９３ｗｔ％の範囲にあれば、良好な回路等の導体形成が可能と判断したのである。ロッド状銀粉の含有量が７５ｗｔ％未満の場合には、いかに分散性が高く微粒のロッド状銀粉を用いても、焼成して形成した回路等の膜密度が低下し比抵抗が高くなるのである。そして、ロッド状銀粉の含有量が９３ｗｔ％を超えると、銀ペーストの粘度が急激に上昇し、ファインピッチ回路形状等を形成するには使いづらい銀ペーストとなる。仮に、粘度を下げるために銀ペースト作製時に溶剤を多く添加すると、形成した回路の膜密度が低くなり、結果的に比抵抗が高くなるのである。 Compounding balance of silver powder and paste: Furthermore, unless the compounding balance of the rod-shaped silver powder and the organic component of the silver paste according to the present invention is appropriate, a good circuit shape cannot be formed. Therefore, as a result of intensive research, the present inventors have formed a conductor using a silver paste and then sintered at about 180 ° C., and the rod-shaped silver powder content in the conductor is more preferably 75 wt% or more. If it is in the range of 80 to 93 wt%, it was determined that a conductor such as a good circuit can be formed. When the content of the rod-shaped silver powder is less than 75 wt%, no matter how highly dispersible and fine-grained rod-shaped silver powder is used, the film density of the circuit formed by firing decreases and the specific resistance increases. . And if content of rod-shaped silver powder exceeds 93 wt%, the viscosity of a silver paste will rise rapidly and it will become a silver paste which is hard to use to form a fine pitch circuit shape etc. If a large amount of solvent is added during the preparation of the silver paste in order to reduce the viscosity, the film density of the formed circuit is lowered, resulting in an increase in specific resistance.
本件発明に係るロッド状銀粒子を用いた銀ペーストは、従来の銀粉を用いた銀ペーストと比べ、フィラーであるロッド状銀粒子の結晶子径が高いことから、当該粒子自体の電気抵抗が低く、当該粒子の含有量が低くとも、形成した導体が良好な電気的導電性を示すものとなるのである。 Since the silver paste using the rod-shaped silver particles according to the present invention has a larger crystallite diameter of the rod-shaped silver particles that are fillers than the silver paste using the conventional silver powder, the electrical resistance of the particles themselves is low. Even if the content of the particles is low, the formed conductor exhibits good electrical conductivity.
＜ロッド状銀粉の製造方法＞
本件発明に係る銀ペーストは、銀粉に、ロッド状銀粉を用いることが前提である。しかも、上述の銀ペースト製造方法の説明から理解できるように、当初から粒度分布に優れ且つ高分散のロッド状銀粉を使用することができれば、極めて有利なものとなる。従って、以下に述べる手法で得られるロッド状銀粉を用いることが好ましいのである。
<Method for producing rod-shaped silver powder>
The silver paste according to the present invention is premised on using rod-shaped silver powder as the silver powder. Moreover, as can be understood from the above description of the silver paste production method, it is extremely advantageous if a rod-shaped silver powder having an excellent particle size distribution and a high dispersion can be used from the beginning. Therefore, it is preferable to use rod-shaped silver powder obtained by the method described below.
本件発明者等は銀化合物の還元について鋭意検討した結果、１，３−ブタンジオールと分散剤との混合溶液中で水溶性銀化合物を還元することにより、粒度分布に優れ且つ高分散のロッド状銀粉が得られることを見いだした。即ち、本件発明のロッド状銀粒子の製造方法は、１，３−ブタンジオールと分散剤との混合溶液に水溶性銀化合物の水溶液を添加し、該銀化合物を銀に還元するのに十分な温度に加熱することを特徴とする。 As a result of intensive studies on the reduction of the silver compound, the inventors of the present invention reduced the water-soluble silver compound in a mixed solution of 1,3-butanediol and a dispersing agent, thereby achieving an excellent particle size distribution and a highly dispersed rod shape. I found that silver powder was obtained. That is, the method for producing rod-shaped silver particles of the present invention is sufficient to add an aqueous solution of a water-soluble silver compound to a mixed solution of 1,3-butanediol and a dispersant, and to reduce the silver compound to silver. Heating to temperature.
本件発明の製造方法で用いることができる分散剤として、例えばポリビニルピロリドン、ポリエチレンイミン、ポリアクリルアミド、ポリ（２−メチル−２−オキサゾリン）等の含窒素有機化合物や、ポリビニルアルコールを挙げることができ、ポリビニルピロリドンを好適に用いることができる。 Examples of the dispersant that can be used in the production method of the present invention include nitrogen-containing organic compounds such as polyvinylpyrrolidone, polyethyleneimine, polyacrylamide, and poly (2-methyl-2-oxazoline), and polyvinyl alcohol. Polyvinyl pyrrolidone can be preferably used.
本件発明の製造方法においては、１，３−ブタンジオールと分散剤との混合溶液中の分散剤の量が１，３−ブタンジオールの質量基準で０．００５質量％以上、好ましくは０．０１〜５質量％であることが好適である。分散剤の量が０．００５質量％未満である場合には、本件発明で目的としている生産性の高さが不十分となる傾向があり、また生成するロッド状銀粒子の形状がイビツになる傾向もある。逆に、５質量％を超えても、生産性の点でそれに見合った効果は得られないだけでなく、反応系の粘度が高くなり、生成銀の回収に不利となる傾向がある。 In the production method of the present invention, the amount of the dispersant in the mixed solution of 1,3-butanediol and the dispersant is 0.005% by mass or more based on the mass of 1,3-butanediol, preferably 0.01. It is suitable that it is -5 mass%. When the amount of the dispersing agent is less than 0.005% by mass, the high productivity aimed at in the present invention tends to be insufficient, and the shape of the generated rod-shaped silver particles becomes ill. There is also a trend. On the contrary, even if it exceeds 5% by mass, not only an effect commensurate with the productivity can be obtained, but also the viscosity of the reaction system becomes high, which tends to be disadvantageous for the recovery of the produced silver.
また、本件発明の製造方法においては、１，３−ブタンジオールと分散剤との混合溶液に添加する水溶性銀化合物水溶液の添加量が銀換算で１，３−ブタンジオールの質量基準で０．１〜１０質量％となり且つ分散剤の質量基準で０．５〜５０倍となる量であることが好ましい。水溶性銀化合物水溶液の添加量が上記の範囲よりも少ない場合には、本件発明で目的としている生産性の高さが不十分となる傾向がある。逆に、水溶性銀化合物水溶液の添加量が上記の範囲より多くても、それに見合った効果は得られない傾向がある。 Moreover, in the manufacturing method of this invention, the addition amount of the water-soluble silver compound aqueous solution added to the mixed solution of 1, 3- butanediol and a dispersing agent is 0.00 on the mass reference | standard of 1, 3- butanediol in silver conversion. The amount is preferably 1 to 10% by mass and 0.5 to 50 times based on the mass of the dispersant. When the addition amount of the water-soluble silver compound aqueous solution is less than the above range, the high productivity aimed at in the present invention tends to be insufficient. On the contrary, even if the addition amount of the water-soluble silver compound aqueous solution is larger than the above range, there is a tendency that an effect corresponding to the addition amount cannot be obtained.
本件発明の製造方法においては、１，３−ブタンジオールと分散剤との混合溶液に、室温で又は所望により該混合溶液を４０〜７０℃に加熱した後に、水溶性銀化合物の水溶液を添加する。その後、銀化合物を銀に還元するのに十分な温度に加熱する必要がある。この加熱温度は、好ましくは、８５℃以上で、分散剤の沸点又は分解温度と１，３一ブタンジオールの沸点との内で一番低い温度未満であり、より好ましくは１００〜１６０℃程度である。従って、分散剤として、その沸点又は分解温度がこの加熱温度よりも高いものを用いる。また、本件発明の製造方法においては、ロッド状銀粒子の成長を確実にするために銀化合物を銀に還元するのに十分な温度に１０分間以上保持することが好ましい。なお、本件発明の製造方法で用いることができる水溶性銀化合物として、例えば硝酸銀、塩素酸銀、過塩素酸銀、シアノ銀酸塩、銀アンミン錯体等を挙げることができる。 In the production method of the present invention, an aqueous solution of a water-soluble silver compound is added to a mixed solution of 1,3-butanediol and a dispersant at room temperature or optionally after heating the mixed solution to 40 to 70 ° C. . It is then necessary to heat the silver compound to a temperature sufficient to reduce it to silver. This heating temperature is preferably 85 ° C. or higher and is lower than the lowest temperature among the boiling point or decomposition temperature of the dispersant and the boiling point of 1,3 monobutanediol, more preferably about 100 to 160 ° C. is there. Therefore, a dispersant whose boiling point or decomposition temperature is higher than the heating temperature is used. Moreover, in the manufacturing method of this invention, in order to ensure the growth of rod-shaped silver particles, it is preferable to hold at a temperature sufficient for reducing the silver compound to silver for 10 minutes or more. Examples of the water-soluble silver compound that can be used in the production method of the present invention include silver nitrate, silver chlorate, silver perchlorate, cyanosilver salt, and silver ammine complex.
以上に述べてきた銀粉製造方法により得られた銀粉は、走査型電子顕微鏡像の画像解析により得られる一次粒子の長径が８．０μｍ以下であり、極めて細いというロッド状銀粉であり、しかも良好な分散性を備える。ペースト加工して、その銀ペーストを用いて形成する回路をファインピッチ化し、形成した回路の導電性確保が容易となるのである。 The silver powder obtained by the silver powder production method described above is a rod-shaped silver powder whose primary particle obtained by image analysis of a scanning electron microscope image has a major axis of 8.0 μm or less, is extremely thin, and is excellent. Provide dispersibility. By processing the paste, the circuit formed using the silver paste is made fine pitch, and it becomes easy to ensure the conductivity of the formed circuit.
＜銀ペーストの製造＞
上述のような製造方法で得られたロッド状銀粉と上述の有機剤（樹脂成分と溶剤とを含む）との混合方法に関して、特に制限はなく常法を適用することができる。
<Manufacture of silver paste>
There is no particular limitation on the method of mixing the rod-shaped silver powder obtained by the above-described production method and the above-mentioned organic agent (including the resin component and the solvent), and a conventional method can be applied.
本件発明に係る銀ペーストは、内包されているロッド状銀粉が、従来に無い微粒且つ高分散の銀粉であるため、微粒で且つ有機剤への優れた分散性を示すため、ファインピッチ回路の形成に最適で、形成した導体の比抵抗を小さくすることが可能となる。 In the silver paste according to the present invention, the encapsulated rod-shaped silver powder is an unprecedented fine and high-dispersion silver powder, so it is fine and exhibits excellent dispersibility in organic agents. The specific resistance of the formed conductor can be reduced.
以下、実施例と比較例とを対比しつつ、より詳細に説明することとする。 Hereinafter, it will be described in more detail while comparing the example and the comparative example.
ロッド状銀粉の製造： ５０ｍｌビーカーに１，３−ブタンジオール（和光純薬工業株式会社製）４４．５３ｇ及びポリビニルピロリドンＫ３０（和光純薬工業株式会社製）０．０９ｇを加え、マグネチックスターラーを用いて攪拌し、溶解させた。この溶液をホットスターラーで加熱して５０℃になった段階で、この溶液に、硝酸銀（大浦貴金属工業株式会社製）０．６７ｇと超純水１．００ｇとからなる水溶液を滴下し、その溶液温度が１２０℃になるまで加熱してその温度に維持した。１２０℃に到達した３０分後にサンプリングを行い、反応進行状態を銀イオンメーター（堀場製作所製のＦ−２３）を用いて確認した。このときの反応前理論銀イオン濃度は９３８１ｐｐｍ、３０分反応後の銀イオン濃度３１０ｐｐｍであり、反応率９６．７０％であり、１２０℃に到達した３０分後には反応は実質的に終了していた。 Production of rod-shaped silver powder: 44.53 g of 1,3-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.09 g of polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Industries, Ltd.) are added to a 50 ml beaker, and a magnetic stirrer is added. Used to stir and dissolve. When this solution is heated with a hot stirrer to reach 50 ° C., an aqueous solution composed of 0.67 g of silver nitrate (manufactured by Oura Kikinzoku Kogyo Co., Ltd.) and 1.00 g of ultrapure water is added dropwise to the solution. It was heated to a temperature of 120 ° C. and maintained at that temperature. Sampling was performed 30 minutes after reaching 120 ° C., and the reaction progress was confirmed using a silver ion meter (F-23 manufactured by Horiba, Ltd.). At this time, the theoretical silver ion concentration before reaction was 9381 ppm, the silver ion concentration after reaction for 30 minutes was 310 ppm, the reaction rate was 96.70%, and the reaction was substantially completed 30 minutes after reaching 120 ° C. It was.
以上のようにして得られたロッド状銀粉を分取するため、ヌッチェを用いて濾過し、１００ｍｌの水と５０ｍｌのメタノールとを用いて洗浄し、更に７０℃×５時間の乾燥を行た。この得られたロッド状銀粉の一次粒子の平均長径Ｌが５．３μｍ、比表面積が２．２８ｍ２／ｇ、粉粒の結晶子径（１１１）が１０８．７ｎｍであった。そして、得られたロッド銀粉の粉粒の走査型電子顕微鏡像が図１に示すものである。 In order to fractionate the rod-shaped silver powder obtained as described above, it was filtered using a Nutsche, washed with 100 ml of water and 50 ml of methanol, and further dried at 70 ° C. for 5 hours. The average primary diameter L of the primary particles of the obtained rod-shaped silver powder was 5.3 μm, the specific surface area was 2.28 m 2 / g, and the crystallite diameter (111) of the powder grains was 108.7 nm. And the scanning electron microscope image of the particle | grains of the obtained rod silver powder is what is shown in FIG.
銀ペーストの製造： 脂環式エポキシ樹脂（日本化薬社製：ＡＫ−６０１）６．１９ｇと酸無水物系硬化剤（日本化薬社製：カヤハードＭＣＤ）１．４３ｇと、アミンアダクト型硬化剤（味の素ファインテクノ社製：アミキュアＭＹ−２４）０．３８ｇと、粘度調整剤としてα−ターピネオール（ヤスハラケミカル社製）をロッド状銀粉の含有率に応じて適宜用い、パドル型混練機で５分間混練した後、上記ロッド状銀粉を加え、さらに１０分間混練した。そして、得られた混練物を引き続き３本ロールで混練した後、脱泡機（シンキー社製：ＡＲ−２５０）を用いて混練物中に含まれる気泡を除去し、銀ペーストＡを得た。このときの銀ペーストＡは、ロッド状銀粉の含有率を９２．２ｗｔ％、８８ｗｔ％、８５ｗｔ％と変化させ、銀ペーストＡ−１、銀ペーストＡ−２、銀ペーストＡ−３の三種類の銀ペーストとした。 Production of silver paste: 6.19 g of alicyclic epoxy resin (Nippon Kayaku Co., Ltd .: AK-601), 1.43 g of acid anhydride curing agent (Nippon Kayaku Co., Ltd .: Kayahard MCD), and amine adduct type curing Agent (Ajinomoto Finetechno Co., Ltd .: Amicure MY-24) 0.38 g and α-terpineol (manufactured by Yasuhara Chemical Co., Ltd.) as a viscosity modifier are appropriately used according to the content of the rod-shaped silver powder, and 5 minutes in a paddle type kneader. After kneading, the above rod-shaped silver powder was added and further kneaded for 10 minutes. And after knead | mixing the obtained kneaded material with 3 rolls, the bubble contained in a kneaded material was removed using the defoaming machine (made by Shinkey: AR-250), and the silver paste A was obtained. The silver paste A at this time changes the content rate of rod-shaped silver powder to 92.2 wt%, 88 wt%, and 85 wt%, and three types of silver paste A-1, silver paste A-2, and silver paste A-3 Silver paste was used.
得られたそれぞれの銀ペーストを、スクリーン印刷機を用いて配線幅５０μｍ、配線と配線の間隔を５０μｍとしアルミナ基板に印刷したところ、配線の断線やニジミが無い良好な印刷性を示した。また、スクリーン印刷機に用いたスクリーンを顕微鏡により観察した結果、スクリーンの目に銀粉は全く目詰まりしていない事を確認した。 Each of the obtained silver pastes was printed on an alumina substrate with a wiring width of 50 μm and a wiring-to-wiring spacing of 50 μm using a screen printing machine, and showed good printability without wiring disconnection or blurring. Moreover, as a result of observing the screen used for the screen printing machine with a microscope, it was confirmed that the silver dust was not clogged at all in the eyes of the screen.
引き続きスクリーン印刷機を用いて、アルミナ基板上に比抵抗測定用のサンプルとして、縦４ｃｍ×横３ｃｍの条件で、上記銀ペーストを印刷した後、温度１８０℃の条件で１時間乾燥させた。このようにして得られた乾燥膜の表面抵抗を４探針抵抗測定器（三菱化学社製：ロレスタＧＰ）で測定し、また、乾燥膜の膜厚をデジタル膜厚計で測定し、比抵抗を算出した。その結果、銀ペーストＡ−１を用いた場合の比抵抗は、５．５９×１０−５Ω・ｃｍ、銀ペーストＡ−２を用いた場合の比抵抗は、６．９４×１０−４Ω・ｃｍ、銀ペーストＡ−３を用いた場合の比抵抗は、１．１６×１０−３Ω・ｃｍであった。 Subsequently, the silver paste was printed as a sample for measuring specific resistance on an alumina substrate using a screen printing machine under the conditions of 4 cm long × 3 cm wide, and then dried for 1 hour at a temperature of 180 ° C. The surface resistance of the dried film thus obtained was measured with a 4-probe resistance measuring instrument (Mitsubishi Chemical Corporation: Loresta GP), and the film thickness of the dried film was measured with a digital film thickness meter. Was calculated. As a result, the specific resistance when the silver paste A-1 was used was 5.59 × 10 −5 Ω · cm, and the specific resistance when the silver paste A-2 was used was 6.94 × 10 −4 Ω. The specific resistance when using cm and the silver paste A-3 was 1.16 × 10 −3 Ω · cm.
この比較例では、実施例のロッド状銀粉に代えて、球状銀粉（平均粒径：１．６５μｍ、結晶子径（１１１）：１２．１ｎｍ）を用い、その他の条件は実施例と同様に、球状銀粉の含有率を９２．２ｗｔ％、８８ｗｔ％、８５ｗｔ％と変化させ、銀ペーストＩ、銀ペーストＩＩ、銀ペーストＩＩＩの三種類の銀ペーストとした。そして、実施例と同様の比抵抗評価を行った。従って、ここでは球状銀粉の製造に関してのみ説明する。 In this comparative example, spherical silver powder (average particle diameter: 1.65 μm, crystallite diameter (111): 12.1 nm) was used instead of the rod-shaped silver powder of the example, and other conditions were the same as in the example. The content of the spherical silver powder was changed to 92.2 wt%, 88 wt%, and 85 wt% to obtain three types of silver pastes of silver paste I, silver paste II, and silver paste III. And the specific resistance evaluation similar to an Example was performed. Accordingly, only the production of spherical silver powder will be described here.
球状銀粉の製造： まず最初に、６３．３ｇの硝酸銀を１．０リットルの純水に溶解させ硝酸銀水溶液を調製し、これに２５０ｍｌの２５ｗｔ％濃度アンモニア水を一括で添加して攪拌することにより銀アンミン錯体水溶液を得たのである。 Production of spherical silver powder: First, 63.3 g of silver nitrate was dissolved in 1.0 liter of pure water to prepare an aqueous silver nitrate solution, and 250 ml of 25 wt% aqueous ammonia was added to the solution in a lump and stirred. A silver ammine complex aqueous solution was obtained.
そして、この銀アンミン錯体溶液を反応槽に入れ、ここに還元剤として２１ｇのヒドロキノンを１．３リットルの純水に溶解させたヒドロキノン水溶液を一括で添加して、液温を２０℃に維持して攪拌し反応させることで銀粉を還元析出させた。 Then, this silver ammine complex solution is put into a reaction vessel, and a hydroquinone aqueous solution in which 21 g of hydroquinone is dissolved in 1.3 liters of pure water as a reducing agent is added all at once to maintain the liquid temperature at 20 ° C. The silver powder was reduced and precipitated by stirring and reacting.
以上のようにして得られた微粒銀粉を、ヌッチェを用いて濾過し、１００ｍｌの水と５０ｍｌのメタノールとを用いて洗浄し、更に７０℃×５時間の乾燥を行い球状銀粉を得たのである。この得られた球状銀粉の一次粒子の平均粒径１．６５μｍ、比表面積が０．４ｍ２／ｇ、粉粒の結晶子径（１１１）が１２．１ｎｍであった。そして、得られたロッド銀粉の粉粒の走査型電子顕微鏡像が図１に示すものである。以下、球状銀粉の含有率を上記のように変化させ、銀ペーストＩ、銀ペーストＩＩ、銀ペーストＩＩＩの三種類の銀ペーストとした。 The fine silver powder obtained as described above was filtered using Nutsche, washed with 100 ml of water and 50 ml of methanol, and further dried at 70 ° C. for 5 hours to obtain spherical silver powder. . The primary particles of the obtained spherical silver powder had an average particle diameter of 1.65 μm, a specific surface area of 0.4 m 2 / g, and a crystallite diameter (111) of the powder grains of 12.1 nm. And the scanning electron microscope image of the particle | grains of the obtained rod silver powder is what is shown in FIG. Hereinafter, the content of the spherical silver powder was changed as described above to obtain three types of silver pastes of silver paste I, silver paste II, and silver paste III.
得られたそれぞれの銀ペーストを、スクリーン印刷機を用いて配線幅５０μｍ、配線と配線の間隔を５０μｍとしアルミナ基板に印刷したところ、配線の断線やニジミが無い良好な印刷性を示した。また、スクリーン印刷機に用いたスクリーンを顕微鏡により観察した結果、スクリーンの目に対する目詰まりは全くしていない事が確認できた。 Each of the obtained silver pastes was printed on an alumina substrate with a wiring width of 50 μm and a wiring-to-wiring spacing of 50 μm using a screen printing machine, and showed good printability without wiring disconnection or blurring. Moreover, as a result of observing the screen used for the screen printing machine with a microscope, it was confirmed that the screen was not clogged at all.
引き続きスクリーン印刷機を用いて、アルミナ基板上に比抵抗測定用のサンプルとして、縦４ｃｍ×横３ｃｍの条件で、上記銀ペーストを印刷した後、温度１８０℃の条件で１時間乾燥させた。このようにして得られた乾燥膜の表面抵抗を４探針抵抗測定器（三菱化学社製：ロレスタＧＰ）で測定し、また、乾燥膜の膜厚をデジタル膜厚計で測定し、比抵抗を算出した。その結果、銀ペーストＩを用いた場合の比抵抗は１．５６×１０＋４Ω・ｃｍ、銀ペーストＩＩ及び銀ペーストＩＩＩを用いた場合の比抵抗の測定は出来なかった。 Subsequently, the silver paste was printed as a sample for measuring specific resistance on an alumina substrate using a screen printing machine under the conditions of 4 cm long × 3 cm wide, and then dried for 1 hour at a temperature of 180 ° C. The surface resistance of the dried film thus obtained was measured with a 4-probe resistance measuring instrument (Mitsubishi Chemical Corporation: Loresta GP), and the film thickness of the dried film was measured with a digital film thickness meter. Was calculated. As a result, the specific resistance when using silver paste I was 1.56 × 10 +4 Ω · cm, and the specific resistance when using silver paste II and silver paste III could not be measured.
＜実施例と比較例との対比＞
上記実施例と比較例との比抵抗の値を対比すれば、比較例の場合の導体の比抵抗がかなり高くなっていることが明らかである。しかも、比較例の場合には、球状銀粉の含有量が９０ｗｔ％以下になると、１８０℃×１時間の乾燥膜での抵抗測定は不可能となり、導体の電気的導電性が得られないことが理解出来るのである。これに対し、実施例のロッド状銀粉を用いると、銀ペースト内の含有率が９０ｗｔ％未満の領域でも、導体の良好な電気的導電性能を得ることが可能であることが理解出来る。
<Contrast between Example and Comparative Example>
If the specific resistance values of the above example and the comparative example are compared, it is clear that the specific resistance of the conductor in the comparative example is considerably high. In addition, in the case of the comparative example, when the content of the spherical silver powder is 90 wt% or less, it is impossible to measure resistance with a dry film at 180 ° C. × 1 hour, and the electrical conductivity of the conductor cannot be obtained. I can understand. On the other hand, when the rod-shaped silver powder of the example is used, it can be understood that good electrical conductivity performance of the conductor can be obtained even in the region where the content in the silver paste is less than 90 wt%.
（参考例１）
銀粉の製造： ここでのロッド状銀粉の製造は、ポリビニルピロリドンＫ３０の量を０．０９ｇから０．０５ｇに変更した以外は実施例と同様に処理したものである。このときの反応前理論銀イオン濃度は９３８１ｐｐｍ、３０分反応後の銀イオン濃度１８５ｐｐｍであり、反応率９８．０３％であった。１２０℃に到達した３０分後には反応は実質的に終了していた。この得られたロッド状銀粉の一次粒子の平均長径Ｌが７．３μｍ、比表面積が２．３４ｍ２／ｇ、粉粒の結晶子径（１１１）が１０７．５ｎｍであった。そして、得られたロッド銀粉の粉粒の走査型電子顕微鏡像が図２に示すものである。
(Reference Example 1)
Production of silver powder: The production of the rod-shaped silver powder here was carried out in the same manner as in the Examples except that the amount of polyvinylpyrrolidone K30 was changed from 0.09 g to 0.05 g. The theoretical silver ion concentration before reaction at this time was 9381 ppm, the silver ion concentration after 30 minutes of reaction was 185 ppm, and the reaction rate was 98.03%. The reaction was substantially completed 30 minutes after reaching 120 ° C. The average primary diameter L of the primary particles of the obtained rod-shaped silver powder was 7.3 μm, the specific surface area was 2.34 m 2 / g, and the crystallite diameter (111) of the powder grains was 107.5 nm. And the scanning electron microscope image of the particle | grains of the obtained rod silver powder is what is shown in FIG.
銀ペーストの製造： 脂環式エポキシ樹脂（日本化薬社製：ＡＫ−６０１）６．１９ｇと酸無水物系硬化剤（日本化薬社製：カヤハードＭＣＤ）１．４３ｇと、アミンアダクト型硬化剤（味の素ファインテクノ社製：アミキュアＭＹ−２４）０．３８ｇと、粘度調整剤としてα−ターピネオール（ヤスハラケミカル社製）をロッド状銀粉の含有率に応じて適宜用い、パドル型混練機で５分間混練した後、上記ロッド状銀粉を加え、さらに１０分間混練した。そして、得られた混練物を引き続き３本ロールで混練した後、脱泡機（シンキー社製：ＡＲ−２５０）を用いて混練物中に含まれる気泡を除去し、銀ペーストＢを得た。このときの銀ペーストＡは、ロッド状銀粉の含有率を８８ｗｔ％とした。 Production of silver paste: 6.19 g of alicyclic epoxy resin (Nippon Kayaku Co., Ltd .: AK-601), 1.43 g of acid anhydride curing agent (Nippon Kayaku Co., Ltd .: Kayahard MCD), and amine adduct type curing Agent (Ajinomoto Finetechno Co., Ltd .: Amicure MY-24) 0.38 g and α-terpineol (manufactured by Yasuhara Chemical Co., Ltd.) as a viscosity modifier are appropriately used according to the content of the rod-shaped silver powder, and 5 minutes in a paddle type kneader. After kneading, the above rod-shaped silver powder was added and further kneaded for 10 minutes. And after knead | mixing the obtained kneaded material with 3 rolls, the bubble contained in a kneaded material was removed using the defoaming machine (made by Shinkey: AR-250), and the silver paste B was obtained. The silver paste A at this time made the content rate of rod-shaped silver powder 88 wt%.
この得られた銀ペーストＢを、スクリーン印刷機を用いて配線幅５０μｍ、配線間ギャップを５０μｍとしアルミナ基板に印刷したところ、配線の断線やニジミが無い良好な印刷性を示した。また、スクリーン印刷機に用いた版を顕微鏡により観察した結果、版に銀粉が全く目詰まりしていない事を確認した。 When the obtained silver paste B was printed on an alumina substrate using a screen printer with a wiring width of 50 μm and a wiring gap of 50 μm, it showed good printability without disconnection or blurring of the wiring. Moreover, as a result of observing the plate used for the screen printing machine with a microscope, it was confirmed that the plate was not clogged with silver powder at all.
更に、スクリーン印刷機を用いて、アルミナ基板上に比抵抗測定用のサンプルとして、縦４ｃｍ×横３ｃｍの条件で銀ペーストＢを印刷した後、温度１８０℃の条件で１時間乾燥させた。このとき得られた乾燥膜の表面抵抗を４探針抵抗測定器（三菱化学社製：ロレスタＧＰ）で測定し、また、乾燥膜の膜厚をデジタル膜厚計で測定し、比抵抗を算出した。その結果、比抵抗は２．４９×１０−４Ω・ｃｍであった。 Furthermore, after printing silver paste B as a sample for measuring specific resistance on an alumina substrate using a screen printing machine under the conditions of 4 cm long × 3 cm wide, it was dried for 1 hour at a temperature of 180 ° C. The surface resistance of the dried film obtained at this time was measured with a 4-probe resistance measuring instrument (Mitsubishi Chemical Corporation: Loresta GP), and the film thickness of the dried film was measured with a digital film thickness meter to calculate the specific resistance. did. As a result, the specific resistance was 2.49 × 10 −4 Ω · cm.
（参考例２）
銀粉の製造： ここでの銀粉の製造は、実施例と共通するため、重複した説明を避けるため、ここでの説明は省略する。
(Reference Example 2)
Manufacture of silver powder : Since manufacture of silver powder here is common with an Example, in order to avoid the duplicate description, description here is abbreviate | omitted.
銀ペーストの製造： エチルセルロース（和光純薬社製）１．５ｇと粘度調整剤としてα−ターピネオール（ヤスハラケミカル製）２８．５ｇとロッド状銀粉とをパドル型混練機で１０分間混練した。 Production of silver paste: 1.5 g of ethyl cellulose ( manufactured by Wako Pure Chemical Industries), 28.5 g of α-terpineol (manufactured by Yasuhara Chemical) as a viscosity modifier, and rod-shaped silver powder were kneaded for 10 minutes with a paddle type kneader.
このようにして得られた混練物を引き続き３本ロールで混練した後、脱泡機（シンキー社製：ＡＲ−２５０）を用いて混練物中に含まれる気泡を除去し、銀ペーストＣを得た。このときの銀ペーストＣは、ロッド状銀粉の含有率を８８ｗｔ％とした。この銀ペーストＣを、スクリーン印刷機を用いて配線幅５０μｍ、配線間ギャップ５０μｍとしアルミナ基板に印刷したところ、配線の断線やニジミが無い良好な印刷性を示した。また、スクリーン印刷機に用いた版を顕微鏡により観察した結果、版に銀粉が全く目詰まりしていない事を確認した。 After the kneaded material thus obtained was continuously kneaded with three rolls, bubbles contained in the kneaded material were removed using a defoaming machine (manufactured by Shinky: AR-250) to obtain a silver paste C. It was. The silver paste C at this time made the content rate of rod-shaped silver powder 88 wt%. When this silver paste C was printed on an alumina substrate with a wiring width of 50 μm and an inter-wiring gap of 50 μm using a screen printing machine, it showed good printability without disconnection or blurring of the wiring. Moreover, as a result of observing the plate used for the screen printing machine with a microscope, it was confirmed that the plate was not clogged with silver powder at all.
更に、スクリーン印刷機を用いて、アルミナ基板上に比抵抗測定用のサンプルとして、縦４ｃｍ×横３ｃｍの条件で銀ペーストＣを印刷した後、温度１８０℃の条件で１時間乾燥させた。このようにして得られた乾燥膜の表面抵抗を４探針抵抗測定器（三菱化学社製：ロレスタＧＰ）で測定し、また、乾燥膜の膜厚をデジタル膜厚計で測定し、比抵抗を算出した。その結果、比抵抗は５．３７×１０−３Ω・ｃｍであった。 Further, a silver paste C was printed as a specific resistance measurement sample on an alumina substrate using a screen printing machine under the conditions of 4 cm in length and 3 cm in width, and then dried at a temperature of 180 ° C. for 1 hour. The surface resistance of the dried film thus obtained was measured with a 4-probe resistance measuring instrument (Mitsubishi Chemical Corporation: Loresta GP), and the film thickness of the dried film was measured with a digital film thickness meter. Was calculated. As a result, the specific resistance was 5.37 × 10 −3 Ω · cm.
（参考例３）
銀粉の製造： ここでの銀粉の製造は、実施例と共通するため、重複した説明を避けるため、ここでの説明は省略する。
(Reference Example 3)
Manufacture of silver powder : Since manufacture of silver powder here is common with an Example, in order to avoid the duplicate description, description here is abbreviate | omitted.
銀ペーストの製造： アクリル酸エステルポリマー（日本純薬社製：ジュリマーＡＴ−５１０）０．６ｇとオキサゾリン基含有ポリマー（日本触媒社製：エポクロスＷＳ−５００）０．６ｇとα−ターピネオール（ヤスハラケミカル社製）２８．７ｇと上記ロッド状銀粉をパドル型混練機で１０分間混練し、銀ペーストＤを得た。このときの銀ペーストＤは、ロッド状銀粉の含有率を８８ｗｔ％とした。 Production of silver paste: 0.6 g of acrylic acid ester polymer (manufactured by Nippon Pure Chemical Co., Ltd .: Jurimer AT-510), 0.6 g of oxazoline group-containing polymer (manufactured by Nippon Shokubai Co., Ltd .: Epocros WS-500) and α-terpineol (Yasuhara Chemical Co., Ltd.) 28.7 g and the above rod-shaped silver powder were kneaded with a paddle type kneader for 10 minutes to obtain a silver paste D. The silver paste D at this time made the content rate of rod-shaped silver powder 88 wt%.
このようにして得られた銀ペーストＤを、スクリーン印刷機を用いて配線幅５０μｍ、配線と配線の間隔を５０μｍとしアルミナ基板に印刷したところ、配線の断線やニジミが無い良好な印刷性を示した。また、スクリーン印刷機に用いた版を顕微鏡により観察した結果、版に銀粉が全く目詰まりしていない事を確認した。 The silver paste D obtained in this way was printed on an alumina substrate with a wiring width of 50 μm and a wiring-to-wiring spacing of 50 μm using a screen printing machine, and showed good printability without wiring disconnection or blurring. It was. Moreover, as a result of observing the plate used for the screen printing machine with a microscope, it was confirmed that the plate was not clogged with silver powder at all.
更に、引き続きスクリーン印刷機を用いて、アルミナ基板上に比抵抗測定用のサンプルとして、縦４ｃｍ×横３ｃｍの条件で銀ペーストＤを印刷した後、温度１８０℃の条件で１時間乾燥させた。このようにして得られた乾燥膜の表面抵抗を４探針抵抗測定器（三菱化学社製：ロレスタＬＰ）で測定し、また、乾燥膜の膜厚をデジタル膜厚計で測定し、比抵抗を算出した。その結果、比抵抗は２．２５×１０−３Ω・ｃｍであった。 Further, using a screen printer, a silver paste D was printed on a alumina substrate as a sample for measuring specific resistance under the conditions of 4 cm long × 3 cm wide, and then dried for 1 hour at a temperature of 180 ° C. The surface resistance of the dried film thus obtained was measured with a 4-probe resistance measuring instrument (Mitsubishi Chemical Corporation: Loresta LP), and the film thickness of the dried film was measured with a digital film thickness meter. Was calculated. As a result, the specific resistance was 2.25 × 10 −3 Ω · cm.
本件発明に係る銀ペーストは、結晶子径の大きな高結晶性のロッド状銀粒子をフィラーとして含有するため、銀ペースト中のロッド状銀粒子の含有量が低くとも、形成した導体の導電性を確保し、且つ当該導体の低抵抗化が図れ、同時に良好な耐熱収縮性能が得られる。従って、高価な素材である銀の使用量の低減が可能であり、安価で且つ高品質な低抵抗導体を備える回路基板等の市場供給が可能となる。 Since the silver paste according to the present invention contains highly crystalline rod-shaped silver particles having a large crystallite size as a filler, the conductivity of the formed conductor can be maintained even if the content of the rod-shaped silver particles in the silver paste is low. The resistance of the conductor can be reduced, and at the same time, good heat shrinkage performance can be obtained. Therefore, it is possible to reduce the amount of silver that is an expensive material, and it is possible to supply a circuit board or the like having a low-resistance conductor that is inexpensive and of high quality.
また、本件発明に係る銀ペーストの製造方法を用いることで、有機剤中での銀粒子の分散性に優れた銀ペーストを効率よく得ることができ、高品質の焼成導体形成用の銀ペーストを安定して生産でき、安価に市場に供給することが可能となるのである。 Further, by using the method for producing a silver paste according to the present invention, a silver paste excellent in dispersibility of silver particles in an organic agent can be efficiently obtained, and a high-quality silver paste for forming a fired conductor can be obtained. It can be produced stably and can be supplied to the market at a low cost.
Claims (6)
前記ロッド状銀粉の粉粒は針状であり、走査型電子顕微鏡像から判断できる一次粒子の平均長径Ｌが１０μｍ以下であることを特徴とする銀ペースト。 A silver paste composed of rod-shaped silver powder, a resin component, and an organic solvent,
A silver paste characterized in that the rod-shaped silver powder has a needle-like shape, and an average major axis L of primary particles that can be judged from a scanning electron microscope image is 10 μm or less.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161102A (en) * | 2011-02-12 | 2011-08-24 | 明基材料有限公司 | Nano silver wire and manufacturing method thereof |
| JP2011233468A (en) * | 2010-04-30 | 2011-11-17 | Murata Mfg Co Ltd | Photosensitive conductive paste, method for manufacturing laminate type electronic component using the same, and laminate type electronic component |
| JP2013503260A (en) * | 2009-08-25 | 2013-01-31 | カンブリオス テクノロジーズ コーポレイション | Method for controlling the morphology of metal nanowires |
| CN103702786A (en) * | 2011-07-29 | 2014-04-02 | 户田工业株式会社 | Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device |
| CN105772705A (en) * | 2016-03-22 | 2016-07-20 | 苏州捷德瑞精密机械有限公司 | Conductive silver powder and preparation method thereof |
| JP2018532048A (en) * | 2015-10-09 | 2018-11-01 | 重▲慶▼文理学院 | Method for producing silver nanowire with uniform aspect ratio |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002057423A (en) * | 2000-08-07 | 2002-02-22 | Matsushita Electric Ind Co Ltd | Circuit board using conductive paste, and its manufacturing method |
| JP2005054223A (en) * | 2003-08-01 | 2005-03-03 | Mitsui Mining & Smelting Co Ltd | Rod-shaped silver particle and manufacturing method therefor |
| JP2006032165A (en) * | 2004-07-16 | 2006-02-02 | Sumitomo Metal Mining Co Ltd | Conductive metal particles and conductive resin composition using them, and conductive adhesive |
-
2004
- 2004-07-26 JP JP2004216705A patent/JP2006040650A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002057423A (en) * | 2000-08-07 | 2002-02-22 | Matsushita Electric Ind Co Ltd | Circuit board using conductive paste, and its manufacturing method |
| JP2005054223A (en) * | 2003-08-01 | 2005-03-03 | Mitsui Mining & Smelting Co Ltd | Rod-shaped silver particle and manufacturing method therefor |
| JP2006032165A (en) * | 2004-07-16 | 2006-02-02 | Sumitomo Metal Mining Co Ltd | Conductive metal particles and conductive resin composition using them, and conductive adhesive |
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| JP2013503260A (en) * | 2009-08-25 | 2013-01-31 | カンブリオス テクノロジーズ コーポレイション | Method for controlling the morphology of metal nanowires |
| JP2011233468A (en) * | 2010-04-30 | 2011-11-17 | Murata Mfg Co Ltd | Photosensitive conductive paste, method for manufacturing laminate type electronic component using the same, and laminate type electronic component |
| CN102161102A (en) * | 2011-02-12 | 2011-08-24 | 明基材料有限公司 | Nano silver wire and manufacturing method thereof |
| CN103702786A (en) * | 2011-07-29 | 2014-04-02 | 户田工业株式会社 | Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device |
| CN103702786B (en) * | 2011-07-29 | 2015-07-29 | 户田工业株式会社 | Silver microparticle and the conductive paste containing this silver-colored microparticle, conductive film and electronic device |
| JP2018532048A (en) * | 2015-10-09 | 2018-11-01 | 重▲慶▼文理学院 | Method for producing silver nanowire with uniform aspect ratio |
| US10357824B2 (en) | 2015-12-03 | 2019-07-23 | Mitsui Mining & Smelting Co., Ltd. | Dendritic silver powder |
| CN105772705A (en) * | 2016-03-22 | 2016-07-20 | 苏州捷德瑞精密机械有限公司 | Conductive silver powder and preparation method thereof |
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